CN101283042A - Methods and materials for fabricating microfluidic devices - Google Patents
Methods and materials for fabricating microfluidic devices Download PDFInfo
- Publication number
- CN101283042A CN101283042A CNA2006800375059A CN200680037505A CN101283042A CN 101283042 A CN101283042 A CN 101283042A CN A2006800375059 A CNA2006800375059 A CN A2006800375059A CN 200680037505 A CN200680037505 A CN 200680037505A CN 101283042 A CN101283042 A CN 101283042A
- Authority
- CN
- China
- Prior art keywords
- functional group
- curable functional
- fluoropolymer
- curable
- pfpe
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Abstract
Materials and methods are provided for fabricating microfluidic devices. The materials include low surface energy fluoropolymer compositions having multiple cure functional groups. The materials can include multiple photocurable and/or thermal-curable functional groups such that laminate devices can be fabricated. The materials also substantially do not swell in the presence of hydrocarbon solvents.
Description
Governmental interests
According to the STC planning of N000140210185 of institute of naval and the National Science Foundation under protocol number CHE-9876674, the present invention makes under United States Government supports.United States Government enjoys some power among the present invention.
The cross reference of related application
The U.S. Provisional Patent Application sequence number 60/706,786 that the application submitted to based on August 9th, 2005; The U.S. Provisional Patent Application sequence number 60/732,727 that on November 2nd, 2005 submitted to; With the U.S. Provisional Patent Application sequence number of submitting on May 10th, 2,006 60/799,317 and require their right of priority; Each piece of writing in them all is incorporated herein by reference at this.
The application still is the part continuation application of the pct international patent patent application serial numbers PCT/US05/04421 that submitted on February 14th, 2005, the U.S. Provisional Patent Application sequence number 60/544 that this international patent application was submitted to based on February 13rd, 2004,905 and require its right of priority, each piece of writing in them all is incorporated herein by reference at this.
Technical field
Generally, the present invention relates to make the material and the method for polymer device.More particularly, this polymer device can be multilayer device such as microfluidic device.
Be called for short
The AC=alternating-current
The Ar=argon gas
℃=degree centigrade
Cm=centimetre
8-CNVE=perfluor (8-cyano group-5-methyl-3,6-Er Evil-1-octene)
CSM=solidifies center monomer
The CTFE=trifluorochloroethylene
The g=gram
H=hour
1-HPFP=1,2,3,3,3-five fluorine propylene
2-HPFP=1,1,3,3,3-five fluorine propylene
The HFP=R 1216
The HMDS=hexamethyldisilazane
The IL=imprint lithography
The IPDI=isophorone diisocyanate
The MCP=micro-contact printing
The Me=methyl
The MEA=membrane electrode assembly
The MEMS=microelectromechanical-systems
MeOH=methyl alcohol
Little molding in the MIMIC=kapillary
The mL=milliliter
The mm=millimeter
The mmol=mmole
M
n=mumber average molar mass
The m.p.=fusing point
The mW=milliwatt
NCM=nanometer contact molding
The NIL=nano-imprint lithography
The nm=nanometer
The Pd=palladium
PAVE=perfluor (alkyl vinyl) ether
PDMS=gathers (dimethyl siloxane)
The PEM=proton exchange membrane
The PFPE=PFPE
PMVE=perfluor (methyl ethylene) ether
PPVE=perfluor (propyl ethylene base) ether
PSEPVE=perfluor-2-(2-fluoro alkylsulfonyl oxyethyl group) propyl vinyl ether
The PTFE=tetrafluoroethylene
The SAMIM=solvent is assisted little molding
The SEM=scanning electron microscopy
Si=silicon
The TFE=tetrafluoroethylene
μ m=micron
The UV=ultraviolet
W=watt
ZDOL=gathers (ptfe ring oxidative ethane-copolymerization-difluoro formaldehyde) α, ω glycol
Background of invention
Microfluidic device in the nineteen nineties early development is to use photoetching and etching technique by hard material, and for example silicon and glass are made.Referring to
Ouellette, J.,TheIndustrial Physicist 2003, August/September, 14-17;
Scherer, people such as A.Science 2000,290,1536-1539.Yet photoetching and etching technique are expensive and labour-intensive, and they require the cleaning chamber condition, and see from the material viewpoint and to have some shortcomings.For this reason, soft material has come out as the equivalent material of microfluidic device manufacturing.The use of soft material has made that making and drive the device that comprises valve, pump and mixing tank becomes possibility.For example referring to
Ouellette, J., The Industrial Physicist 2003, August/September, 14-17;
Scherer, people such as A.Science 2000,290,1536-1539;
Unger, people such as M.A.Science 2000,288,113-116;
McDonald, people such as J.C.Acc.Chem.Res.2002,35,491-499 and
Thorsen, people such as T.Science2002,298,580-584.For example, a kind of such microfluidic device allow not use machinery valve and controlling flow to.Referring to
Zhao, people such as B.Science 2001,291,1023-1026.
The complicacy that microfluidic device increases has day by day required to use such device in the application that number increases rapidly.For this reason, the use of soft material has made micro-fluidic technologies develop into useful technology, and this technology has been used for gene order-checking, sharp separation, transmitter, the nano level reaction, ink jet printing, drug delivery, chip lab (Lab-on-a-Chip), in-vitro diagnosis, injection nozzle, biological study and drug screening.For example referring to
Ouellette, J., TheIndustrial Physicist 2003, August/September, 14-17;
Scherer, people such as A.Science 2000,290,1536-1539;
Unger, people such as M.A.Science 2000,288,113-116;
McDonald, people such as J.C.Acc.Chem.Res.2002,35,491-499;
Thorsen, people such as T.Science 2002,298,580-584 and
Liu, people such as JAnal.Chem.2003,75,4718-4723.
Poly-(dimethyl siloxane) is to use selected soft material for many microfluidic devices (PDMS).For example referring to
Scherer, people such as A.Science 2000,290,1536-1539;
Unger, people such as M.A.Science 2000,288,113-116;
McDonald, people such as J.C.Acc.Chem.Res.2002,35,491-499;
Thorsen, people such as T.Science2002,298,580-584 and
Liu, people such as JAnal.Chem.2003,75,4718-4723.The PDMS material provides many attractive performances in microfluidic applications.After crosslinked, PDMS becomes and has low Young's modulus, for example the about elastomer material of 750kPa.Referring to
Unger, M.A. Deng the peopleScience 2000,288,113-116.This performance merges PDMS and surperficial kissing and forms the reversible sealing.In addition, PDMS has low surface energy, for example, and about 20erg/cm
2, this can promote its behind patterning with the disengaging of mould.Referring to
Scherer, people such as A.Science2000,290,1536-1539;
McDonald.J.C. wait the peopleAcc.Chem.Res.2002,35,491-499.
The important feature of another of PDMS is its excellent ventilation property.This performance allows the bubble in the microfluidic device raceway groove (channel) to ooze out outside the device.This performance also can be used for maintaining the interior cell and the microorganism of parts (feature) of microfluidic device.Silicone, for example the nontoxic character of PDMS also is favourable at this on the one hand, and allows it to be used for the medical implant field.
McDonald, people such as J.C.Acc.Chem.Res.2002,35,491-499.
Many current PDMS microfluidic devices are based on SYLGARD
184 (Dow Corning, Midland, Michigan, United States of America).SYLGARD
The 184th, by the catalytic hydrosilation reaction thermofixation of platinum.SYLGARD
184 completely solidified may spend and reach five hours.Yet, reported the synthetic of photo curable PDMS material recently, this PDMS material has and the SYLGARD that is used for soft lithographic
184 similar mechanical propertys.Referring to
Choi.K.M. wait the peopleJ.Am.Chem.Soc.2003,125,4060-4061.
Although above-mentioned advantage is arranged, PDMS still has many defectives in micro-fluidic technologies is used.At first, PDMS swelling in most of organic solvents.Therefore, PDMS class microfluidic device and various organic solvent have limited consistency.Referring to
Lee, people such as J.N.Anal.Chem.2003,75,6544-6554.Make those organic solvents of PDMS swollen comprise hexane, ethyl ether, toluene, methylene dichloride, acetone and acetonitrile.Referring to
Lee, people such as J.N.Anal.Chem.2003,75,6544-6554.Organic solvent makes PDMS microfluidic device swelling may destroy its micron order parts (feature), for example, and raceway groove or a plurality of raceway groove, and may limit or close fully organic solvent flowing by this raceway groove.Therefore, adopt the microfluidic applications of PDMS class device to be limited to and use the not fluid of swelling PDMS, for example water.As a result, require those application with an organic solvent may use, for example the microfluid system of glass and silicon manufacturing by hard material.Referring to
Lee, people such as J.N.Anal.Chem.2003,75,6544-6554.Yet this approach is subjected to being made by hard material the restriction of the shortcoming of microfluidic device.
Secondly, well-known PDMS class device and material make it even can't be used for water base chemistry owing to inertia is not enough.For example, the bronsted lowry acids and bases bronsted lowry reaction that PDMS is easy and weak and strong.PDMS class device also comprises extractable content as everyone knows, and for example extractible oligopolymer and annular siloxane are particularly after being exposed to bronsted lowry acids and bases bronsted lowry.Because PDMS is easily by the organism swelling, so hydrophobic material also can in use infiltrate the PDMS class material that is used for constructing PDMS class microfluidic device even be slightly soluble in those hydrophobic materials of water.
Therefore, show the attractive mechanical property of PDMS and in organic solvent commonly used the elastomer material of swell-resistant will make the purposes of microfluidic device expand to the many new chemistry that current PDMS class device can't be applied to use.Therefore, the approach of disclosure theme performance uses the elastomer material of anti-swollen the in organic solvent commonly used, and more particularly functionalized PFPE (PFPE) material is made microfluidic device.
Functionalized PFPE material at room temperature is a liquid, shows low surface energy, low modulus, high ventilation property and low toxicity, and has the supplementary features of high chemical resistance.Referring to
Scheirs, J., Modern Fluoropolymers; John Wiley ﹠amp; Sons, Ltd.:NewYork, 1997; Pp 435-485.In addition, the PFPE material shows hydrophobicity and lyophoby performance.For this cause, the PFPE material is used as the lubricant of the high-performance mechanical that turns round usually in severe condition.Reported the synthetic and solvability of PFPE material in supercritical carbon dioxide.Referring to
Bunyard, people such as W.Macromolecules 1999,32,8224-8226.Except that PFPE, fluoroelastomer can also comprise Fluorine containing olefine class material, includes but not limited to the multipolymer of tetrafluoroethylene, R 1216, vinylidene fluoride and alkyl vinyl ether, adds additional curing center monomer usually and is used for crosslinked.
The PFPE microfluidic device before this by
Rolland, people such as J.JACS2004,126,2322-2323 carried out report.(for example, make, and this functionalized PFPE material has the roughly viscosity of this functionalised materials of 800cSt by PFPE dimethacrylate (MW=4,000g/mol)) by functionalized PFPE material for this device.This material is by methacrylate based end-functionalization of free redical polymerization, and by light trigger with free radical mode UV photocuring.
Rolland, people such as J.Above, use specific part UV curing technology to prepare multilayer PFPE device, yet adhesivity is weak and generally is not strong enough to and can be used for many microfluidic applications.In addition,
Rolland.J. wait the peopleThe attachment technique of describing does not provide adhesivity for other base material such as glass.
Subject description disclosed herein the use fluoroelastomer, especially functionalized PFPE is as the material of making solvent-proof micron and nanoscale structures (as microfluidic device).Use the particularly functionalized PFPE of fluoroelastomer to solve the relevant problem of the swelling in organic solvent that shows with the microfluidic device of making by other polymer materials such as PDMS as the material of making microfluidic device.Therefore, PFPE class microfluidic device can be used in combination with the chemical reaction that other micro polymer fluid device can not carry out.
In addition, not all to be performance during great majority are used even enough adhesivityes of the interlayer of multilayer microfluidic device may influence yet.For example, adhesivity may influence microfluidic device, as
People such as UngerScience, 288, the performance in those microfluidic devices that 113-6 (2000) describes, described microfluidic device comprises the layer that a plurality of permissions form pneumavalve.Therefore, still need described layer with microfluidic device to adhere to each other in this area or adhere to other lip-deep improving one's methods.
In addition, many devices are formed by polymer materials as instruments, medical device, prosthesis implant, contact lens etc.The polymer materials that is usually used in medical device industry (for example includes but not limited to urethane, polyolefine, polyethylene and polypropylene), poly-(methyl) acrylate, polyester (for example, polyethylene terephthalate), polymeric amide, polyvinyl resin, silicone resin (for example, silicone rubber and polysiloxane), polycarbonate, poly-fluorocarbon resin, synthetic resins, polystyrene, various biological erodable materials etc.Though these and other material that is commonly used for implant material have proved useful, still there are many defectives in these materials.A defective is to adopt any implant, always biological fouling on this implant surface.Because the interfacial gap of tissue/implant and the surface characteristic of implant material may produce biological fouling.Therefore, still need to improve described polymer materials and/or with the functionalisation of surfaces of described material or described medical device material to produce better tissue/device interfaces and to reduce biological fouling.
Summary of the invention
According to one embodiment of the invention, polymer composition comprises first component and second component, and this first component comprises the fluoropolymer that contains first curable functional group, and this second component comprises the fluoropolymer that contains second curable functional group.In some embodiments, said composition also comprises the 3rd component, and the 3rd component comprises the fluoropolymer that contains the 3rd curable functional group.According to some embodiments, describedly contain the fluoropolymer of first curable functional group or contain at least a PFPE that comprises in the fluoropolymer of second curable functional group.In alternate embodiment, the described fluoropolymer that contains first curable functional group, contain the fluoropolymer of second curable functional group or contain at least a low surface energy polymeric material that comprises in the fluoropolymer of the 3rd curable functional group.
In some embodiments, this first curable functional group comprises the first photocurable functional group.In some embodiments, this first photocurable functional group comprises photo curable diurethanes methacrylic ester.In some embodiments, this second curable functional group comprises the second photocurable functional group, and this second photocurable functional group can comprise photo curable diepoxy group.
According to some embodiments, this second curable functional group comprises the first thermal curable functional group.In some embodiments, this first thermal curable functional group comprises vulcabond, diepoxy group or diamines.In some embodiments, the 3rd curable functional group comprises the second thermal curable functional group, and this second thermal curable functional group comprises triol or tetrol.Said composition can comprise below in conjunction with thing: wherein first curable functional group comprises photo curable diurethanes methacrylic ester, and second curable functional group comprises vulcabond, and the 3rd curable functional group comprises triol.According to other embodiment, said composition can comprise below in conjunction with thing: wherein first curable functional group comprises photo curable diurethanes methacrylic ester, second curable functional group comprises vulcabond, the 3rd curable functional group comprises following tetrol: in other embodiment, said composition can comprise below in conjunction with thing: wherein first curable functional group comprises photo curable diurethanes methacrylic ester, second curable functional group comprises the diepoxy group, and the 3rd curable functional group comprises diamines.In other embodiment, said composition can comprise below in conjunction with thing: wherein first curable functional group comprises photo curable diurethanes methacrylic ester, and second curable functional group comprises photo curable diepoxy group.In other embodiment, said composition can comprise below in conjunction with thing: wherein first curable functional group comprises photo curable diurethanes methacrylic ester, and second curable functional group comprises vulcabond.According to some embodiments, material of the present invention can comprise the fluoropolymer of being made by fluoro-alkyl iodine precursor.
According to some embodiments, this first photocurable functional group reacts under first wavelength, and the second photocurable functional group reacts under second wavelength.In other embodiment, this first thermal curable functional group reacted in first period, and the second thermal curable functional group reacted in second period.According to other embodiment, this first thermal curable functional group reacts under first temperature, and the second thermal curable functional group reacts under second temperature.According to some embodiments, after described first curable functional group is activated this second curable functional group keep available so that this second curable functional group can with the group that constitutes another kind of polymkeric substance, hydroxyl, another kind of functional group and its combination keyed jointing.
In some embodiments, this PFPE is by cycloaliphatic epoxide structure division end-blocking.In some embodiments, this PFPE has about 16000 molecular weight and the about modulus of 800kPa.In other embodiment, this PFPE has the molecular weight less than about 16000.In other embodiments, this PFPE has the modulus greater than about 500kPa.In other embodiment, this PFPE has about 16000 molecular weight and about 200% elongation at break.According to some embodiments, this PFPE has the elongation at break less than about 200%.In other embodiment, a kind of elongation at break that comprises in described first component or second component is about 300% fluoropolymer.In other embodiment, a kind of elongation at break that comprises in described first component or second component is about 200% fluoropolymer.In other embodiment, a kind of elongation at break that comprises in described first component or second component is the fluoropolymer of about 100%-about 300%.According to some embodiments, a kind of elongation at break that comprises in described first component or second component is the PFPE of about 200%-about 300%.
According to some embodiments, polymer composition comprises the fluoropolymer that contains at least two kinds of functional groups, wherein after making this fluoropolymer polymerization, second functional group keeps can activating so that this fluoropolymer is adhered on another chemical group in that first functional group is activated.In some embodiments, this another chemical group is selected from group, hydroxyl, another kind of functional group and their combination of another kind of polymkeric substance.
According to embodiments more of the present invention, microfluidic device comprises first fluoropolymer component, and wherein this first fluoropolymer component comprises PFPE.In some embodiments, this first fluoropolymer component comprises first curable functional group, and this embodiment can also comprise second fluoropolymer component that contains second curable functional group.In some embodiments, this first curable functional group comprises the first photocurable functional group, and second curable functional group comprises the first thermal curable functional group.According to other embodiment, second curable functional group comprises the second photocurable functional group.
In some embodiments, this first photocurable functional group comprises photo curable diurethanes methacrylic ester, or photo curable diepoxy group.In some embodiments, this first thermal curable functional group comprises vulcabond, diepoxy group or diamines.In other embodiments, microfluidic device also comprises the 3rd fluoropolymer component, and wherein the 3rd fluoropolymer component comprises the 3rd curable functional group.In some embodiments, the 3rd curable functional group comprises the second thermal curable functional group, as triol or tetrol.
According to some embodiments, microfluidic device comprises composition, and wherein first curable functional group comprises photo curable diurethanes methacrylic ester, and second curable functional group comprises vulcabond, and the 3rd curable functional group comprises triol.According to some embodiments, microfluidic device comprises composition, and wherein first curable functional group comprises photo curable diurethanes methacrylic ester, and second curable functional group comprises vulcabond, and the 3rd curable functional group comprises tetrol.According to some embodiments, microfluidic device comprises composition, and wherein first curable functional group comprises photo curable diurethanes methacrylic ester, and second curable functional group comprises the diepoxy group, and the 3rd curable functional group comprises diamines.According to some embodiments, this microfluidic device comprises composition, and wherein first curable functional group comprises photo curable diurethanes methacrylic ester, and second curable functional group comprises photo curable diepoxy group.According to some embodiments, this microfluidic device comprises composition, and wherein first curable functional group comprises photo curable diurethanes methacrylic ester, and second curable functional group comprises vulcabond.According to some embodiments, microfluidic device comprises composition, and wherein first curable functional group comprises the first photocurable functional group, and wherein this first photocurable functional group reacts to different wavelength with the second photocurable functional group.According to some embodiments, microfluidic device comprises composition, wherein at least a PFPE that comprises in first fluoropolymer component, second fluoropolymer component and the 3rd fluoropolymer component.According to some embodiments, microfluidic device comprises composition, and wherein first fluoropolymer component, second fluoropolymer component and the 3rd fluoropolymer component comprise PFPE.
In other embodiment, microfluidic device comprises and the first fluoropolymer component link coupled silicone components.In some embodiments, microfluidic device has and silicone components link coupled first fluoropolymer component, thereby forms the adhesive power that can tolerate up to about 120 pounds/square inch (psi).In some embodiments, first fluoropolymer component of this microfluidic device has about 300% elongation at break.In other embodiment, this first fluoropolymer component has about 200% elongation at break.In other embodiments, this first fluoropolymer component has the elongation at break of about 100%-about 300%.In other embodiments, this first fluoropolymer component has the elongation at break of about 200%-about 300%.In other embodiment, this fluoropolymer comprises the low surface energy fluoropolymer.In some embodiments, this low surface energy fluoropolymer comprises the surface energy less than about 20 dynes per centimeter.In other embodiment, this low surface energy fluoropolymer comprises less than about 18 dynes per centimeter, less than about 15 dynes per centimeter, or less than the surface energy of about 12 dynes per centimeter.
According to some embodiments, microfluidic device comprises the component that is selected from following material: the diurethanes methacrylic ester; The diurethanes methacrylic ester of chain extension; Vulcabond; The vulcabond of chain extension; End capped vulcabond; The triol of PFPE three arms; The PFPE toluylene; Diepoxy resin; Diamines; The PU-tetrol of thermofixation; The PU-triol of thermofixation; The Resins, epoxy of thermofixation; The Resins, epoxy of photocuring and their combination.
In some embodiments, microfluidic device comprises first fluoropolymer component that is substantially free of trace-metal.In other embodiment, this first fluoropolymer component is solvent-proof basically.In some embodiments, when being communicated with organic solvent, this first fluoropolymer component swelling is less than about 10wt%.In other embodiment, when being communicated with organic solvent, this fluoropolymer component swelling is less than about 5wt%.
In some embodiments, described fluoropolymer component has about 1: 2 carbon and fluorine ratio, and in other embodiment, described fluoropolymer component has about 1: 1 carbon and fluorine ratio.According to some embodiments, this fluoropolymer component has about 2: 1 carbon and fluorine ratio.In other embodiments, described fluoropolymer component has about 1: carbon and fluorine ratio that 1-is about 2: 1.In other embodiment, described fluoropolymer component has about 1: carbon and fluorine ratio that 1-is about 1: 2.
According to some embodiments, microfluidic device also comprises laminated (lamination) between first parts and second parts; Wherein this laminated (laminate) comprises the chemical bond between first parts and second parts; Wherein under about 120 pounds/square inch pressure these first parts not with this second component layer from.In some embodiments, this microfluidic device comprises first parts of qualification raceway groove wherein; With the valve that is positioned at this raceway groove; Wherein this valve can drive under the pressure of about about 60psi of 40psi-and can not damage this microfluidic device.In some embodiments, microfluidic device comprises first fluoropolymer component, and this first fluoropolymer component is included in the coating on the raceway groove of this microfluidic device.
In some embodiments, microfluidic device comprises having about 16000 molecular weight and about first fluoropolymer component of the modulus of 800kPa.In other embodiment, this first fluoropolymer component has the molecular weight less than about 16000.In some embodiments, this first fluoropolymer component has the modulus greater than about 500kPa.In other embodiments, this first fluoropolymer component has about 16000 molecular weight and about 200% elongation at break.In some embodiments, this first fluoropolymer component has the elongation at break less than about 200%.
According to some embodiments, microfluidic device comprises the PFPE Resins, epoxy that contains PAG; Wherein this binding substances is selected from 2, the free radical photo-initiation blend of 2-dimethoxy-acetophenone, 1-hydroxycyclohexylphenylketone or diethoxy acetophenone with about about 5 moles of % of 1-.In other embodiment, microfluidic device comprises the PFPE Resins, epoxy that contains PAG, its can be under two or more wavelength photocuring.In some embodiments, microfluidic device comprises by first parts of PFPE structure and second parts of being constructed by silicone.According to one embodiment of the invention, micro element is by the preparation of the method that may further comprise the steps: handles this device so that this fluorine and hydrogen atom in this device with the solution that comprises 0.5% fluorine gas in nitrogen and carry out free radical reaction also so make the surface passivation of this device.
According to some embodiments, prepare microfluidic device by the method that may further comprise the steps: fluorinated fluids is added in the polymer precursor of this microfluidic device, wherein this polymer precursor comprises photo curable or heat-setting precursor; By handling this polymkeric substance with optical radiation or heat energy respectively with this polymer cure; With from this cured polymer, remove fluorinated fluids.In some embodiments, this to remove be method of evaporating or dissolving method.According to alternate embodiment, the concentration of this fluorinated fluids is less than about 15%, less than about 10%, or less than about 5%.
In some embodiments, micro element of the present invention comprises by the surface of end capped precursor passivation.In some embodiments, this end capped precursor comprises the end capped Liquid precursor of vinylbenzene.In alternate embodiment, this surface comprises the surface of valve, raceway groove, reservoir, film or wall.
According to alternative embodiment of the present invention, the component parts of microfluidic device comprises valve, film, raceway groove, reservoir, well, lid etc.In some embodiments, this component parts is by first polymeric constituent and the second polymeric constituent manufacturing, wherein this first polymeric constituent comprises the fluoropolymer that contains first curable functional group, and wherein this second polymeric constituent comprises the fluoropolymer that contains second curable functional group.In some embodiments, this component parts comprises the terpolymer component, and wherein this terpolymer component comprises the fluoropolymer that contains the 3rd curable functional group.According to some embodiments, this component parts comprises composition, wherein contain first curable functional group fluoropolymer, contain the fluoropolymer of second curable functional group or contain at least a PFPE that comprises in the fluoropolymer of the 3rd curable functional group.In other embodiment, this component parts comprises composition, wherein contain first curable functional group fluoropolymer, contain the fluoropolymer of second curable functional group or contain at least a low surface energy polymeric material that comprises in the fluoropolymer of the 3rd curable functional group.In some embodiments, described fluoropolymer has first curable functional group that comprises photocurable functional group.In some embodiments, this component parts comprises fluoropolymer, and this fluoropolymer has second curable functional group that comprises thermal curable functional group.In other embodiment, described component parts comprises the photocurable functional group that is selected from photocurable diurethanes methacrylic ester, photocurable diepoxy group and its combination.In some embodiments, this thermal curable functional group can be triol, vulcabond, tetrol, diepoxy group, diamines or their combination.In other embodiment, described first curable functional group and second curable functional group are selected from the diurethanes methacrylic ester; The diurethanes methacrylic ester of chain extension; Vulcabond; The vulcabond of chain extension; End capped vulcabond; The triol of PFPE three arms; The PFPE toluylene; The diepoxy group; Diamines; The PU-tetrol of thermofixation; The PU-triol of thermofixation; The epoxide group of thermofixation; The epoxide group of photocuring and their combination.In some embodiments, described component parts comprises film or the valve with at least two layers, and wherein this layer comprises the PFPE laminate, and this laminate has the toluylene material that is laminated on the PFPE diurethanes methacrylic acid ester material.
In some embodiments, this component parts comprises fluoropolymer, and this fluoropolymer has the hole that is limited to wherein.In alternate embodiment, described hole is less than about 15%, less than about 10%, or less than about 5%.
According to embodiments more of the present invention, the manufacture method of micro element comprises by fluoropolymer makes microfluidic device.In some embodiments, this fluoropolymer comprises PFPE.In other embodiment, this fluoropolymer comprises first fluoropolymer component that contains first curable functional group and second fluoropolymer component that contains second curable functional group.According to some embodiments, this first curable functional group comprises photocurable functional group, and second curable functional group comprises thermal curable functional group.
According to some embodiments, the manufacture method of microfluidic device comprises removes trace-metal and uses this polymkeric substance to make microfluidic device from polymkeric substance, and wherein this microfluidic device is substantially free of trace-metal.In some embodiments, this polymkeric substance comprises fluoropolymer, and in some embodiments, this fluoropolymer comprises PFPE.
According to embodiments more of the present invention, the method for reacting comprises provides microfluidic device, and this microfluidic device comprises the polymkeric substance that is substantially free of trace-metal; With the reaction that in this microfluidic device, relates to F-so that this F-basically not by the trace-metal quencher in the polymkeric substance of this microfluidic device.
In some embodiments of the present invention, the manufacture method of microfluidic device comprises: fluoropolymer is cast on the caster (master template), and wherein this caster comprises space pattern (dimensional pattern); This fluoropolymer solidified so that this fluoropolymer keeps the basic mirror image of this space pattern; To gather (dimethyl siloxane) is cast on this cured fluoropolymer; (dimethyl siloxane) curing will be gathered so that the basic mirror image that (dimethyl siloxane) keeps the pattern of this curing fluoropolymer should be gathered; Be used for other fluoropolymer component of molding with this solidified of use poly-(dimethyl siloxane) as mould.
According to other embodiments of the present invention, the method for the manufacturing of microfluidic device comprises: the thin layer of uncured polymer is spun in the first part of microfluidic device; This first part is arranged on the second section of this microfluidic device so that the thin layer of this spin coating is communicated with the second section of this microfluidic device; Solidify with the thin layer that this binding substances is solidified consequently this spin coating.
According to some embodiments, the method that improves the chemical compatibility of polymer device comprises: with comprising that the solution-treated of the end capped precursor solution of vinylbenzene comprises the polymer device of potential methacrylic ester, acrylate and/or styrene group; The film of this solution evaporation or dissolving so that the end capped precursor of this vinylbenzene is retained on the surface of this polymer device; With with the film hardening of the end capped precursor of this vinylbenzene so that this film via adhering on the surface of this polymer device with the reaction of potential methacrylic ester, acrylate and/or the styrene group of this polymer device.
In some embodiments of the present invention, the using method of micro element comprises: make microfluidic device by fluoropolymer, wherein this microfluidic device comprises raceway groove; With allow liquid flow through this raceway groove at least in part.In some embodiments, this liquid comprises organic solvent, as hydrocarbon solvent.In alternate embodiment, described hydrocarbon solvent is selected from tetrahydrofuran (THF), toluene, methylene dichloride, hexane, chloroform, Virahol, hexanaphthene, methyl ethyl ketone, acetone and their combination.Other using method according to microfluidic device provides a kind of method, wherein this microfluidic device by the fluoropolymer manufacturing that is substantially free of trace-metal and wherein this liquid comprise F-.In alternate embodiment, the using method of microfluidic device comprises: the microfluidic device with raceway groove is provided, wherein scribbles to this channel part fluoropolymer; With material is introduced in the raceway groove of this microfluidic device, wherein this material comprises organic solvent such as hydrocarbon solvent.
In some embodiments, fluoropolymer component is combined with polymeric constituent.In some embodiments, this fluoropolymer and this polymkeric substance can not mixings.In some embodiments, but this fluoropolymer and this polymkeric substance are mixings.
According to other embodiment, microfluidic device comprises first component and second component, and this first component comprises the polymkeric substance that contains first curable functional group, and this second component comprises the polymkeric substance that contains second curable functional group.In some embodiments, this first curable functional group comprises photocurable functional group, and second curable functional group comprises thermal curable functional group.In some embodiments, this first curable functional group comprises the first photocurable functional group, second curable functional group comprises the second photocurable functional group, and this first photocurable functional group can solidify under first wavelength, and the second photocurable functional group can solidify under second wavelength.In some embodiments, this first curable functional group comprises the first thermal curable functional group, second curable functional group comprises the second thermal curable functional group, and this first thermal curable functional group can solidify under first temperature, and the second thermal curable functional group can solidify under second temperature.According to some embodiments, this first curable functional group comprises the first thermal curable functional group, second curable functional group comprises the second thermal curable functional group, and this first thermal curable functional group can solidify under first elapsed time, and the second thermal curable functional group can solidify under second elapsed time.
In some embodiments, this photocurable functional group comprises photo curable diurethanes methacrylic group, and thermal curable functional group comprises vulcabond.In other embodiment, this photocurable functional group comprises photo curable diurethanes methacrylic ester, and thermal curable functional group comprises the diepoxy group.In some embodiments, this photocurable functional group comprises photo curable diurethanes methacrylic ester, and thermal curable functional group comprises diamines.In some embodiments, this first photocurable functional group comprises photo curable diurethanes methacrylic ester, and the second photocurable functional group comprises photo curable diepoxy group.
According to some embodiments, described composition also comprises the polymkeric substance that contains the 3rd curable functional group.In some embodiments, this first curable functional group comprises photo curable diurethanes methacrylic ester, and second curable functional group comprises heat-setting vulcabond, and the 3rd curable functional group comprises heat-setting triol.In some embodiments, this first curable functional group comprises photo curable diurethanes methacrylic ester, and second curable functional group comprises heat-setting vulcabond, and the 3rd curable functional group comprises heat-setting tetrol.In some embodiments, this first curable functional group comprises photo curable diurethanes methacrylic ester, and second curable functional group comprises heat-setting diepoxy group, and the 3rd curable functional group comprises heat-setting diamines.
According to embodiments more of the present invention, microfluidic device comprises film.This film comprises first component and second component, and this first component comprises the polymkeric substance that contains first curable functional group; This second component comprises the polymkeric substance that contains second curable functional group.In some embodiments, this first curable functional group comprises photocurable functional group, and second curable functional group comprises thermal curable functional group.In some embodiments, this first curable functional group comprises the first photocurable functional group, second curable functional group comprises the second photocurable functional group, and this first photocurable functional group can solidify under first wavelength, and the second photocurable functional group can solidify under second wavelength.In other embodiment, this first curable functional group comprises the first thermal curable functional group, second curable functional group comprises the second thermal curable functional group, and this first thermal curable functional group can solidify under first temperature, and the second thermal curable functional group can solidify under second temperature.In other embodiment, this first curable functional group comprises the first thermal curable functional group, second curable functional group comprises the second thermal curable functional group, and this first thermal curable functional group can solidify under first elapsed time, and the second thermal curable functional group can solidify under second elapsed time.
According to some embodiments, microfluidic device comprises expanded ptfe, and this expanded ptfe has solidified PFPE in its hole.In some embodiments, this PFPE comprises curable functional group.According to some embodiments, this curable functional group comprises photocurable functional group, as photo curable diurethanes methacrylic ester, or photo curable diepoxy group.In other embodiment, this curable functional group comprises thermal curable functional group, as heat-setting vulcabond, diepoxy group, diamines, triol, tetrol or their combination.In other embodiment, PFPE comprises the PFPE toluylene.
According to some embodiments, the manufacture method of microfluidic device comprises: the surface that is made of expanded ptfe at least in part is provided; Enter the hole of this expanded ptfe with wetting this expanded ptfe of curable PFPE so that this PFPE; With this PFPE of curing.In some embodiments, this curable PFPE comprises the curable functional group and second curable functional group.According to some embodiments, this curable functional group comprises photocurable functional group or thermal curable functional group.In other embodiment, this curable PFPE comprises photocurable functional group and thermal curable functional group.
The accompanying drawing summary
Figure 1A-1C is a series of end views of description according to the patterned layer forming process of the polymer materials of disclosure theme.
Fig. 2 A-2D is a series of end views of description according to the forming process of the device of the patterned layer that comprises the two layers of polymers material of disclosure theme.
Fig. 3 A-3C is the diagram that is used for functionalized device is adhered to the embodiment on the treated base material of disclosure method.
Fig. 4 A-4C is the diagram of embodiment that is used to make multilayer device of disclosure method.
Fig. 5 A and 5B are the diagrams that is used for the embodiment that the raceway groove internal surface is functionalized of disclosure method.
Fig. 5 A is the diagram that is used for the embodiment that the raceway groove internal surface is functionalized of disclosure method.
Fig. 5 B is the diagram that is used for the embodiment that device surface is functionalized of disclosure method.
Fig. 6 A-6D is the use degradable of disclosure method and/or the diagram that alternative dissolved material is made the embodiment of microstructure.
Fig. 7 A-7C is the use degradable of disclosure method and/or the diagram that alternative dissolved material is made the embodiment of the complex construction in the device.
Fig. 8 is the floor map according to the device of disclosure theme.
Fig. 9 is the synoptic diagram that is used for biomacromolecule synthetic integrated microfluidic system.
Figure 10 be according to disclosure theme be used for make solution stream cross microfluidic device or carry out the synoptic diagram of the system of chemical reaction at microfluidic device.
Figure 11 a-11e shows the manufacturing processed of device according to an embodiment of the invention.
Figure 12 A-12B is the Photomicrograph of the air actuation pneumavalve in the disclosure PFPE microfluidic device that drives under the pressure of about 45psi.Figure 12 A is the Photomicrograph of opening valve, and Figure 12 B is the Photomicrograph of the valve of closure under about 45psi.
Figure 13 shows by material of one embodiment of the invention and method and makes device.
Figure 14 shows material and the method for using one embodiment of the invention and repairs the system that destroys member.
Figure 15 shows the molding and the reconstruction of moulded product according to an embodiment of the invention.
Figure 16 A-16C shows the device of the inner chamber (lumen) that has according to an embodiment of the invention.
Figure 17 shows the device that forms in proper order via according to an embodiment of the invention caster patterning.
Figure 18 shows sacrifice layer manufacture method and device according to an embodiment of the invention.
Detailed Description Of The Invention
Now describe disclosure theme hereinafter more completely with embodiment with reference to the accompanying drawings, wherein show representational embodiment.Yet, can and should not be construed by multi-form enforcement disclosure theme and be limited to embodiment given herein.These embodiments are provided, will will be thoroughly and completely just, and pass on the scope of embodiment to those skilled in the art comprehensively in order to make present disclosure.
Unless otherwise defined, employed all technology of this paper and scientific terminology have the identical meanings as the theme those of ordinary skill in the field common sense of current description.All publications, patent application, patent and other reference are integrally introduced for reference referred in this.
In whole specification sheets and claims, chemical formula that provides or title will contain all optics and steric isomer, and the racemic mixture that wherein has this type of isomer and mixture.
I. definition
Term as used herein " microfluidic device " is often referred to can be via its device of carrying material (especially the material of fluid load, as liquid), and in some embodiments, this device is a micron order, is nano level in some embodiments.Therefore, the microfluidic device of disclosure subject description can comprise micron order parts (feature), nanoscale component and/or their combination.
Therefore, microfluidic device comprises that typically size is about millimeter level or lower structure or functional component, and they can be that mul/min or lower flow velocity are handled fluid with the order of magnitude.Typically, these parts include but not limited to raceway groove, fluid reservoir, reaction chamber, mixing section and disengaging zone.In some instances, this raceway groove comprises at least one cross-sectional dimension in the scope of the about 500 μ m of about 0.1 μ m-.Use the size of this magnitude to allow in less zone, to introduce the raceway groove of greater number, and use the fluid of smaller size smaller.
Microfluidic device can Individual existence maybe can be the part of microfluid system, this system for example but can not comprise with not limiting to: in system, introduce fluid (for example sample, reagent, damping fluid etc.) and/or make the pump of fluid by system; Test set or system; Reagent, product or data storage system; Controlling System with the residing envrionment conditions of fluid (for example temperature, flow etc.) in fluid conveying in the control device and/or direction, monitoring and the control device.
Term as used herein " device " includes but not limited to, microfluidic device, microtiter plate, pipe arrangement, flexible pipe, medical implant device, operation device, sticking patch, orthopaedic implant, medical device member, instrument etc.
Term as used herein " raceway groove ", " micron order raceway groove " and " microfluid raceway groove " use interchangeably, and can mean by the pattern of patterned substrate being given material or being removed technology and the groove or the cavity that in material, form, perhaps can mean the groove or the cavity that combine with any suitable flow-guiding structure of in described groove or cavity, installing (as pipe, kapillary etc.) by any suitable material.
Term as used herein " runner " and " control raceway groove " are used interchangeably and can be meant wherein material, the raceway groove in the microfluidic device that can flow through as fluid (for example gas or liquid).More particularly, term " runner " is meant the material of being considered, for example solvent or the chemical reagent raceway groove that can flow through.In addition, term " control raceway groove " is meant wherein material, the runner that can flow through by the mode that drives valve or pump as fluid (for example gas or liquid).More particularly, this kind raceway groove is filled with the gas or the liquid of the material of impermeable microfluidic device, medical device or medical implant.The example of this type of gas comprises sulfur hexafluoride.The example of this class I liquid I comprises mineral oil, silicone oil, propylene glycol and ethylene glycol.Alternatively, in some embodiments, " runner " of the present disclosure and/or " control raceway groove " is for being placed in one and/or the fluid (for example gas or liquid) above just described of mobile is impermeable therein.
Except as otherwise noted, term as used herein " valve " is meant that the elastomerics fragment (for example PFPE fragment) that wherein is applied to the motivating force on another raceway groove (for example controlling raceway groove) by response and can be displaced to a raceway groove (for example runner) or therefrom withdrawal separates the structure of two raceway grooves.Term " valve " also comprises check valve, and they comprise the raceway groove that is separated by pearl." valve " can also mean synthetic or natural biological valve as, vascular valve, heart valve etc.
Term as used herein " pattern " can mean the integrated network of raceway groove or microfluid raceway groove or microfluid raceway groove, and in some embodiments, they can intersect at predetermined point.Pattern can also comprise one or more of micron or nano level fluid reservoir, micron or nano level reaction chamber, micron or nano level mixing section, micron or nano level disengaging zone, surface tissue (texture) is at the pattern that can comprise on micron or nano-scale groove and/or the raised surface.This picture on surface can be a rule or irregular.
Term as used herein " intersection " can mean at certain point meets, and meets and runs through or intersect at certain point, or meet and overlapping at certain point.More particularly, term as used herein " intersection " is described an embodiment, and wherein two raceway grooves meet at certain point, meets and runs through each other or intersect at certain point, or meet and overlap each other at certain point.Therefore, in some embodiments, two raceway grooves can intersect, and promptly meet or meet and run through each other at certain point at certain point, and be fluid communication with each other.In some embodiments, two raceway grooves can intersect, and promptly meet and overlap each other at certain point, and be not fluid communication with each other, the situation that Here it is when runner and control raceway groove intersect.
" connection " (for example for term as used herein, first member " is communicated with " or " being in connected state " with second member) and its phraseological variant be used for representing structure, function, machinery, electricity, optics or fluidity relation between two or more members or the element or their any combination.Thereby, say the fact that is communicated with second member not wish to get rid of additional member a member and may reside between first and second members, and/or with this first and second member the operation on relevant or mutually the linking possibility.
Refer to use the microfluidic device treat fluid hold or when mobile, term " in device ", " on device ", " in device ", " to device ", " by device " and " crossing device " has equivalent meaning usually.
Term as used herein " integral body " is meant to have or serve as structure single, uniform structure.
Term as used herein " abiotic organic materials " is meant the organic materials except that biomaterial, promptly has those compounds of covalency C-C.Term as used herein " biomaterial " comprises that nucleic acid molecule (for example, DNA, RNA), the amino acid macromole (for example, enzyme, protein etc.) and little organic compound is (for example, steroid, hormone), wherein said little organic compound biologically active, especially to human or commercially important animal, as pet and domestic animal biologically active, and wherein said little organic compound is mainly used in treatment or diagnostic purpose.When biomaterial has interests for medicine and biotechnology applications, widely apply to relate to by the material except that biomaterial (being abiotic organic materials) enhanced chemical process.
Term as used herein " partly solidified " is meant about 100% process that reacts that is less than of polymerizable groups wherein.Therefore, term " partly solidified material " is meant the material that has experienced partly solidified process.
Term as used herein " completely solidified " is meant wherein about 100% process that reacts of polymerizable groups.Therefore, term " completely crued material " is meant the material that has experienced the completely solidified process.
Term as used herein " photocuring " is meant the reaction of polymerizable groups, wherein can pass through actinic radiation, triggers this reaction as UV light.In this application, UV curing can be the synonym of photocuring.
Term as used herein " thermofixation " or " thermofixation " are meant the reaction of polymerizable groups, wherein can trigger reaction by the material heating is surpassed threshold value.
Follow long-standing patent law convention, the term " a " that uses among the application's (comprising claims), " an " and " the " refer to " one or more ".Therefore, for example, so-called " microfluid raceway groove " comprises a plurality of this kind microfluid raceway grooves, and be like that.
II. material
In certain embodiments, solvent-proof low surface energy polymeric material is described and used to theme of the present disclosure widely.According to some embodiments, low surface energy polymeric material includes but not limited to, PFPE (PFPE), poly-(dimethyl siloxane) (PDMS), poly-(butylene oxide ring), poly-(oxyethane), poly-(trimethylene oxide), polyisoprene, polyhutadiene, Fluorine containing olefine class fluoroelastomer etc.Example with this type of material casting device comprises: liquid PFPE precursor material is cast on the patterned substrate, then this liquid PFPE precursor material is solidified to produce the patterned layer of functionalized PFPE material, it can be used for forming device, as medical device or microfluidic device.In order to simplify, most of descriptions will concentrate on the PFPE material, yet, be understandable that other this base polymer can be applied to method of the present invention, material and device equally as above-named those.
The representational elastomerics of anti-solvent class material includes but not limited to fluorinated elastomer class material.Term as used herein " anti-solvent " is meant in hydrocarbon organic solvent commonly used or acidity or alkaline aqueous solution the neither undissolved again material of swelling, as elastomer material.Representational fluorinated elastomer class material includes but not limited to PFPE (PFPE) class material.
In certain embodiments, functionalized liquid PFPE material demonstrates the desirable performance that is used for microfluid and/or medical device.For example, functionalized PFPE material has low surface energy usually, be nontoxic, saturating UV and visible light, highly breathable; Be solidified into toughness, durable, highly fluorinated elastomerics or vitreous material, this material has excellent anti-adhesion performance, anti-swelling, anti-solvent, physiologically acceptable, their combination etc.The performance of these materials can be adjusted in wide scope by reasonably selecting additive, filler, reactive comonomer and functionalized agent (their example will further describe in this article).
Wish that improved those performances include but not limited to, modulus, tear strength, surface energy, perviousness, functionality, curing pattern, solubility, toughness, hardness, elasticity, swelling character, their combination etc.Regulating the machinery of finished-product material and/or the certain methods example of chemical property includes but not limited to, molecular weight between the minimizing cross-linking set improves the modulus of material, the monomer that adds the formation high-tg polymer is to improve the modulus of material, add charged monomer or material in the material to improve the surface energy or the wettability of material, their combination etc.In some embodiments, material of the present invention has low surface energy, and wherein " low " is defined as about 30 dynes per centimeter.According to an embodiment, surface energy is lower than about 30 dynes per centimeter.According to another embodiment, surface energy is lower than about 20 dynes per centimeter.According to a preferred embodiment, surface energy is lower than about 18 dynes per centimeter.According to another embodiment, surface energy is lower than about 15 dynes per centimeter.According to another embodiment, surface energy is lower than about 12 dynes per centimeter.According to other embodiment, surface energy is lower than about 10 dynes per centimeter.
In some embodiments, when standing the hydrocarbon solvent processing, fluorinated polymer of the present invention (such as but not limited to PFPE) swelling is less than about 15% volume change.In alternate embodiment, described hydrocarbon solvent can be tetrahydrofuran (THF), toluene, methylene dichloride, hexane, chloroform, Virahol, hexanaphthene, methyl ethyl ketone, acetone, their combination etc.In alternate embodiment, fluoropolymer of the present invention can change so that the swelling of this fluoropolymer to this kind solvent is reduced to less than about 10wt% through embodiment and the method for this paper.In other embodiments, the swelling of the solvent enumerated of fluoropolymer response this paper is less than the about changes in weight of 8wt%.In other embodiments, the swelling that can the solvent that the composition of fluoropolymer and structure so that this fluoropolymer response this paper enumerate be set by method disclosed herein is less than the about changes in weight of 5wt%.Can be applied to material disclosed herein other solvent can referring to
People such as Lee J.N.Solvent Compatibility ofPoly (dimethylsiloxane) Based Microfluidic Devices, Anal.Chem.75,6544-6554 (2003), document integral body is hereby incorporated by, and comprises all reference of wherein quoting.The not swelling property of PFPE material of the present disclosure and easy release property allow to make microfluidic device.
According to some embodiments, fluoropolymer of the present invention has about 1: 2 carbon and fluorine ratio.In some embodiments, this carbon is about 1: 1 with the fluorine ratio.In alternate embodiment, this carbon is about 2: 1 with the fluorine ratio.According to other embodiment, this carbon is about 1 with the fluorine ratio: about 2: 1 of 1-.According to other embodiment, this carbon is about 1 with the fluorine ratio: about 1: 2 of 1-.
According to an aspect of the present invention, for material described herein, the molecular weight of polymkeric substance can for example pass through chain extension, mix with other component, increase or minimizing functional group wait to be selected or modification, has predetermined mechanical property with generation, as modulus, elongation at break, toughness, shearing, their the gained material of combination etc.In some embodiments, the modulus of fluorinated polymer material described herein can reduce by the molecular weight that improves this fluoropolymer.In one embodiment, the molecular weight of fluoropolymer be about 16000 and modulus be about 800kPa.According to other embodiment, the modulus of this material can be about 500kPa.According to other embodiment, the modulus of this material can be about 400kPa.According to other embodiment, the modulus of this material can be about 200kPa.According to other embodiment, the modulus of this material can be about 100kPa.According to other embodiment, the modulus of this material can be about about 5megaPa of 100kPa-.
In some embodiments, the elongation at break of this material is along with the molecular weight of this material increases and increases.According to some embodiments, the elongation at break of fluoropolymer of the present invention be about 200% and this molecular weight be about 16000.According to an embodiment, the elongation at break of this fluoropolymer is about 300%.According to an embodiment, the elongation at break of this fluoropolymer is about 250%.According to an embodiment, the elongation at break of this fluoropolymer is about 200%.According to an embodiment, the elongation at break of this fluoropolymer is about 100%.According to some embodiments, the elongation at break of this fluoropolymer is about 300%-about 100%.
II.A. poly-by viscosity less than the perfluor of the liquid PFPE precursor material preparation of about 100 centistokes
The ether material
As those of ordinary skills admitted, PFPE (PFPE) had been used for many application and has surpassed 25 years.Commercial PFPE material is by the polymerization preparation of perfluorinated monomer.First member of this class material is prepared by the cesium fluoride catalyzed polymerization of Propylene oxide hexafluoride (HFPO), thereby has produced a series of called after KRYTOX
The branched polymer of (DuPont, Wilmington, Delaware, UnitedStates of America).Similarly polymkeric substance produces (FOMBLIN by the UV catalysis photo-oxidation of R 1216
Y) (Solvay Solexis, Brussels, Belgium).In addition, by similar method, but be to use tetrafluoroethylene to prepare linear polymer (FOMBLIN
Z) (Solvay).At last, the 4th kind of polymkeric substance (DEMNUM
) (Osaka Japan) then directly fluoridizes preparation by the polymerization of tetrafluoro trimethylene oxide for DaikinIndustries, Ltd..These fluidic structures provide in Table I.Table II comprises some members' of PFPE series lubricant agent performance data.Similarly, the physicals of functionalized PFPE provides in Table III.Except the PFPE fluid that these are purchased, preparing a series of new structures by direct fluorination technology.The exemplary configuration of these new PFPE materials provides in Table IV.In above-mentioned PFPE fluid, KRYTOX only
And FOMBLIN
Z has been widely used for using.Referring to
Jones, W.R., Jr., The Properties of Perfluoropolyethers Used forSpace Applications, NASA Technical Memorandum 106275 (in July, 1993), the document is incorporated herein by reference in this integral body.Therefore, the purposes of this type of PFPE material is provided in the disclosure theme.
Table I. commercial PFPE fluidic title and chemical structure
Table II .PFPE physicals
Table III. the PFPE physicals of functionalized PFPE
Table IV. representational PFPE fluidic title and chemical structure
Name structure
a
Perfluoropoly(methylene?oxide)(PMO)?CF
3O(CF
2O)
xCF
3
Perfluoropoly(ethylene?oxide)(PEO) CF
3O(CF
2CF
2O)
xCF
3
Perfluoropoly(dioxolane)(DIOX) CF
3O(CF
2CF
2OCF
2O)
xCF
3
Perfluoropoly(trioxocane)(TRIOX) CF
3O[(CF
2CF
2O)
2CF
2O]
xCF
3
aWherein x is any integer
In some embodiments, the PFPE precursor comprises poly-(ptfe ring oxidative ethane-copolymerization-difluoro formaldehyde) α, the ω glycol, it in some embodiments can photocuring and forms a kind of in PFPE dimethacrylate and the PFPE diphenylethylene compounds.The representative solution synthetic and photocuring of functionalized PFPE is provided in the scheme 1.
Synthetic and the photocuring of scheme 1. functionalized PFPE
II.B. poly-by viscosity greater than the perfluor of the liquid PFPE precursor material preparation of about 100 centistokes
The ether material
Provided belowly be used to promote and/or improve the layer and the adhesivity between another kind of material and/or the base material of PFPE material and be used for adding the chemical functionality to lip-deep method comprise the PFPE material, this PFPE material have the viscosity of being selected from greater than about 100 centistokes (cSt) and viscosity less than the about characteristic of 100cSt, condition is a viscosity less than the liquid PFPE precursor material of 100cSt is not the photo curable PFPE material of free radical.The viscosity of the liquid PFPE precursor material that this paper provided is meant functionalized, for example with the viscosity of this material before methacrylic ester or the styrenic group functionalization.
Therefore, in some embodiments, prepare the PFPE material greater than the liquid PFPE precursor material of about 100 centistokes (cSt) by viscosity.In some embodiments, this liquid PFPE precursor is by the polymerizable groups end-blocking.In some embodiments, this polymerizable groups is selected from acrylate, methacrylic ester, epoxy group(ing), amino, carboxyl, acid anhydrides, maleimide, isocyano, olefinic and styrenic group.
In some embodiments, the PFPE material comprises the skeleton structure that is selected from following structure:
Wherein X exists or does not exist, and comprises capping group when existing, and n is the integer of 1-100.
In some embodiments, the PFPE Liquid precursor is synthetic by Propylene oxide hexafluoride or ptfe ring oxidative ethane, shown in scheme 2.
Scheme 2. by Propylene oxide hexafluoride or ptfe ring oxidative ethane synthetic fluid PFPE precursor material in some embodiments, liquid PFPE precursor is synthetic by Propylene oxide hexafluoride or ptfe ring oxidative ethane, shown in scheme 3.
Scheme 3. is by Propylene oxide hexafluoride or ptfe ring oxidative ethane synthetic fluid PFPE precursor material
In some embodiments, liquid PFPE precursor comprises that the material of chain extension so that two or more chains were joined together before adding polymerizable groups.Therefore, in some embodiments, " connecting base " is connected to two chains on the molecule.In some embodiments, shown in scheme 4, connect base and connect three or tall person's chain more.
In some embodiments, X is selected from isocyanic ester, acyl chlorides, epoxy group(ing) and halogen.In some embodiments, R is selected from acrylate, methacrylic ester, vinylbenzene, epoxy group(ing), carboxyl, acid anhydrides, maleimide, isocyanic ester, olefinic and amine.In some embodiments, this circle is represented any multiple functionalized molecule.In some embodiments, multiple functionalized molecule comprises ring molecule.PFPE is meant any PFPE material provided above.
In some embodiments, the hyperbranched polymer that provides in the scheme 5 is provided liquid PFPE precursor, and wherein PFPE is meant any PFPE material provided above.
Scheme 5: hyperbranched PFPE liquid precursor material
In some embodiments, liquid PFPE material comprises the material that is selected from following end-functionalization:
In some embodiments, the PFPE Liquid precursor can be made the epoxy group(ing) structure division end-blocking with light acid producing agent photocuring.The light acid producing agent that is suitable for disclosure theme comprises, but be not limited to: two (4-tert-butyl-phenyl) iodine of tosic acid, two (4-tert-butyl-phenyl) iodine of trifluoromethanesulfonic acid, trifluoromethanesulfonic acid (4-bromo-phenyl) phenylbenzene sulfonium, trifluoromethanesulfonic acid (tert-butoxycarbonyl methoxyl group naphthyl) phenylbenzene sulfonium, trifluoromethanesulfonic acid (tert-butoxycarbonyl p-methoxy-phenyl) phenylbenzene sulfonium, trifluoromethanesulfonic acid (4-tert-butyl-phenyl) phenylbenzene sulfonium, trifluoromethanesulfonic acid (4-chloro-phenyl-) phenylbenzene sulfonium, phenylbenzene iodo-9,10-dimethoxy-anthracene-2-sulfonate, phosphofluoric acid phenylbenzene iodine, nitric acid phenylbenzene iodine, perfluor-1-butane sulfonic acid phenylbenzene iodine, tosic acid phenylbenzene iodine, trifluoromethanesulfonic acid phenylbenzene iodine, trifluoromethanesulfonic acid (4-fluorophenyl) phenylbenzene sulfonium, trifluoromethanesulfonic acid N-hydroxyl naphthalimide, perfluor-1-butane sulfonic acid N-hydroxyl-5-norbornylene-2, the 3-dicarboximide, trifluoromethanesulfonic acid N-hydroxyphthalimide, hexafluoro-antimonic acid [4-[(2-hydroxyl tetradecyl) oxygen] phenyl]-phenyl-iodide, trifluoromethanesulfonic acid (4-iodine substituted phenyl) phenylbenzene sulfonium, trifluoromethanesulfonic acid (4-p-methoxy-phenyl) phenylbenzene sulfonium, 2-(4-methoxyl-styrene)-4, two (trichloromethyl)-1 of 6-, 3, the 5-triazine, trifluoromethanesulfonic acid (4-aminomethyl phenyl) phenylbenzene sulfonium, trifluoromethanesulfonic acid (4-methyl thio-phenyl) aminomethyl phenyl sulfonium, trifluoromethanesulfonic acid 2-naphthyl phenylbenzene sulfonium, trifluoromethanesulfonic acid (4-Phenoxyphenyl) phenylbenzene sulfonium, trifluoromethanesulfonic acid (4-phenyl thio-phenyl) phenylbenzene sulfonium, thiobis (phosphofluoric acid triphenylsulfonium), the hexafluoro-antimonic acid triarylsulfonium salt, the phosphofluoric acid triarylsulfonium salt, perfluor-1-butane sulfonic acid triphenylsulfonium, the trifluoromethanesulfonic acid triphenylsulfonium, perfluor-1-butane sulfonic acid three (4-tert-butyl-phenyl) sulfonium and trifluoromethanesulfonic acid three (4-tert-butyl-phenyl) sulfonium.
In some embodiments, liquid PFPE precursor cures becomes the elastomerics of height UV and/or highly-visible optical transparency.In some embodiments, this liquid PFPE precursor cures becomes the elastomerics of highly permeable oxygen, carbonic acid gas and nitrogen (can promote to keep the performance of the survivability of the biofluid/cell that is placed in one).In some embodiments, interpolation additive or manufacturing layer come enhance device to molecule, as the barrier property of oxygen, carbonic acid gas, nitrogen, dyestuff, reagent etc.
In some embodiments, be suitable for comprising silicone material that it comprises the functionalized polydimethylsiloxane (PDMS) of fluoro-alkyl with following structure with the material that disclosure theme uses:
Wherein:
R is selected from acrylate, methacrylic ester and vinyl;
R
fComprise the fluoro-alkyl chain;
N is 1-100,000 integer.
In some embodiments, be suitable for comprising styrenic material that it has and is selected from following fluorinated styrenic macromonomers with the material that disclosure theme uses:
R wherein
fComprise the fluoro-alkyl chain.
In some embodiments, be suitable for comprising the acrylate material that it comprises fluorinated acrylic ester or the fluorinated methyl acrylate with following structure with the material that disclosure theme uses:
Wherein:
R is selected from the aryl of alkyl, aryl and the replacement of H, alkyl, replacement; With
R
fComprise the fluoro-alkyl chain, this fluoro-alkyl chain has between perfluoroalkyl chain and ester bond-CH
2-or-CH
2-CH
2-spacer.In some embodiments, described perfluoroalkyl has the hydrogen substituting group.
In some embodiments, be suitable for comprising triazine fluoropolymer with fluorinated monomer with the material that disclosure theme uses.
In some embodiments, can comprise functionalized alkene by metathesis polymerization reactive polymeric or crosslinked fluorinated monomer or fluorinated oligomeric thing.In some embodiments, this functional olefines comprises functionalized cyclic olefin.
According to an alternate embodiment, the carbamate block by following structrual description that provides in the scheme 6 and demonstration is provided the PFPE material:
PFPE carbamate four functionalized methacrylic esters
Scheme 6.PFPE carbamate four functionalized methacrylic esters
According to one embodiment of the invention, PFPE carbamate four functionalized methacrylic acid ester materials can or can be used in combination with other material described herein and method as material of the present invention and method as described above, and this is that those of ordinary skills can understand.
According to some embodiments, the carbamate system comprises the material with following structure:
Scheme 7. is used for the PFPE carbamate system of microfluid
According to this scheme (scheme 7), part A is the curable precursor of UV, and part B and C constitute the thermal curable components of this carbamate system.The 4th precursor component (part D) is end capped precursor (for example, the end capped Liquid precursor of vinylbenzene).According to some embodiments, part D and the potential methacrylic ester, acrylate or the styrene group reaction that are included in the base mateiral, thereby the functionality of adding chemical compatibility or surface passivation and this base mateiral of raising of this base mateiral.
II.C. Fluorine containing olefine class material
In addition, in some embodiments, the employed material of this paper is selected from highly fluorinated fluoroelastomer, for example contains the fluoroelastomer of 58wt% fluorine at least, as
TangU.S. Patent number 6,512,063 described, the document is incorporated herein by reference in this integral body.This type of fluoroelastomer can be partially fluorinated or fluoridized, and can comprise 25-70wt% (based on the weight of this fluoroelastomer) first monomer (vinylidene fluoride (VF for example
2) or tetrafluoroethylene (TFE)) the copolymerization unit.The remaining unit of this fluoroelastomer comprises one or more additional copolymerization monomers, and they are different from first monomer, and be selected from Fluorine containing olefine, contain fluorovinyl ether, hydrocarbon olefin and their combination.
These fluoroelastomers comprise VITON
(DuPont Dow Elastomers, Wilmington, Delaware, United States of America) and Ke1-F type polymkeric substance, as
People such as UngerU.S. Patent number 6,408,878 in the polymkeric substance described for microfluidic applications.Yet these commercially available polymkeric substance have the mooney viscosity of about 40-65 (ML 1+10 is under 121 ℃), give that they are clamminess, gelationus viscosity.When solidified, they become rigidity, opaque solid.Current obtainable VITON
Has limited application with Ke1-F for the micron order molding.In Application Areas described herein, need to have similar composition, but have the curable materials of lower viscosity and bigger optical clarity.Lower viscosity (for example, 2-32 (ML 1+10 is under 121 ℃) or more preferably low to 80-2000cSt under 20 ℃, this composition produces can the pourable liquid of more effective solidified.
More particularly, Fluorine containing olefine includes but not limited to, vinylidene fluoride, R 1216 (HFP), tetrafluoroethylene (TFE), 1,2,3,3,3-five fluorine propylene (1-HPFP), trifluorochloroethylene (CTFE) and vinyl fluoride.
This contains fluorovinyl ether and includes but not limited to perfluor (alkyl vinyl) ether (PAVE).More particularly, perfluor (alkyl vinyl) ether that comprises following general formula as monomeric perfluor (alkyl vinyl) ether:
CF
2＝CFO(R
fO)
n(R
fO)
mR
f
Each R wherein
fBe linearity or branching C independently
1-C
6Perfluorinated alkylidene, m and n are the integer of 0-10 independently of one another.
In some embodiments, perfluor (alkyl vinyl) ether comprises the monomer of following general formula:
CF
2＝CFO(CF
2CFXO)
nR
f
Wherein X is F or CF
3, n is the integer of 0-5, R
fBe linearity or branching C
1-C
6Perfluorinated alkylidene.In some embodiments, n is 0 or 1, R
fComprise 1-3 carbon atom.The representative example of these perfluors (alkyl vinyl) ether comprises perfluor (methyl ethylene) ether (PMVE) and perfluor (propyl ethylene base) ether (PPVE).
In some embodiments, perfluor (alkyl vinyl) ether comprises the monomer of following general formula:
CF
2＝CFO[(CF
2)
mCF
2CFZO)
nR
f
R wherein
fBe the perfluoroalkyl that contains 1-6 carbon atom, m is 0 or 1 integer, and n is the integer of 0-5, and Z is F or CF
3In some embodiments, R
fBe C
3F
7, m is 0, n is 1.
In some embodiments, perfluor (alkyl vinyl) ether monomer comprises the compound of following general formula:
CF
2＝CFO[(CF
2CF{CF
3}O)
n(CF
2CF
2CF
2O)
m(CF2)
p]C
xF
2x+1
Wherein m and n are the integer of 0-10 independently of one another, and p is the integer of 0-3, and x is the integer of 1-5.In some embodiments, n is 0 or 1, and m is 0 or 1, and x is 1.
Other example of useful perfluor (alkyl vinyl ether) comprises:
CF
2＝CFOCF
2CF(CF
3)O(CF
2O)
mC
nF
2n+1
Wherein n is the integer of 1-5, and m is the integer of 1-3.In some embodiments, n is 1.
The copolymerization unit of perfluor (alkyl vinyl) ether (PAVE) is present in the embodiment in the fluoroelastomer of current description therein, and in the gross weight of this fluoroelastomer, this PAVE content is generally 25-75wt%.If PAVE is perfluor (methyl ethylene) ether (PMVE), then fluoroelastomer comprises the PMVE unit of 30-55wt% copolymerization.
The hydrocarbon olefin that can be used for the fluoroelastomer of current description includes but not limited to, ethene (E) and propylene (P).The copolymerization unit of hydrocarbon olefin is present in the embodiment in the fluoroelastomer of current description therein, and this hydrocarbon olefin content is generally 4-30wt%.
In addition, in some embodiments, the fluoroelastomer of current description can comprise that one or more solidify the unit of center monomer.The example of the curing center monomer that is fit to comprises: i) brominated alkene; Ii) contain iodine alkene; Iii) brominated vinyl ether; Iv) contain iodoethylene base ether; The Fluorine containing olefine that v) has itrile group; The fluorovinyl ether that contains that vi) has itrile group; Vii) 1,1,3,3,3-five fluorine propylene (2-HPFP); Viii) perfluor (2-phenoxy propyl vinyl) ether; And ix) non-conjugated diene.
Bromination is solidified center monomer can comprise other halogen, preferred fluorine.The example that brominated olefins is solidified center monomer is CF
2=CFOCF
2CF
2CF
2OCF
2CF
2Br; The bromo trifluoro-ethylene; 4-bromo-3,3,4,4-tetrafluoro butene-1 (BTFB); And other is as bromine ethene, 1-bromo-2,2-difluoroethylene; The perfluor allyl bromide 98; 4-bromo-1,1,2-trifluoro butene-1; 4-bromo-1,1,3,3,4,4 ,-the hexafluoro butylene; 4-bromo-3-chloro-1,1,3,4,4-five fluorine butylene; 6-bromo-5,5,6,6-tetrafluoro hexene; 4-bromo perfluorobuttene-1 and 3,3-difluoro allyl bromide 98.Ethylene bromide base ether solidifies center monomer and comprises 2-bromo-perfluoroethyl perfluorovinyl base ether and CF
2Br-R
f-O-CF=CF
2Class fluorinated compound (R wherein
fBe perfluorinated alkylidene), as CF
2BrCF
2O-CF=CF
2And ROCF=CFBr or ROCBr=CF
2Class fluorinated ethylene base ether (wherein R is low alkyl group or fluoro-alkyl) is as CH
3OCF=CFBr or CF
3CH
2OCF=CFBr.
The iodate alkene that center monomer comprises following general formula: CHR=CH-Z-CH is solidified in the iodate that is fit to
2CHR-I, wherein R be-H or-CH
3Z is C
1-C
18(entirely) fluoro alkylidene group, this fluoro alkylidene group is linearity or branching, chooses wantonly to contain one or more ether oxygen atoms, or disclosed (entirely) fluoro polyoxy alkylidene group in the U.S. Patent number 5,674,959.Other example that center monomer is solidified in useful iodate is the unsaturated ethers of following general formula: I (CH
2CF
2CF
2)
nOCF=CF
2And ICH
2CF
2O[CF (CF
3) CF
2O]
nCF=CF
2, etc., wherein n is the integer of 1-3, and is as U.S. Patent number 5,717, disclosed in 036.In addition, center monomer is solidified in the iodate that is fit to, and comprises iodoethylene, 4-iodo-3,3,4,4-tetrafluoro butene-1 (ITFB); 3-chloro-4-iodo-3,4,4-trifluoro butylene; 2-iodo-1,1,2,2-tetrafluoro-1-(vinyl oxygen base) ethane; 2-iodo-1-(perfluorovinyl sulfide oxygen base)-1,1 ,-2, the 2-tetrafluoroethylene; 1,1,2,3,3,3-hexafluoro-2-iodo-1-(perfluorovinyl sulfide oxygen base)-propane; 2-iodo ethyl vinyl ether; 3,3,4,5,5,5-hexafluoro-4-iodo amylene; With the iodo trifluoro-ethylene at U.S. Patent number 4,694, disclose in 045.Allyl iodide and 2-iodo-perfluoroethyl perfluorovinyl base ether also are useful curing center monomer.
Useful contain nitrile solidify center monomer comprise below shown in those of general formula:
CF
2＝CF-O(CF
2)
n-CN
Wherein n is the integer of 2-12.In some embodiments, n is the integer of 2-6.
CF
2＝CF-O[CF
2-CF(CF)-O]
n-CF
2-CF(CF
3)-CN
Wherein n is the integer of 0-4.In some embodiments, n is the integer of 0-2.
CF
2＝CF-[OCF
2CF(CF
3)]
x-O-(CF
2)
n-CN
Wherein x is 1 or 2, and n is the integer of 1-4; With
CF
2＝CF-O-(CF
2)
n-O-CF(CF
3)-CN
Wherein n is the integer of 2-4.In some embodiments, solidifying center monomer is the perfluorinated polyether with itrile group and trifluoro vinyl ether.
In some embodiments, solidifying center monomer is:
CF
2＝CFOCF
2CF(CF
3)OCF
2CF
2CN
That is, perfluor (8-cyano group-5-methyl-3,6-Er Evil-1-octene) or 8-CNVE.
The example that non-conjugated diene solidifies center monomer includes but not limited to, 1, and the 4-pentadiene; 1, the 5-hexadiene; 1, the 7-octadiene; 3,3,4,4-tetrafluoro-1,5-hexadiene; And other, as those disclosed among Canadian Patent numbers 2,067,891 and the european patent number 0784064A1.The triolefin that is fit to is 8-methyl-4-ethidine-1, the 7-octadiene.
To use therein in the embodiment of peroxide cure fluoroelastomer, this curing center monomer is preferably selected from 4-bromo-3,3,4,4-tetrafluoro butene-1 (BTFB); 4-iodo-3,3,4,4-tetrafluoro butene-1 (ITFB); Allyl iodide; Bromo trifluoro-ethylene and 8-CNVE.In therein will the embodiment with the polyvalent alcohol cured fluoroelastomer, 2-HPFP or perfluor (2-phenoxy propyl vinyl) ether be preferably to solidify center monomer.In therein will the embodiment with tetramine, two (amino-phenols) or two (sulfo-amino phenol) cured fluoroelastomer, 8-CNVE preferably solidifies center monomer.
In the time of in being present in fluoroelastomer of the present disclosure, the unit that solidifies center monomer is usually in 0.05-10wt% (with the gross weight of fluoroelastomer), preferred 0.05-5wt%, and most preferably the level of 0.05-3wt% exists.
The fluoroelastomer that can be used for disclosure theme includes but not limited to, have at least the 58wt% fluorine and have following copolymerization unitary those: i) vinylidene fluoride and R 1216; Ii) vinylidene fluoride, R 1216 and tetrafluoroethylene; Iii) vinylidene fluoride, R 1216, tetrafluoroethylene and 4-bromo-3,3,4,4-tetrafluoro butene-1; Iv) vinylidene fluoride, R 1216, tetrafluoroethylene and 4-iodo-3,3,4,4-tetrafluoro butene-1; V) vinylidene fluoride, perfluor (methyl ethylene) ether, tetrafluoroethylene and 4-bromo-3,3,4,4-tetrafluoro butene-1; Vi) vinylidene fluoride, perfluor (methyl ethylene) ether, tetrafluoroethylene and 4-iodo-3,3,4,4-tetrafluoro butene-1; Vii) vinylidene fluoride, perfluor (methyl ethylene) ether, tetrafluoroethylene and 1,1,3,3,3-five fluorine propylene; Viii) tetrafluoroethylene, perfluor (methyl ethylene) ether and ethene; Ix) tetrafluoroethylene, perfluor (methyl ethylene) ether, ethene and 4-bromo-3,3,4,4-tetrafluoro butene-1; X) tetrafluoroethylene, perfluor (methyl ethylene) ether, ethene and 4-iodo-3,3,4,4-tetrafluoro butene-1; Xi) tetrafluoroethylene, propylene and vinylidene fluoride; Xii) tetrafluoroethylene and perfluor (methyl ethylene) ether; Xiii) tetrafluoroethylene, perfluor (methyl ethylene) ether and perfluor (8-cyano group-5-methyl-3,6-Er Evil-1-octene); Xiv) tetrafluoroethylene, perfluor (methyl ethylene) ether and 4-bromo-3,3,4,4-tetrafluoro butene-1; Xv) tetrafluoroethylene, perfluor (methyl ethylene) ether and 4-iodo-3,3,4,4-tetrafluoro butene-1; And xvi) tetrafluoroethylene, perfluor (methyl ethylene) ether and perfluor (2-phenoxy propyl vinyl) ether.
In addition, by in the preparation process of fluoroelastomer, using chain-transfer agent or molecular weight regulator, contain iodine end group, brominated end group or their combination and can randomly be present in fluorine-containing elastomer polymer terminated one or both ends.When using, the amount of chain-transfer agent makes as calculated that iodine in the fluoroelastomer or bromine water are flat and is 0.005-5wt%, preferred 0.05-3wt%.
The example of chain-transfer agent comprises and contains iodine compound, and it makes the iodine of introducing keyed jointing in the one or both ends of polymer molecule.Methylene iodide; 1,4-diiodo perfluo-normal butane and 1,6-two iodo-3,3,4,4-tetrafluoro hexane is the representative of this type of reagent.Other iodinated chain transfer agents comprises 1,3-diiodo perfluo propane; 1,6-diiodo perfluo hexane; 1,3-two iodo-2-chlorine perfluoropropane; 1,2-two (iodo difluoromethyl) perfluorocyclobutane; One iodo perfluoro ethane; One iodo perfluoro butane; 2-iodo-1-hydrogenation R 116 etc.Also comprise the disclosed cyano group of european patent number 0868447A1-iodine chain-transfer agent.Especially preferred is diiodinated chain transfer agents.
The example of brominated chain transfer agents comprises 1-bromo-2-iodo perfluoro ethane; 1-bromo-3-iodo perfluoro propane; 1-iodo-2-bromo-1,1-C2H4F2 C2H4F2 and other, as U.S. Patent number 5,151, those disclosed in 492.
Other chain-transfer agent that be fit to use comprises U.S. Patent number 3,707, those disclosed in 529.Examples of such agents comprises Virahol, diethyl malonate, ethyl acetate, tetracol phenixin, acetone and dodecyl mercaptans.
II.D. dual photocurable and thermal curable material
According to another embodiment, material according to the invention comprises one or more in photocurable composition and the thermal curable composition.In one embodiment, photocurable composition and thermal curable composition are irrelevant, so that this material can experience multi-curing.The material that can experience multi-curing is useful, for example, and the other parts or the member that form the stratiform device or device connected or be attached to other device or the part or the member of device connected or be attached to device.For example, the fluent material that contains photocurable and thermal curable composition can be via for example, and photocuring process or curing process experience first are solidified to form first device.Then, first device of photocuring or thermofixation can be adhered to and have same material or have on second device with any material of this materials similar (this material is with thermofixation or photocuring and be bonded on the material of first device).By the layout that this first device and second device is adjacent one another are and allow this experience thermofixation of first and second devices or photocuring, it is at the arbitrary component that is not activated when first solidifies.After this, the photocuring process of passing through of first device still keeps first thermofixation of passing through of the non-activated thermofixation composition or first device still to keep non-activated photocuring composition second device that will be activated and bond.In one embodiment, use this method and material, first and second devices become and adhere to each other.To the order that one of ordinary skill in the art will appreciate that solidification process is independent to determine, and can at first carry out thermofixation and then carry out photocuring or can at first carry out photocuring and then carry out thermofixation.
According to another embodiment, multiple thermal curable composition can be included in the material so that this material can experience multiple and curing process independently.For example, this multiple thermal curable composition can have different activation temperature scopes, so that this material can experience first thermofixation under first temperature range, experience second thermofixation etc. under second temperature range.Therefore, in one embodiment, can via different thermofixations with material adhesion to other multiple material, thereby form multiple lamination layer device.In alternate embodiment, material can be included in the different thermofixation composition that reacts or be activated under the different speed, therefore, for the user provides preference, for example under first rate, at first solidify this material, allow this material solidify with this at first on solidified material adhesion to the second kind of the material then in experience second under the different speed.
In another embodiment, material of the present invention can comprise dual photo-curing material, and it can comprise can be in solidified heterogeneity under the different wave length.For example, the first photocuring composition can be a solidified dimethacrylate under the wavelength of about 365nm.This material also can comprise the second photocuring composition, for example at another kind of wavelength, and activatory bicyclic oxygen material under the 254nm for example.Like this, a plurality of layer of device can and adhere on other base material (as glass, silicon, other polymer materials, laminate, their combination etc.) at the different manufacturing stage keyed jointings of entire device.
The example of chemical group that may be the end-capping reagent that is fit to of UV curable components comprises: methacrylic ester, acrylate, styrenic, epoxide, tetramethylene and other 2+2 cycloaddition thing, their combination etc.Be suitable for the right example of the end capped chemical group of thermal curable components is comprised: epoxy group(ing)/amine; epoxy group(ing)/hydroxyl; triol/vulcabond; tetrol/vulcabond; carboxylic acid/amine, carboxylic acid/hydroxyl, ester/amine; ester/hydroxyl; amine/acid anhydrides, acyl halide/hydroxyl, acyl halide/amine; amine/halogenide; hydroxyl/halogenide, hydroxyl/chlorosilane, trinitride/acetylene and other so-called " link chemistry (click chemistry) " reaction; with the replacement(metathesis)reaction that relates to use Grubb type catalyzer, their combination etc.According to some embodiments, the example of the end-blocking combination of UV and heat comprises: UV diurethanes methacrylic ester and heat three pure and mild vulcabond components, UV diurethanes methacrylic ester and hot tetrol and vulcabond component, UV diurethanes methacrylic ester and UV bicyclic oxygen, UV diurethanes methacrylic ester and hot bicyclic oxygen and diamine components, UV diurethanes methacrylic ester and hot vulcabond, their combination etc.
A plurality of layer with device of the present disclosure is adhering to each other or adhere to independent lip-deep method and can be applied to PFPE class material, and various other material, comprises PDMS and other liquid polymer.The example that is suitable for the liquid polymer material of adhesion method of the present disclosure includes but not limited to, PDMS, poly-(butylene oxide ring), poly-(oxyethane), poly-(trimethylene oxide), polyisoprene, polyhutadiene and Fluorine containing olefine class fluoroelastomer are as can registered trademark VITON
And KALREZ
Those that obtain.
Therefore, in one embodiment, disclosure method can be used for layer with different polymer materialss and adhere to each other and form device, as the member of microfluidic device, medical device, operation device, instrument, medical device, implant material, laminate etc.For example, a plurality of PFPE and PDMS layer can adhere to each other in given microfluid and/or medical device.In some embodiments, different polymer materials comprise with same device in the fluoropolymer of mixed with polymers.According to some embodiments, this polymkeric substance can with this fluoropolymer mixing.According to other embodiment, this polymkeric substance not with this fluoropolymer mixing.
According to some embodiments, device can be formed by the composition with the fluoropolymer of mixed with polymers, and wherein this fluoropolymer comprises first functional group, and this polymkeric substance comprises second functional group.According to these embodiments, this functional group can be photocurable disclosed herein and/or thermal curable functional group.In other embodiment, device can be formed by the composition that contains first polymkeric substance and second polymkeric substance, and wherein this first polymkeric substance comprises first functional group, and this second polymkeric substance comprises second functional group.According to these embodiments, described first and second functional groups can comprise functional group disclosed herein, as photocurable and/or thermal curable functional group.In other embodiment, device can be formed by the composition that comprises first fluoropolymer and second fluoropolymer, and wherein this first fluoropolymer comprises first functional group, and this second fluoropolymer comprises second functional group.According to these embodiments, described first and second functional groups can comprise functional group disclosed herein, as photocurable and/or thermal curable functional group.Just now the composition of Miao Shuing can be by with first curable functional group of one of component of said composition (promptly, photocurable functional group) first curing is experienced in activation, then, after a plurality of members that form (via the photocuring of this material) device, thereby this member can be arranged opposite to each other and treatedly carry out second and solidify and to activate second functional group (that is thermal curable functional group) and should a plurality of members curing or laminated together.
According to other embodiment, the different component of device can be formed by differing materials, and for example first member of device can be formed by polymer materials, and second member of this device can be formed by fluorinated polymer material.According to these embodiments, this polymkeric substance and this fluoropolymer can comprise dual cure functional group, for example photocurable and thermal curable functional group.Therefore, each member of device can be by allowing this material experience first solidify (promptly, photocuring) makes to make this member, described then each member can be arranged opposite to each other and form required device and experience second curing (that is thermofixation) described each member is bondd and form this device.
II.E. silicone material
According to alternative embodiment, novel silicon ketone material comprises one or more photocurables and thermal curable components.In these alternative embodiments, the silicone material can comprise one or more photocurable components and one or more thermal curable components, so that this silicone material has dual cure ability described herein.The silicone material compatible with the present invention reaches in this article in whole introducing the application bibliography for reference and is described.
II.F. the polymkeric substance that contains phosphonitrile
According to some embodiments, Apparatus and method for disclosed herein can form with the material that comprises the polymkeric substance that contains phosphonitrile, and this polymkeric substance that contains phosphonitrile has following structure.According to these embodiments, below R in the structure contain fluoroalkyl chain.This type of example that contains fluoroalkyl chain can be referring to Langmuir, and 2005,21,11604, the disclosure of the document is incorporated herein by reference in this integral body.Disclosed device can be formed by polymer formation that contains phosphonitrile or the PFPE that combines with the polymkeric substance that contains phosphonitrile among the application.
IIG. use the end capped material of aryl trifluoro vinyl ether (TVE)
In some embodiments, Apparatus and method for disclosed herein can form with comprising by the material of the basic end capped material of one or more aryl trifluoro vinyl ethers (TVE), shown in following structure.Can be with the example of the end capped material of TVE base referring to Macromolecules, 2003,36,9000, the document is incorporated herein by reference in this integral body.These structures form the perfluorocyclobutanearyl structure division by the 2+2 addition reaction under about 150 ℃.In some embodiments, Rf can be a fluoropolymer, for example the PFPE chain.In some embodiments, three or more TVE bases are present on the 3 arm PFPE polymkeric substance so that this material is cross-linked into network.
II.H. sodium naphthalene etching reagent
In some embodiments, allow the sodium naphthalene etching reagent, as commercially available tetraetch
TMContact with the layer of device (as fluoropolymer device disclosed herein).In other embodiment, allow the sodium naphthalene etching reagent contact with the layer of PFPE class device (as microfluidic device disclosed herein).According to these embodiments, the C-F key reaction in the polymkeric substance of this etching reagent and this device, thus form functional group along the surface of this device.In some embodiments, these functional groups can go up with other layer then, the feature (modality) on the silicon face, on the glass surface, in their combination etc. reacts, thereby form adhesive bond.In some embodiments, can improve the layer of two devices, device, the adhesivity between their combination etc. in obtainable these adhesive bond on the surface of device disclosed herein (as microfluidic device).The bond joint strength that improves the interlayer of microfluidic device can be for example, and by the manipulable pressure range of the raceway groove that improves this device, the raising valve pressure waits and improves the functional of this device.
II.I trifunctional PFPE precursor
According to some embodiments, trifunctional PFPE precursor can be used for making device disclosed herein, as microfluidic device.In one embodiment, trifunctional PFPE precursor disclosed herein can improve the functional of entire device by improving the number that can add the functional group in this material to.In addition, trifunctional PFPE precursor can provide the crosslinked ability of raising for material.According to these embodiments, device can be synthetic by following reaction process.
In other embodiments, be used to make device, for example the trifunctional PFPE precursor of microfluidic device disclosed herein is synthetic by following reaction process.
II.J. be used to produce the fluoro-alkyl iodine precursor of fluoropolymer and/or PFPE
In some embodiments, functionalized PFPE or other fluoropolymer can use fluoro-alkyl iodine precursor to produce.According to these embodiments, these materials can modification be transformed into many functional groups commonly used then by the insertion of ethylidene, include but not limited to: silane, Gringard reagent, alcohol, cyano group, mercaptan, epoxide, amine and carboxylic acid.
Rf-I+＝＝→Rf-CH
2·CH
2-I
II.K. bicyclic oxygen material
According to some embodiments, can be used for making in the PFPE precursor of device disclosed herein such as microfluidic device one or more and comprise the bicyclic oxygen material.This bicyclic oxygen material can be synthetic by the reaction of PFPE glycol and Epicholorohydrin is come according to following reaction process.
II.L. the end capped PFPE chain that has cycloaliphatic epoxide
In some embodiments, the PFPE chain can be by cycloaliphatic epoxide structure division such as cyclohexane ring oxide compound, pentamethylene epoxide, their end-blockings such as combination.In some embodiments, the PFPE diepoxy resin comprises the chain extension material with following structure, and this structure is synthesized by the ratio that changes glycol and Epicholorohydrin in building-up process.The example of some synthesis programs, is described among the Vol 34,3263 at Journal of Polymer Science:Part A:PolymerChemistry 1996 by people such as Tonelli, and the document is incorporated herein by reference in this integral body.Use this method, the physics of solidify material and chemical property as performances such as machinery, optics, calorifics, comprise that elasticity, solvent resistance, translucency, toughness, adhesivity etc. can be adjusted to predetermined requirement.
In other embodiment, the secondary alcohol that forms in this reaction can be used for connecting other functional group.An example like this shows below, and wherein, this secondary alcohol and 2-isocyanatoethyl methacrylic ester react, and produces to have the material that free radical and cationic curing all is reactive material.In some embodiments, the functional group in functional group such as this example can be used for the surface is connected to together, for example the layer of the fluoropolymer in the microfluidic device (as PFPE) material.In other embodiment, can connect via this secondary alcohol class material along the structure division of the wall of micro-fluid chip such as biomolecules, protein, charge species, catalyzer etc.
II.M. use diamines solidified PFPE diepoxy resin
In some embodiments, the PFPE diepoxy resin can solidify with conventional diamines, includes but not limited to 1, the 6-hexanediamine; Isophorone diamine; 1; Their combination etc.According to some embodiments, diepoxy resin can be used imidazolium compounds, comprise that those imidazolium compoundss with following or dependency structure solidify, wherein R1, R2 and R3 can be hydrogen atom or other alkyl substituent such as methyl, ethyl, propyl group, butyl, fluorinated alkyl compound, their combination etc.According to some embodiments,, this imidazoles reagent is added in this PFPE diepoxy resin by the concentration that is about about 1-25mol% with respect to epoxy group content.In some embodiments, the PFPE diepoxy resin that contains imidazole catalyst is the hot part of dual cure systems, as described in other place of this paper.
II.N. use light acid producing agent solidified PFPE
In some embodiments, can solidify the PFPE diepoxy resin by making with light acid producing agent (PAG).In some embodiments, PAG is dissolved in the PFPE material and by being exposed under the UV light by the concentration of the about 5mol% of about 1-with respect to epoxy group(ing) and is solidified.Specifically, for example, these light acid producing agents can have following structure (Rhodorsil
TM) 2074 (Rhodia, Inc):
In other embodiment, this light acid producing agent can for example be the Cyracure with following structure
TM(Dow Corning):
II.O. the PFPE glycol that contains poly-(ethylene glycol)
In some embodiments, commercially availablely contain many poly-(ethylene glycol) unitary PFPE glycol, as commercial as ZDOL TX
TMThose of (Solvay Solexis) sale can be as making device, as the material of microfluidic device.In other embodiment, commercially available poly-(ethylene glycol) the unitary PFPE glycol of given number that contains is used in combination with other material disclosed herein.This type of material can be used for being dissolved in the PFPE diepoxy resin above-mentioned light trigger and the mechanical property that also can help to regulate this material, can and can introduce final network with the epoxy group(ing) unit process that increases because contain poly-(ethylene glycol) unitary PFPE glycol.
IIP. with PFPE diepoxy resin blended PFPE glycol and/or polyvalent alcohol
In other embodiments, commercially available PFPE glycol and/or polyvalent alcohol (show below and commercial as ZDOL
TMAnd Z-Tetrol
TM(Solvay Solexis) sells) can with PFPE diepoxy resin compound to regulate mechanical property by in solidification process, being incorporated in the epoxy group(ing) network that increases.
II.Q. with the PFPE Resins, epoxy that contains PAG of light trigger blend
In some embodiments, contain PAG PFPE Resins, epoxy can with the about 5 moles of % free radical photo-initiations of about 1-, for example, 2,2-dimethoxy-acetophenone, 1-hydroxycyclohexylphenylketone, diethoxy acetophenone, their blend such as combination.These materials form reactive cationic substance when with the PAG blend, when radical initiator during by the UV photoactivation, this cationic substance is the oxidation products of PAG, Macromolecules2005 as people such as Crivello, 38, as described in 3584 parts, the document is incorporated herein by reference in this integral body.In some embodiments, this kind cationic substance can cause epoxy-based polymerization and/or curing.Use this method to allow the PFPE diepoxy resin under various wavelength, to solidify.
II.R. contain the light acid producing agent and with the PFPE diepoxy resin of PFPE diepoxy resin blend
In some embodiments, contain the light acid producing agent PFPE diepoxy resin material can with the blend of PFPE dimethacrylate material, this dimethacrylate material comprises free radical photo-initiation and has following structure:
In one embodiment, this intermingling material comprises the dual cure material, this dual cure material can (for example solidify under a kind of wavelength, under 365nm, solidify this dimethacrylate), then via at another kind of wavelength, for example 254nm down the activation second diepoxy resin material curing and with other layer keyed jointing of material.Like this, a plurality of layer of patterning PFPE material can the different manufacturing stage keyed jointings of entire device and adhere to base material such as glass, silicon, other polymer materials, their combination etc. on.
II.S. other material
According to alternate embodiment, following material can use individually, uses in combination with other material disclosed herein, or by other material modification disclosed herein and be applied to method disclosed herein, in some embodiments, make device disclosed herein.In addition, disclosed end group in the disclosed herein and U.S. Patent number 3,810,874 and 4,818,801, each piece of writing in these documents is hereby incorporated by, and comprises all reference of wherein quoting.
II.S.i diurethanes methacrylic ester
In some embodiments, material is or comprises diurethanes methacrylic ester by modulus following reaction manufacturing and that have about 4.0MPa, and is that UV is curable and have a following structure:
II.S.ii. the diurethanes methacrylic ester of chain extension
In some embodiments, this material is or comprises by following reaction manufacturing and have title: the chain extension diurethanes methacrylic ester of 2M-240,2M-340,2M-440; Molecular weight between the increase of the chain extension before end-blocking cross-linking set; Modulus is 2.0MPa roughly; And be that UV is curable, have following structure:
In some alternate embodiments, the diurethanes methacrylic ester of this chain extension has following structure:
II.S.iii. vulcabond
In some embodiments, this material is or comprises title: 2I-140; This material is a component of two-pack heat-curable systems normally; Can solidify via the wet curing technology (disclosed herein) self that causes; Can and have following structure by following reaction manufacturing:
In some alternate embodiments, the functionalized PFPE of vulcabond has following structure:
II.S.iv. the vulcabond of chain extension
In some embodiments, this material is or comprises title: 2I-240,2I-340,2I-440 (depending on the chain extension degree); Wherein this material is a kind of component of two-pack heat-curable systems; By being linked together, several PFPE chains carry out chain extension; Can solidify self curing via wet causing; Can and comprise following structure by following reaction manufacturing:
II.S.v. end-blocking vulcabond
In some embodiments, this material is or comprises: title: 2I-140B; Comprise with the similar function of 2I-140 but to moisture insensitive (capping group at high temperature decompose and form again isocyanic ester); Material can be a kind of component in the two-pack heat-curable systems; Can and comprise following structure by following reaction manufacturing:
II.S.vi.PFPE three arm triols
In some embodiments, this material is or comprises: title: 3A-115; It is a kind of component of two-pack thermal curable carbamate system; Comprise can with the advantage of other PFPE composition height mixing; Can and comprise following structure by following reaction manufacturing:
The II.S.vii.PFPE toluylene
In some embodiments, this material is or comprises: title: 2S-140; Be that UV is curable; The height chemically stable; Can be used for making the lamination coating with other composition; Can and comprise following structure by following reaction manufacturing:
II.S.viii. diepoxy resin
In some embodiments, this material is or comprises: title: 2E-115,2E-140 (MW that depends on this chain); It can be the UV solidified; Can be to use imidazoles self thermofixation; Also can thermofixation in two-pack two amine systems; Be highly chemically stable; Can and comprise following structure by following reaction manufacturing:
II.S.ix. diamines
In some embodiments, this material is or comprises: title: 2A-115,2A-140 (MW that depends on chain); Can thermofixation in two-pack two amine systems; Has 6 functionality (can obtain 3 amine on each is terminal); Be highly chemically stable; Can and comprise following structure by following reaction manufacturing:
II.S.x. the PU-tetrol of thermofixation
In some embodiments, this material is or comprises: title: the 2I-140+Z-tetrol; Can thermofixation in bicomponent system, for example about 100-about 130 ℃ down by 2: 1 mixed in molar ratio; Form the network of toughness, mechanically stable; Because the not compatibility of tetrol, this curing network are muddy slightly; And comprise following:
II.S.xi. the PU-triol of thermofixation
In some embodiments, this material is or comprises: title: 2I-140+3A-115; Can thermofixation in bicomponent system, for example about 100-about 130 ℃ down by 3: 2 mixed in molar ratio; Form the network of toughness, mechanically stable; Wherein this curing network is transparent and colourless; And comprise following:
II.S.xii. the Resins, epoxy of thermofixation
In some embodiments, this material is or comprises: title: 2E-115+2A-115; Can thermofixation in bicomponent system, for example about 100-about 130 ℃ down by 3: 1 mixed in molar ratio; Form the network of mechanically stable; Wherein this curing network is transparent and colourless; Has high chemical stability; And comprise following:
II.S.xiii.UV solidified Resins, epoxy
In some embodiments, this material is or comprises: title: 2E-115+ZDOL TX; It is the UV curable compositions; Comprise and be used for the ZDOL TX of solubilising PAG; Wherein this solidified network is transparent and xanchromatic; Has high chemical stability; And comprise following:
The hot dual cure of II.S.xiv.UV-
In some embodiments, this material is or comprises: title: 2M-240,2I-140, Z-tetrol; Can be in 2: 1 ratio (UV: heat) mix; Form muddy network (tetrol); Has high viscosity; Form very strong adhesion; Has extraordinary mechanical property; And comprise following:
II.S.xv. the quadrature with triol solidifies (orthogonal cure)
In some embodiments, this material is or comprises: title: 2M-240,2I-140,3A-115; Can be in 2: 1 ratio (UV: heat) mix; Form transparent and colourless network; Has high viscosity; Form very strong adhesion; Has extraordinary mechanical property; And comprise following:
II.S.xvi.UV quadrature system
In some embodiments, this material is or comprises: title: 2M-240,2E-115, ZDOL-TX; Can be in 1: 1 ratio (epoxy group(ing): methacrylic ester) mix; Form transparent and xanchromatic network; Has strong adhesion property; The mechanical property that tool is good; And comprise following:
II.S.xvii.UV and Resins, epoxy dual cure
In some embodiments, this material is or comprises: title: 2M-240,2E-115, DA-115; This material forms little yellow network; Comprise ratio (2: 1 UV: heat); The mechanical property that tool is good; Good adhesion; It is the height chemical stability; And comprise following:
II.S.xviii. with the vulcabond quadrature
In some embodiments, this material is or comprises: title: 2M-240,2I-140; It is a kind of component of heat cured system (the amino-formate bond reaction on isocyanic ester and the carbamate dimethacrylate); Has good mechanical property; Form strong adhesion; Be solidified into transparent, yellowish network; And comprise following:
II.S.xix. the ePTFE that combines with PFPE
In some embodiments, will expand poly-(tetrafluoroethylene) (ePTFE) combine with PFPE.EPTFE gathers (tetrafluoroethylene) (PTFE) film by the micropore that the PTFE expansion is formed.Because the surprising low surface energy of PFPE disclosed herein (PFPE) material, this PFPE can be cast on the ePTFE film and make the hole of this ePTFE wetting effectively, thereby form interpenetrating polymer networks.
PFPE can comprise functional group, as functional group disclosed herein.In some embodiments, PFPE can comprise photocurable functional group and/or thermal curable functional group.In some embodiments, when PFPE comprises photocurable functional group, can by being exposed under the UV light this PFPE be solidified after to ePTFE in that this PFPE is wetting.The gained film of ePTFE and PFPE comprises, for example, and hope flexible, chemical resistant properties and to the ventilation property of solvent vapour and air.The ePTFE of this film partly provides a kind of continuous structure, and this continuous structure itself is compared with flexible body only and is used for greatly making material toughness reinforcing.Some films at United States Patent (USP) 6,673, have carried out general description in 455 by people such as Zumbrum, and the document is incorporated herein by reference in this integral body, comprises all reference of wherein quoting.
III. form the method for microfluidic device via the hot radical solidification process
In some embodiments, theme of the present disclosure provides the method that forms microfluidic device, by this method, allows functionalized liquid PFPE (PFPE) precursor material and patterned substrate, be main body (master) contact, and use radical initiator to carry out thermofixation.As more detailed providing hereinafter, in some embodiments, liquid PFPE precursor material is fully solidified to form completely crued PFPE network, then it is removed and contact to form reversible, gas-tight seal with second base material from patterned substrate.
In some embodiments, liquid PFPE precursor material is partly solidified to form partly solidified PFPE network.In some embodiments, allow this partly solidified network contact and curing reaction is carried out fully, thereby between the PFPE layer, form persistent keyed jointing with the second section solidified layer of PFPE material.
In addition, can allow this partly solidified PFPE network with comprise another kind of polymer materials, as the layer or the base material contact of poly-(dimethyl siloxane) or another kind of polymkeric substance, in addition thermofixation so that this PFPE network adhere on other polymer materials then.In addition, can make partly solidified PFPE network and solid substrate, as glass, quartz or silicon contact, then by using silane coupling agent that it is keyed on the base material.
III.A. form the method for the patterned layer of elastomer material
In some embodiments, disclosure theme provides the method for the patterned layer that forms elastomer material.The Fluorine containing olefine class material that disclosure method is suitable for describing among the PFPE material described with part II.A. and II.B. and the part II.C. uses together.The advantage of the PFPE material of use viscosity higher especially allows the higher molecular weight between the cross-linking set.Higher molecular weight between the cross-linking set can improve the elastomer performance of material, and this especially can prevent to form crackle.Referring now to Figure 1A-1C, show the diagram of an embodiment of disclosure theme.Described the base material 100 with patterned surface 102, this patterned surface 102 has the projection 104 of rise.Therefore, the patterned surface 102 of base material 100 comprises the projection 104 of at least one rise, and this projection 104 has formed the shape of pattern.In some embodiments, the patterned surface 102 of base material 100 comprises the projection 104 of a plurality of rises that form complex pattern.
As being best viewed in Figure 1B, liquid precursor material 106 is arranged on the patterned surface 102 of base material 100.Shown in Figure 1B, handle this liquid precursor material 102 with treatment process Tr.After the processing of liquid precursor material 106, formed the patterned layer 108 (shown in Fig. 1 C) of elastomer material.
Shown in Fig. 1 C, the patterned layer 108 of elastomer material is included in the groove 110 that forms in the basal surface of patterned layer 108.The size of groove 110 is corresponding with the size of the projection 104 of the rise of the patterned surface 102 of base material 100.In some embodiments, groove 110 comprises at least one raceway groove 112, and this raceway groove comprises the micron order raceway groove in some embodiments of disclosure theme.Remove patterned layer 108 and produce microfluidic device 114 from the patterned surface 102 of base material 100.In some embodiments, use " disengaging (the lift-off) " solvent that removes of microfluidic device 114 carries out, and wetting lentamente below this device of this solvent also makes it and patterned substrate breaks away from.The example of this kind solvent includes but not limited to can be sharply and the interactional any solvent of functional ized components of this microfluidic device or this microfluidic device.The example of this kind solvent includes but not limited to: water, Virahol, acetone, N-Methyl pyrrolidone and dimethyl formamide.
In some embodiments, this patterned substrate comprises etched silicon wafer.In some embodiments, this patterned substrate comprises the photo-resist patterned substrate.In some embodiments, handle this patterned substrate with coating, this coating can help the disengaging of this device and this patterned substrate or prevent potential radical reaction on this device and the photo-resist that constitutes this patterned substrate.The example of this coating can include but not limited to, silane or by the film of plasma-deposited metal, as gold/palladium coating.For the purpose of disclosure theme, this patterned substrate can include but not limited to photoetching, beamwriter lithography and ion milling by any working method manufacturing as known in the art.
In some embodiments, the patterned layer of PFPE is about 0.1 micron-about 100 micron thickness.In some embodiments, the patterned layer of PFPE is about 0.1 millimeter-about 10 mm thick.In some embodiments, the patterned layer of PFPE is about 1 micron-about 50 micron thickness.In some embodiments, the patterned layer of PFPE is about 20 micron thickness.In some embodiments, the patterned layer of PFPE is about 5 mm thick.
In some embodiments, the patterned layer of PFPE comprises a plurality of micron order raceway grooves.In some embodiments, raceway groove has the width of the about 1000 μ m of about 0.01 μ m-; The width of the about 1000 μ m of about 0.05 μ m-; And/or the width of the about 1000 μ m of about 1 μ m-.In some embodiments, raceway groove has the width of the about 500 μ m of about 1 μ m-; The width of the about 250 μ m of about 1 μ m-; And/or the width of the about 200 μ m of about 10 μ m-.Exemplary channel width includes but not limited to, 0.1 μ m, 1 μ m, 2 μ m, 5 μ m, 10 μ m, 20 μ m, 30 μ m, 40 μ m, 50 μ m, 60 μ m, 70 μ m, 80 μ m, 90 μ m, 100 μ m, 110 μ m, 120 μ m, 130 μ m, 140 μ m, 150 μ m, 160 μ m, 170 μ m, 180 μ m, 190 μ m, 200 μ m, 210 μ m, 220 μ m, 230 μ m, 240 μ m and 250 μ m.
In some embodiments, raceway groove has the degree of depth of the about 1000 μ m of about 1 μ m-and/or the degree of depth of about 1 μ m-100 μ m.In some embodiments, raceway groove has the degree of depth of the about 1000 μ m of about 0.01 μ m-; The degree of depth of the about 500 μ m of about 0.05 μ m-; The degree of depth of the about 250 μ m of about 0.2 μ m-; The degree of depth of the about 100 μ m of about 1 μ m-; The degree of depth of the degree of depth of the about 20 μ m of about 2 μ m-and/or the about 10 μ m of about 5 μ m-.Exemplary channel depth includes but not limited to, 0.01 μ m, 0.02 μ m, 0.05 μ m, 0.1 μ m, 0.2 μ m, 0.5 μ m, 1 μ m, 2 μ m, 3 μ m, 4 μ m, 5 μ m, 7.5 μ m, 10 μ m, 12.5 μ m, 15 μ m, 17.5 μ m, 20 μ m, 22.5 μ m, 25 μ m, 30 μ m, 40 μ m, 50 μ m, 75 μ m, 100 μ m, 150 μ m, 200 μ m and 250 μ m.
In some embodiments, raceway groove has about 0.1: the form ratio that 1-is about 100: 1.In some embodiments, raceway groove has about 1: the form ratio that 1-is about 50: 1.In some embodiments, raceway groove has about 2: the form ratio that 1-is about 20: 1.In some embodiments, raceway groove has about 3: the form ratio that 1-is about 15: 1.In some embodiments, raceway groove has about 10: 1 form ratio.
Those skilled in the art will also recognize that, the size of the raceway groove of disclosure theme is not limited to above-described exemplary range, and can make material flow through this raceway groove and/or make the size of valve driving with the mobile desired power that is controlled at material wherein changing aspect the width and the degree of depth with influence.In addition, as hereinafter inciting somebody to action in greater detail, the raceway groove of bigger width is considered as fluid reservoir, reaction chamber, mixing raceway groove, disengaging zone etc.
III.B. form the method for multilayer pattern formed material
In some embodiments, the disclosure subject description formation multilayer pattern formed material, the method for for example multi-layered patterned PFPE material.In some embodiments, use multi-layered patterned PFPE material to make whole PFPE class microfluidic device.
Referring now to Fig. 2 A-2D, show the preparation diagram of an embodiment of disclosure theme.Patterned layer 200 and 202 are provided, and each in them in some embodiments, comprises the PFPE material by the preparation of liquid PFPE precursor material, and this precursor material has the viscosity greater than about 100cSt.In this embodiment, each in the patterned layer 200 and 202 comprises a plurality of raceway grooves 204.In this embodiment of disclosure theme, these a plurality of raceway grooves 204 comprise the micron order raceway groove.In patterned layer 200, this raceway groove is illustrated by the broken lines, and is promptly represented by the dotted line in the shade among Fig. 2 A-2C.Patterned layer 202 superposes on patterned layer 200 by the predetermined alignment mode.In this embodiment, predetermined aligned is to make raceway groove 204 perpendicular each other in patterned layer 200 and 202.In some embodiments, as described in Fig. 2 A-2D, patterned layer 200 is superimposed upon on the non-patterned layer 206.Non-patterned layer 206 can comprise PFPE.
Continuation is with reference to Fig. 2 A-2D, by treatment process Tr pattern Processing layer 200 and 202 and in some embodiments non-patterned layer 206.As hereinafter in greater detail, by treatment process Tr processing layer 200,202 and, in some embodiments, non-patterned layer 206, to promote patterned layer 200 and 202 adhesivity each other, in some embodiments, promote the adhesion of 200 pairs of non-patterned layers 206 of patterned layer, shown in Fig. 2 C and 2D.The microfluidic device 208 of gained comprises the integrated network 210 of micron order raceway groove 204, and this micron order raceway groove 204 is 212 intersections in predetermined point of crossing, as the sectional view best image that provides among Fig. 2 D.Also show the film 214 of the upper surface of the raceway groove 204 that comprises patterned layer 200 among Fig. 2 D, this film 214 separates the raceway groove 204 of patterned layer 202 and the raceway groove 204 of patterned layer 200.
Continuation is with reference to Fig. 2 A-2C, and in some embodiments, patterned layer 202 comprises a plurality of holes, and this hole is called input hole 216 and delivery outlet 218.In some embodiments, the hole, for example input hole 216 and delivery outlet 218 are communicated with raceway groove 204 fluids.In some embodiments, the hole comprises by for example, the side driver's valve door of the film configuration of PFPE material, and it can be driven and limit flowing in the raceway groove.Yet apparent, this side driver's valve door can be by other material structure disclosed herein.
In some embodiments, with first patterned layer of the PFPE material of the sort of thickness casting photocuring of giving the certain mechanical stability of PFPE structure.Therefore, in some embodiments, first patterned layer of the PFPE material of this photocuring is that about 50 μ m-count cm thick.In some embodiments, first patterned layer of the PFPE material of this photocuring is about 10 mm thick of 50 μ m-.In some embodiments, first patterned layer of the PFPE material of this photocuring is that 5mm is thick.In some embodiments, first patterned layer of PFPE material is that about 4mm is thick.In addition, in some embodiments, the thickness of first patterned layer of PFPE material is the about 10cm of about 0.1 μ m-; The about 5cm of about 1 μ m-; The about 2cm of about 10 μ m-; With the about 10mm of about 100 μ m-.
In some embodiments, second patterned layer of the PFPE material of photocuring is about 1 micron-about 100 micron thickness.In some embodiments, second patterned layer of the PFPE material of photocuring is about 1 micron-about 50 micron thickness.In some embodiments, second patterned layer of the material of this photocuring is about 20 micron thickness.
Though Fig. 2 A-2C discloses wherein the formation with two patterned layer bonded microfluidic devices of PFPE material, in some embodiments of disclosure theme, might form the patterned layer with PFPE material and the microfluidic device of a non-patterned layer.Therefore, first patterned layer can comprise the integrated network of micron order raceway groove or micron order raceway groove, then this first patterned layer is superimposed upon the top of non-patterned layer and can uses the photocuring step, application as UV-light disclosed herein adheres to the non-patterned layer of itself and this, comprises the one-piece construction of airtight raceway groove wherein with formation.
Therefore, in some embodiments, first and second patterned layers of photocuring PFPE material, perhaps the non-patterned layer of first patterned layer of photocuring PFPE material and photocuring PFPE material is adhering to each other, thereby forms whole PFPE class microfluidic device.
III.C. form the method for patterning PFPE layer by the hot radical solidification process
In some embodiments, with thermal free radical initiator, include but not limited to, superoxide and/or azo-compound and the blend of liquid PFPE (PFPE) precursor are to form blend, this precursor is by polymerizable groups, include but not limited to that acrylate, methacrylic ester and styrenic unit are functionalized.Shown in Figure 1A-1C, make this blend and patterned substrate then, i.e. " main body " contact, and heat so that this PFPE precursor cures is become network.
In some embodiments, this PFPE precursor is fully solidified to form completely crued PFPE precursor.In some embodiments, the radically curing reaction is only partly carried out to form partly solidified network.
III.D. by the hot radical solidification process layer of PFPE material is adhered to side on the base material
Method
In some embodiments, completely crued PFPE precursor from patterned substrate, is promptly removed on the main body, for example peel off, and make it to contact to form reversible, gas-tight seal with second base material.
In some embodiments, allow this partly solidified network contact and curing reaction is carried out fully, thereby between the PFPE layer, form persistent keyed jointing with the second section solidified layer of PFPE material.
In some embodiments, use the partly solidified method of free radical that at least one layer of partly solidified PFPE material is keyed on the base material.In some embodiments, use the partly solidified method of free radical that a plurality of layers of partly solidified PFPE material are keyed on the base material.In some embodiments, base material is selected from glass material, quartz material, silicon materials, fused silica material and plastic material.In some embodiments, handle base material with silane coupling agent.
The embodiment that layer with the PFPE material of the present disclosure adheres to the method on the base material is illustrated among Fig. 3 A-3C.Referring now to Fig. 3 A, base material 300 is provided, wherein, in some embodiments, base material 300 is selected from glass material, quartz material, silicon materials, fused silica material and plastic material.By treating processes T
R1Handle base material 300.In some embodiments, treating processes T
R1Comprise with alkali/alcohol mixture (for example KOH/ Virahol) and handle this base material, to give base material 300 hydroxy functionalities.
Referring now to Fig. 3 B, make functionalized base material 300 and silane coupling agent, for example R-SiCl
3Or R-Si (OR
1)
3React to form the base material 300 of silanization, wherein R and R
1Represent functional group described herein.In some embodiments, silane coupling agent is selected from a halogenated silanes, dihalide halosilanes, trihalosilane, an organoalkoxysilane, dialkoxy silicane and trialkoxy silane; It is functionalized that wherein this halogenated silanes, dihalide halosilanes, trihalosilane, an organoalkoxysilane, dialkoxy silicane and trialkoxy silane are selected from the structure division of amine, methacrylic ester, acrylate, styrenic, epoxy group(ing), isocyanic ester, halogen, alcohol, benzophenone derivates, maleimide, carboxylic acid, ester, acyl chlorides and alkene.
Referring now to Fig. 3 C, the base material 300 of silanization contacts with the patterned layer 302 of partly solidified PFPE material, and processed process T
R2Handle and between the patterned layer 302 of PFPE material and base material 300, form persistent keyed jointing.
In some embodiments, use that free radical is partly solidified to adhere to the PFPE layer on second polymer materials, as poly-(dimethyl siloxane) (PDMS) material, polyurethane material, the polyurethane material that contains silicone and PFPE-PDMS block copolymer material.In some embodiments, second polymer materials comprises functionalized polymer materials.In some embodiments, second polymer materials is by the polymerizable groups end-blocking.In some embodiments, polymerizable groups is selected from acrylate, vinylbenzene and methacrylic ester.In addition, in some embodiments, handle second polymer materials so that required functionality is introduced second polymer materials with plasma body and silane coupling agent.
The embodiment that patterned layer with the PFPE material of the present disclosure adheres to the method on another patterned layer of polymer materials is illustrated among Fig. 4 A-4C.Referring now to Fig. 4 A, provide the patterned layer of first polymer materials 400.In some embodiments, first polymer materials comprises the PFPE material.In some embodiments, first polymer materials comprises the polymer materials that is selected from poly-(dimethyl siloxane) material, polyurethane material, the polyurethane material that contains silicone and PFPE-PDMS block copolymer material.By treating processes T
R1Handle the patterned layer of first polymer materials 400.In some embodiments, treating processes T
R1Be included in O
3With under the existence of R functional group the patterned layer of first polymer materials 400 is exposed under the UV light, so that R functional group is added in the patterned layer of polymer materials 400.
Referring now to Fig. 4 B, the functionalized patterned layer of first polymer materials 400 contacts with the upper surface of the functionalized patterned layer of PFPE material 402, processed then process T
R2Handle and form two-layer hydridization assembly 404.Therefore, the functionalized patterned layer of first polymer materials 400 therefore with the functionalized patterned layer keyed jointing of PFPE material 402.
Referring now to Fig. 4 C, in some embodiments, double layer hybridized assembly 404 contacts with base material 406 and forms multilayer hybrid structure 410.In some embodiments, base material 406 scribbles the layer of liquid PFPE precursor material 408.By treating processes T
R3Handle multilayer hybrid structure 410 so that two layer assemblies 404 are keyed on the base material 406.
IV. form the method for device by the two-pack solidification process
Disclosure theme provides the method that forms device; by this method; make polymkeric substance; contact with patterned surface then via two kinds of components as functionalized PFPE (PFPE) precursor; epoxy group(ing)/amine for example; epoxy group(ing)/hydroxyl; triol/vulcabond; carboxylic acid/amine; carboxylic acid/hydroxyl; ester/amine; ester/hydroxyl; amine/acid anhydrides; acyl halide/hydroxyl; acyl halide/amine; amine/halogenide; hydroxyl/halogenide; hydroxyl/chlorosilane; the reaction of trinitride/acetylene and other so-called " link chemistry " react and relate to the replacement(metathesis)reaction of using Grubb type catalyzer and be cured to form completely solidified or partly solidified PFPE network.According to some embodiments, the example of UV and the combination of heat-sealing end comprises: UV diurethanes methacrylic ester and heat three pure and mild vulcabond components, UV diurethanes methacrylic ester and hot tetrol and vulcabond component, UV diurethanes methacrylic ester and UV bicyclic oxygen, UV diurethanes methacrylic ester and hot bicyclic oxygen and diamine components, UV diurethanes methacrylic ester and hot vulcabond, their combination etc.
Term as used herein " link chemistry " is meant and is used for describing the term that uses many carbon-heteroatom bonds to form any synthetic compound in the reaction in this area." link chemistry " reaction is more insensitive to the oxygen G﹠W usually, has high stereoselective and productive rate and about 20kcal/mol or bigger thermodynamic driving force.In some embodiments, useful " link chemistry " reaction comprises the cycloaddition reaction of unsaturated compound, comprises 1,3-dipolar addition and Diels-Alder reaction; Nucleophilic substitution reaction especially relates to those of open loop of small strain ring such as epoxide and aziridine; Become the addition reaction of carbon-to-carbon multiple bond; With the reaction that relates to non-aldol carbonylation, as the reaction of the formation of urea and acid amides.
In addition, term " replacement(metathesis)reaction " is meant that wherein two kinds of compounds reactions form two kinds of new compounds, and Oxidation Number not have the reaction of variation in the final product.For example, the alkene displacement relates to the 2+2 cycloaddition of alkene and transition metal alkylidene title complex and forms new alkene and new alkylidene.In ring-opening metathesis polymerization (ROMP), alkene is the strain cyclic olefin, and the 2+2 cycloaddition that relates to transition-metal catalyst relates to opening of this strain ring.The polymkeric substance retained part transition metal complex that is increasing for example, becomes aldehyde by the 2+2 cycloaddition up to end-blocking.The Grubbs catalyzer that is used for replacement(metathesis)reaction at first 1996 (referring to
Schwab, people such as P.J.Am.Chem.Soc, 118,100-110 (1996)) be described in year.The Grubbs catalyzer is to contain the transition metal alkylidene of the ruthenium that is supported by the phosphine part and is unique, because they can stand the different functionality in this alkene part.
Therefore, in one embodiment, photo curable component can comprise the functional group that can experience photochemistry 2+2 cycloaddition.This type of group comprises alkene, aldehyde, ketone and alkynes.Photochemistry 2+2 cycloaddition can for example be used for forming tetramethylene and trimethylene oxide.
Therefore, in some embodiments, allow partly solidified PFPE network contact, and finish curing then so that this PFPE network is adhered on this base material with another kind of base material.This method can be used for a plurality of layers of PFPE material are adhered on the base material.
In addition, in some embodiments, base material comprises second polymer materials, as PDMS, or another kind of polymkeric substance.In some embodiments, second polymer materials comprises the elastomerics except that PDMS, as Kratons
TM(Shell Chemical Company), Buna rubber, natural rubber, fluoroelastomer, chloroprene, isoprene-isobutylene rubber, paracril, urethane or thermoplastic elastomer.In some embodiments, second polymer materials comprises rigid thermoplastic material, includes but not limited to: polystyrene, poly-(methyl methacrylate), polyester is as poly-(ethylene glycol terephthalate), polycarbonate, polyimide, polymeric amide, polyvinyl chloride, polyolefine, poly-(ketone), poly-(ether ether ketone) and poly-(ether sulfone).
In some embodiments, via using silane coupling agent that the PFPE layer is adhered on the solid substrate, as glass material, quartz material, silicon materials and fused silica material.
IV.A. form the method for patterning PFPE layer by the two-pack solidification process
In some embodiments, the reaction via the functionalized Liquid precursor system of two-pack forms the PFPE network.The general method of the patterned layer of the formation polymer materials of use shown in Figure 1A-1C allows the liquid precursor material that comprises bicomponent system contact and form the patterned layer of PFPE material with patterned substrate.In some embodiments, this two ingredient liquids precursor systems is selected from epoxy group(ing)/amine, epoxy group(ing)/hydroxyl; triol/vulcabond, carboxylic acid/amine, carboxylic acid/hydroxyl; ester/amine, ester/hydroxyl, amine/acid anhydrides; acyl halide/hydroxyl, acyl halide/amine, amine/halogenide; hydroxyl/halogenide; hydroxyl/chlorosilane, trinitride/acetylene and other so-called " link chemistry " react and relate to the replacement(metathesis)reaction of use Grubb type catalyzer.Should functionalized Liquid precursor blend make it then to contact by proper proportion with patterned surface or main body.By using heat, catalyzer etc. that this curing reaction is carried out, form up to network.
In some embodiments, formed completely crued PFPE precursor.In some embodiments, two-part reaction is only partly carried out, therefore form partly solidified PFPE network.
IV.B. via the two-pack solidification process PFPE layer is adhered to method on the base material
IV.B.1. adopt the completely solidified of two-pack solidification process
In some embodiments, completely crued PFPE two-pack precursor is removed from main body, for example peel off, and make it to contact to form reversible, gas-tight seal with base material.In some embodiments, allow this partly solidified network contact and to make to react and carry out fully, thereby between layer, form persistent keyed jointing with another partly solidified layer of PFPE.In some embodiments, this curing component can be to be exposed to the light-cured components that light or UV radiation following time are activated.In alternate embodiment, this curing component can be the thermofixation component that is activated when applying heat energy.In other alternate embodiment, curing component can be activated by the wet curing mechanism that causes.Wet and cause curing mechanism at people's such as S.Turri Surf.Interface Anal.29, disclose among the 873-886, the document is incorporated herein by reference in this integral body, comprises all reference of wherein quoting.
IV.B.2. adopt the partly solidified of bicomponent system
Shown in Fig. 3 A-3C, in some embodiments, use the partly solidified method of two-pack that at least one layer of partly solidified PFPE material is keyed on the base material.In some embodiments, use the partly solidified method of two-pack that a plurality of layers of partly solidified PFPE material are keyed on the base material.In some embodiments, base material is selected from glass material, quartz material, silicon materials, fused silica material and plastic material.In some embodiments, handle base material with silane coupling agent.
Shown in Fig. 4 A-4C, in some embodiments, use that two-pack is partly solidified to adhere to the PFPE layer on second polymer materials, as poly-(dimethyl siloxane) (PDMS) material.In some embodiments, the PDMS material comprises functionalized PDMS material.In some embodiments, handle PDMS required functionality is introduced this PDMS material with plasma body and silane coupling agent.In some embodiments, the PDMS material is by the polymerizable groups end-blocking.In some embodiments, this polymerizable groups comprises epoxy group(ing).In some embodiments, this polymerizable groups comprises amine.
In some embodiments, second polymer materials comprises the elastomerics except that PDMS, as Kratons
TM, Buna rubber, natural rubber, fluoroelastomer, chloroprene, isoprene-isobutylene rubber, paracril, urethane or thermoplastic elastomer.In some embodiments, second polymer materials comprises the rigid thermoplastic, includes but not limited to: polystyrene, poly-(methyl methacrylate), polyester is as poly-(ethylene glycol terephthalate), polycarbonate, polyimide, polymeric amide, polyvinyl chloride, polyolefine, poly-(ketone), poly-(ether ether ketone) and poly-(ether sulfone).
IV.B.3. adopt the excessive curing of bicomponent system
Disclosure theme provides the method that forms microfluidic device; by this method; functionalized PFPE (PFPE) precursor is contacted with patterned substrate then via two kinds of components; epoxy group(ing)/amine for example; epoxy group(ing)/hydroxyl; triol/vulcabond; carboxylic acid/amine; carboxylic acid/hydroxyl; ester/amine; ester/hydroxyl; amine/acid anhydrides; acyl halide/hydroxyl; acyl halide/amine; amine/halogenide; hydroxyl/halogenide; hydroxyl/chlorosilane; the reaction of trinitride/acetylene and other so-called " link chemistry " react and relate to the replacement(metathesis)reaction of using Grubb type catalyzer and be cured to form the layer of solidified PFPE material.In this specific method, can be following the layer of solidified PFPE material be adhered on second base material: will this layer fully solidify and make layer contacting of solidified PFPE material with excessive a kind of component, make this excessive group react and make a layer adhesion with second base material with second excessive component.
Therefore, in some embodiments, with bicomponent system; as epoxy group(ing)/amine, epoxy group(ing)/hydroxyl, triol/vulcabond; carboxylic acid/amine, carboxylic acid/hydroxyl, ester/amine; ester/hydroxyl, amine/acid anhydrides, acyl halide/hydroxyl; acyl halide/amine, amine/halogenide, hydroxyl/halogenide; hydroxyl/chlorosilane, trinitride/acetylene and other so-called " link chemistry " react and relate to the replacement(metathesis)reaction blend of use Grubb type catalyzer.In some embodiments, at least a component of this bicomponent system surpasses another kind of component.Then by heating, use catalyzer etc. that reaction is carried out fully, remaining curing network has a plurality of functional groups that the existence owing to excessive component produces.
In some embodiments, allow two layers of the completely solidified PFPE material that comprises the excessive group of complementary contact with each other, wherein make excessive radical reaction, thereby between layer, form persistent keyed jointing.
Shown in Fig. 3 A-3C, in some embodiments, allow the completely crued PFPE network that comprises excessive functional group contact with base material.In some embodiments, base material is selected from glass material, quartz material, silicon materials, fused silica material and plastic material.In some embodiments, with functionality on silane coupling agent processing base material so that this coupling agent and the excessive functionality complementation on this completely solidified network.Therefore, formation is to the lasting keyed jointing of base material.
Shown in Fig. 4 A-4C, in some embodiments, use the excessive curing of two-pack that the PFPE network bonds is received on second polymer materials, as gathering (dimethyl siloxane) (PDMS) material.In some embodiments, the PDMS material comprises functionalized PDMS material.In some embodiments, handle the PDMS material to introduce required functionality with plasma body and silane coupling agent.In some embodiments, the PDMS material is by the polymerizable groups end-blocking.In some embodiments, this polymerizable material comprises epoxide.In some embodiments, this polymerizable material comprises amine.
In some embodiments, second polymer materials comprises the elastomerics except that PDMS, as Kratons
TM, Buna rubber, natural rubber, fluoroelastomer, chloroprene, isoprene-isobutylene rubber, paracril, urethane or thermoplastic elastomer.In some embodiments, second polymer materials comprises the rigid thermoplastic, includes but not limited to: polystyrene, poly-(methyl methacrylate), polyester is as poly-(ethylene glycol terephthalate), polycarbonate, polyimide, polymeric amide, polyvinyl chloride, polyolefine, poly-(ketone), poly-(ether ether ketone) and poly-(ether sulfone).
IV.B.4 is with heat-setting component and photo curable material blend
According to another embodiment, by a plurality of layers of formation microfluidic device that adheres to each other with material.In one embodiment, with two-pack thermal curable material and photo curable material blend, thereby make the multi-stage curing material.In certain embodiments, bicomponent system can comprise functional group, as epoxy group(ing)/amine; epoxy group(ing)/hydroxyl, triol/vulcabond, carboxylic acid/amine; carboxylic acid/hydroxyl, ester/amine, ester/hydroxyl; amine/acid anhydrides, acyl halide/hydroxyl, acyl halide/amine; amine/halogenide, hydroxyl/halogenide, hydroxyl/chlorosilane; trinitride/acetylene and other so-called " link chemistry " react and relate to the replacement(metathesis)reaction of use Grubb type catalyzer.In one embodiment, photo curable component can comprise that this type of functional group is as acrylate, styrenic, epoxy group(ing), tetramethylene and other 2+2 cycloaddition thing.
In some embodiments, in different ratios with two-pack thermal curable material and photo curable material blend.In one embodiment, this material can be deposited on the above-mentioned patterned substrate then.This type of system can be exposed to actinic radiation, for example under the UV light, and is solidified into network, and but it is unreacted simultaneously thermal curable components mechanically being wrapped in this network keeping.The layer that can prepare this material then, for example, the cutting, the finishing, with the hand-hole/punching press of portalling, and by preposition align second photocuring layer on.In case the layer of this photocuring is aligned and seals, just can be with this device heats with the thermal curable components of activation in this layer.When by this thermal curable components of heat-activated, this layer is owing to reaction at the interface adheres to each other.
In some embodiments, thermal response is carried out fully.In other embodiment, only partly carry out this thermal response at first and after a plurality of layers are aligned, this thermal response is carried out fully, thereby should adhere to each other by a plurality of layers.In other embodiment, form multilayer device and it is adhered on the non-patterned layer in last plane via thermofixation.
In some embodiments, at first carry out the thermofixation reaction.Prepared layer for example, cuts then, and finishing with the hand-hole/punching press of portalling, and aligns.Next, by being exposed to actinic radiation, for example under the UV light with photo curable activation of component, and make this layer adhesion reacting at the interface of interlayer by functional group.
In some embodiments, use the two-pack thermal curable and the photocurable materials of blend that the PFPE network bonds is received second polymer materials, on poly-(dimethyl siloxane) PDMS material.In some embodiments, the PDMS material comprises functionalized PDMS material.As those of ordinary skills will understand, this functionalized PDMS material was the PDMS material that comprises reactive chemical group, as described in other place of this paper.In some embodiments, handle the PDMS material to introduce required functionality with plasma body and silane coupling agent.In some embodiments, the PDMS material is by the polymerizable groups end-blocking.In some embodiments, this polymerizable material comprises epoxide.In some embodiments, this polymerizable material comprises amine.
In some embodiments, second polymer materials comprises the elastomerics except that PDMS, as Kratons
TM, Buna rubber, natural rubber, fluoroelastomer, chloroprene, isoprene-isobutylene rubber, paracril, urethane or thermoplastic elastomer.In some embodiments, second polymer materials comprises the rigid thermoplastic, includes but not limited to: polystyrene, poly-(methyl methacrylate), polyester is as poly-(ethylene glycol terephthalate), polycarbonate, polyimide, polymeric amide, polyvinyl chloride, polyolefine, poly-(ketone), poly-(ether ether ketone) and poly-(ether sulfone).
In some embodiments, the blend of preparation photocurable PFPE Liquid precursor and two-pack thermal curable PFPE Liquid precursor requires a kind of component in this two-pack thermal curable blend to surpass another kind of component.Like this, can be via being present in residual complementary functional groups in a plurality of layer with a plurality of layers of adhesion.
According to an embodiment preferred, add thermofixation in this material and photocuring amount of substance to and adhere to through selecting to produce between the layer with the device finished, this device of finishing can tolerate the pressure up to required pressure/square inch.According to some embodiments, the thermofixation and the photocuring amount of substance that add in this material produce adhesion between selecting with the layer at device, and this device can tolerate the pressure up to about 120psi.According to other embodiment, this lamination device can tolerate the pressure up to about 110psi.According to other embodiment, this lamination device can tolerate the pressure up to about 100psi.According to other embodiment, this lamination device can tolerate the pressure up to about 90psi.According to other embodiment, this lamination device can tolerate the pressure up to about 80psi.According to other embodiment, this lamination device can tolerate the pressure up to about 70psi.In alternate embodiment, the adhesion between the layer through structurizing so that device can tolerate the about 120psi of about 5psi-in the different steps at this device pressure and can leafing.According to another embodiment, add thermofixation in this material and photocuring amount of substance to and between selecting, produce and adhere to layer at this device, this device can tolerate the about 60psi of about 10psi-pressure and can leafing.The example of the valve that drives under about 45psi in the PFPE device is shown in Figure 12.After the time period that repeatedly this valve circulation is prolonged, do not observe leafing.
Now the illustrative examples of the manufacture method of multilayer microfluidic device will be described according to Figure 11 a-11e.Will with the two-pack thermal curable material arrangements of photocurable materials blend on patterning template 5006,5008 (being sometimes referred to as caster or template), shown in Figure 11 a.According to alternative embodiment of the present invention, the material of this blend can be spun on this patterning template or be cast on this patterning template by this material being converged in the pad inboard.In some embodiments, use spin coating to form thin layer such as the first layer 5002 and use casting technique and form the thick-layer such as the second layer 5004, as those of ordinary skills will understand.Next, with the intermingling material of arranging on initial solidification such as photocuring processing template 5006 and 5008, to form the first layer 5002 and the second layer 5004 respectively.But the thermofixation component that this photocuring partly solidifies material does not cause this material.Remove the template 5008 of patterning then from this second layer 5004.This paper has described patterning template removing from this layer in more detail.Next, arrange the second layers 5004 and with this binding substances of second solidification treatment, shown in Figure 11 b, this causes the keyed jointing between the first layer 5002 and the second layer 5004 with respect to the first layer 5002, or adhere to, be referred to as " two adherent layers 5002 and 5004 " hereinafter.In some embodiments, second curing is the initial thermofixation that causes the two-pack thermofixation of this material.Next, remove two adherent layers 5002 and 5004 from patterning template 5006, shown in Figure 11 c.In Figure 11 d, two adherent layers 5002 and 5004 are arranged on the plane layer 5014, and wherein this plane layer 5014 is applied in advance on the flat formwork 5012 and by initial solidification and handles.Processing layer 5002,5004 and 5014 binding substances are to finally solidifying so that whole three layers are adhered to each other fully, shown in Figure 11 e then.
According to alternate embodiment, can apply patterning templates 5006 to promote to solidify or the removing of partly solidified layer (referring to Figure 11 c) with release layer 5010.In addition, template, for example, the coating of patterning template 5006 and/or patterning template 5008 can reduce the reaction of the potential group that exists on hot component and the template.For example, release layer 5010 can be gold/palladium coating.
According to alternate embodiment, removing of partly solidified and solidified layer can be by peeling off, suction, and air pressure via solvent being applied to this partly solidified or solidified layer, or is realized via the combination of these instructions.
V. the functionizing method on the micron and/or the surface of nanoscale devices
In some embodiments, disclosure theme provides material and method that the raceway groove in microfluidic device and/or the micro-well is functionalized.In some embodiments, this type of functionalized including but not limited to, peptide and other natural polymer is synthetic and/or be attached on the internal surface of the raceway groove in the microfluidic device.Therefore, disclosure theme can be applied to microfluidic device, as
Rolland, J. Deng the peopleJACS 2004,126, those that 2322-2323 describes, the disclosure of the document is incorporated herein by reference in this integral body.
In some embodiments, this method comprises small molecules is attached on the surface of the internal surface of microfluid raceway groove or micro-well.In these embodiments, in case combination, this small molecules just can be brought into play various functions.In some embodiments, this small molecules plays the cleavable group, it can change the polarity of this raceway groove and therefore change this raceway groove when activation wettability.In some embodiments, this small molecules plays the binding site effect.In some embodiments, this small molecules plays catalyzer, medicine, a kind of binding site effect of medicine in substrate, analyte and the transmitter.In some embodiments, this reacting property of small molecules functional group effect.In some embodiments, this reactive functional groups generation zwitter-ion that reacts.In some embodiments, this zwitter-ion provides polarity, ionic raceway groove.
The embodiment that the internal surface of microfluid raceway groove and/or micro-well is functionalized that is used for of disclosure method is illustrated in Fig. 5 A and 5B.Referring now to Fig. 5 A, provide microfluid raceway groove 500.In some embodiments, microfluid raceway groove 500 is formed by the functionalized PFPE material with R functional group, as described herein.In some embodiments, little raceway groove 500 comprises the PFPE network that has experienced the post curing treatment process, and by this, the R of functional group is introduced in the internal surface 502 of microfluid raceway groove 500.
Referring now to Fig. 5 B, provide micro-well 504.In some embodiments, micro-well 504 scribbles the layer of functionalized PFPE material 506, and this PFPE material comprises R functional group, functionality is given micro-well 504.
V.A. functional group is connected to the method for PFPE network
In some embodiments, use comprises that the PFPE network of excessive functionality is with the internal surface of microfluid raceway groove or the functionalisation of surfaces of micro-well.In some embodiments, the functionalized structure of charge species that is selected from protein, oligonucleotide, medicine, part, catalyzer, dyestuff, transmitter, analyte by connection and can changes the raceway groove wettability is partly with the internal surface of microfluid raceway groove or the functionalisation of surfaces of micro-well.
In some embodiments, potential functional group is introduced in the completely crued PFPE network.In some embodiments, potential methacrylate based group is present in the surface by photochemistry or the radical-cured PFPE network of calorifics mode.Allow a plurality of layers of completely crued PFPE contact then, form sealing member, and react, for example, make this potential reacted with functional groups and form persistent keyed jointing at interlayer by heating with the functionalized surfaces of this PFPE network.
In some embodiments, potential functional group reacts by the photochemistry mode under the wavelength different with the wavelength that is used for solidifying the PFPE precursor each other.In some embodiments, use this method that completely crued layer is adhered on the base material.In some embodiments, base material is selected from glass material, quartz material, silicon materials, fused silica material and plastic material.In some embodiments, use with this potential functional group complementary silane coupling agent and handle this base material.
In some embodiments, use potential functional group that completely crued PFPE network is adhered to second polymer materials, on poly-(dimethyl siloxane) PDMS material.In some embodiments, the PDMS material comprises functionalized PDMS material.In some embodiments, handle the PDMS material to introduce required functionality with plasma body and silane coupling agent.In some embodiments, the PDMS material is by the polymerizable groups end-blocking.In some embodiments, polymerizable groups is selected from acrylate, vinylbenzene and methacrylic ester.
In some embodiments, second polymer materials comprises the elastomerics except that PDMS, as Kratons
TM, Buna rubber, natural rubber, fluoroelastomer, chloroprene, isoprene-isobutylene rubber, paracril, urethane or thermoplastic elastomer.In some embodiments, second polymer materials comprises the rigid thermoplastic, includes but not limited to: polystyrene, poly-(methyl methacrylate), polyester is as poly-(ethylene glycol terephthalate), polycarbonate, polyimide, polymeric amide, polyvinyl chloride, polyolefine, poly-(ketone), poly-(ether ether ketone) and poly-(ether sulfone).
V.B. in the generation of liquid PFPE precursor, introduce the method for functionality
Disclosure theme provides the method that forms microfluidic device, by this method, makes the PFPE layer of photochemical solidification contact (conformal contact) placement with second base material is conformal, thereby forms sealing member.Heat this PFPE layer then at elevated temperatures this layer is adhered on the base material via potential functional group.In some embodiments, second base material also comprises solidified PFPE layer.In some embodiments, second base material comprises second polymer materials, as gathering (dimethyl siloxane) (PDMS) material.
In some embodiments, second polymer materials comprises the elastomerics except that PDMS, as Kratons
TM, Buna rubber, natural rubber, fluoroelastomer, chloroprene, isoprene-isobutylene rubber, paracril, urethane or thermoplastic elastomer.In some embodiments, second polymer materials comprises the rigid thermoplastic, includes but not limited to: polystyrene, poly-(methyl methacrylate), polyester is as poly-(ethylene glycol terephthalate), polycarbonate, polyimide, polymeric amide, polyvinyl chloride, polyolefine, poly-(ketone), poly-(ether ether ketone) and poly-(ether sulfone).
In some embodiments, this potential group is included in nonreactive methacrylate unit in the photocuring process.In addition, in some embodiments, in the generation of liquid PFPE precursor, introduce potential group.For example, in some embodiments, by using glycidyl methacrylate methacrylate unit is added in the PFPE glycol, the reaction of hydroxyl and epoxy group(ing) produces secondary alcohol, and this secondary alcohol can be as the carrier (handle) of introducing the chemical functional group.In some embodiments, via these potential functional groups that a plurality of layers of completely crued PFPE are adhering to each other.In some embodiments, use this potential functional group that completely crued PFPE layer is adhered on the base material.In some embodiments, base material is selected from glass material, quartz material, silicon materials, fused silica material and plastic material.In some embodiments, handle base material with silane coupling agent.
In addition, this method can be used for completely crued PFPE layer is adhered to second polymer materials, on poly-(dimethyl siloxane) PDMS material.In some embodiments, the PDMS material comprises functionalized PDMS material.In some embodiments, handle the PDMS material to introduce required functionality with plasma body and silane coupling agent.In some embodiments, the PDMS material is by the polymerizable groups end-blocking.In some embodiments, this polymerisable material is selected from acrylate, vinylbenzene and methacrylic ester.
In some embodiments, second polymer materials comprises the elastomerics except that PDMS, as Kratons
TM, Buna rubber, natural rubber, fluoroelastomer, chloroprene, isoprene-isobutylene rubber, paracril, urethane or thermoplastic elastomer.In some embodiments, second polymer materials comprises the rigid thermoplastic, includes but not limited to: polystyrene, poly-(methyl methacrylate), polyester is as poly-(ethylene glycol terephthalate), polycarbonate, polyimide, polymeric amide, polyvinyl chloride, polyolefine, poly-(ketone), poly-(ether ether ketone) and poly-(ether sulfone).
In some embodiments, use the PFPE network that comprises potential functional group that the internal surface of microfluid raceway groove or micro-well is functionalized.Example comprises the charge species that connects protein, oligonucleotide, medicine, part, catalyzer, dyestuff, transmitter, analyte and can change the raceway groove wettability.
V.C. with a plurality of chains of PFPE material and the functionalized method that base connects that is connected
In some embodiments, disclosure method is added functionality in microfluid raceway groove or the micro-well to by chemistry " connect base " structure division being added in the elastomerics itself.In some embodiments, the skeleton along this precursor material adds functional group.The example of this method is shown in the scheme 8.
Scheme 8. is added the exemplary process of functional group along the skeleton of precursor material
In some embodiments, this precursor material comprises the macromole of hydroxy functional groups.In some embodiments, as described in scheme 8, hydroxy functional group comprises functionalized with glycols group.In some embodiments, two or more in this functionalized with glycols group connect via trifunctional " connection base " molecule.In some embodiments, trifunctional connects basic molecule and has two kinds of functional groups, R and R '.In some embodiments, R ' group and macromolecular hydroxyl reaction.In scheme 8, circle can be represented link molecule; And wave line can be represented the PFPE chain.
In some embodiments, the R group offers required functionality on the surface of the internal surface or the micro-well of microfluid raceway groove.In some embodiments, R ' group is selected from, and includes but not limited to acyl chlorides, isocyanic ester, halogen and ester structure part.In some embodiments, the R group is selected from, but is not limited to, a kind of in shielded amine and the shielded alcohol.In some embodiments, with the methacrylate based group of polymerizable that macromolecular diol is functionalized.In some embodiments, by
Rolland, people such as J.JACS 2004,126, the photochemical method that 2322-2323 describes is with should curing of functionalized macromolecular diol and/or molding, the disclosure of the document is incorporated herein by reference in this integral body.
Therefore, disclosure theme provides the method that connects base with the potential introducing photocurable PFPE of functional group material via functionalized.Therefore, in some embodiments, a plurality of chains of PFPE material are linked together, then with polymerizable groups with this chain end-blocking.In some embodiments, this polymerisable group is selected from methacrylic ester, acrylate and styrenic.In some embodiments, potential functional group is so that the mode chemistry that they will be present in the completely crued network is connected in this type of " connection base " molecule.
In some embodiments, use a plurality of layer keyed jointing of the potential functional group of introducing like this with PFPE, completely crued PFPE layer is keyed to by on silane coupling agent treated base material such as glass material or the silicon materials, or completely crued PFPE layer is keyed to second polymer materials, on the PDMS material.In some embodiments, handle the PDMS material to introduce required functionality with plasma body and silane coupling agent.In some embodiments, the PDMS material is by the polymerizable groups end-blocking.In some embodiments, polymerizable groups is selected from acrylate, vinylbenzene and methacrylic ester.
In some embodiments, second polymer materials comprises the elastomerics except that PDMS, as Kratons
TM, Buna rubber, natural rubber, fluoroelastomer, chloroprene, isoprene-isobutylene rubber, paracril, urethane or thermoplastic elastomer.In some embodiments, second polymer materials comprises the rigid thermoplastic, includes but not limited to: polystyrene, poly-(methyl methacrylate), polyester is as poly-(ethylene glycol terephthalate), polycarbonate, polyimide, polymeric amide, polyvinyl chloride, polyolefine, poly-(ketone), poly-(ether ether ketone) and poly-(ether sulfone).
In some embodiments, use comprises that the PFPE network of the functional group that connects with " being connected base " molecule is with the internal surface of microfluid raceway groove and/or the functionalisation of surfaces of micro-well.In some embodiments, be selected from protein, oligonucleotide, medicine, part, catalyzer, dyestuff, transmitter, analyte by connection and can change functionalized structure inboard functionalized with the microfluid raceway groove partly of the charge species of raceway groove wettability.
V.D. improve the method for the chemical compatibility on surface
According to embodiments more of the present invention, can with by the surface passivation of the device of material described herein and method manufacturing to give this device chemical compatibility.According to these materials and method, as be issued to surface passivation: the surface of handling the device of making by material described herein with end capped UV and/or thermal curable Liquid precursor (for example, the end capped precursor of vinylbenzene).Behind the light or thermofixation component of activation this vinylbenzene end capped precursor, the potential methacrylic ester of this precursor and this material, vinylbenzene and/or acrylate group react and with this material keyed jointing, thereby provide surface passivation for the surface of this device.
According to another embodiment, handle the device of making by PFPE with the curable PFPE Liquid precursor of the end capped UV of vinylbenzene, this PFPE comprises the described potential methacrylic ester of whole application documents, acrylate and/or styrene group.According to these embodiments, the solution that the curable precursor of the end capped UV of vinylbenzene can be dissolved in solvent is coated on the surface of the device of being made by PFPE, and described solvent includes but not limited to 3-pentafluorobutane.Make this solvent evaporation, thereby make this PFPE surface of thin film coated of the curable precursor of the end capped UV of vinylbenzene.In one embodiment, then by being exposed under the UV light, and therefore adhere to potential methacrylic ester, acrylate and/or the styrene group of this PFPE material with this film hardening.The surface that scribbles the end capped precursor of this vinylbenzene does not comprise acid-unstable group such as carbamate and/or ester bond, thereby produces surface passivation and improve the chemical compatibility of this basis PFPE material.
According to another embodiment, the surface passivation of the device that will make by base mateiral described herein by gaseous passivation.According to these embodiments, device is exposed in the mixture of 0.5% fluorine gas in nitrogen.Hydrogen atom generation free radical reaction in this fluorine and this base mateiral, thereby the device surface passivation that the described gas processing of this usefulness is crossed.
VI. the functionalized monomer is added to the method in the PFPE precursor material
In some embodiments, this method comprises the functionalized monomer is added in the uncured precursor material.In some embodiments, the functionalized monomer is selected from functionalized vinylbenzene, methacrylic ester and acrylate.In some embodiments, this precursor material comprises fluoropolymer.In some embodiments, this functionalized monomer comprises highly fluorinated monomer.In some embodiments, this highly fluorinated monomer comprises perfluoroethylvinyl ether (EVE).In some embodiments, this precursor material comprises poly-(dimethyl siloxane) (PDMS) elastomerics.In some embodiments, this precursor material comprises polyurethane elastomer.In some embodiments, this method also comprises by curing schedule this functionalized monomer is introduced in the network.
In some embodiments, directly the functionalized monomer is added in the liquid PFPE precursor for the treatment of after crosslinked, to be incorporated in the network.For example, monomer can be introduced in the following network: the back crosslinking reaction can take place in this network, with a plurality of layers of adhesion with PFPE, completely crued PFPE layer is keyed to by on silane coupling agent treated base material such as glass material or the silicon materials, or completely crued PFPE layer is keyed to second polymer materials, on the PDMS material.In some embodiments, handle the PDMS material to introduce required functionality with plasma body and silane coupling agent.In some embodiments, the PDMS material is by the polymerizable groups end-blocking.In some embodiments, this polymerisable material is selected from acrylate, vinylbenzene and methacrylic ester.
In some embodiments, second polymer materials comprises the elastomerics except that PDMS, as Kratons
TM, Buna rubber, natural rubber, fluoroelastomer, chloroprene, isoprene-isobutylene rubber, paracril, urethane or thermoplastic elastomer.In some embodiments, second polymer materials comprises the rigid thermoplastic, includes but not limited to: polystyrene, poly-(methyl methacrylate), polyester is as poly-(ethylene glycol terephthalate), polycarbonate, polyimide, polymeric amide, polyvinyl chloride, polyolefine, poly-(ketone), poly-(ether ether ketone) and poly-(ether sulfone).
In some embodiments, directly the functionalized monomer is added in the liquid PFPE precursor and be used for the attached functionalized structure part that is selected from protein, oligonucleotide, medicine, catalyzer, dyestuff, transmitter, analyte and can changes the charge species of raceway groove wettability.
This type of monomer includes but not limited to, methacrylic tert-butyl acrylate, tert-butyl acrylate, the amino propyl ester of dimethylaminoethyl acrylate methyl base, glycidyl methacrylate, hydroxyethyl methylacrylate, the amino propyl ester of methacrylic acid, allyl acrylate, cyanoacrylate, the cyano methyl acrylate, the Trimethoxy silane acrylate, Trimethoxy silane methacrylic ester, isocyano methacrylic ester, the acrylate and the methacrylic ester that contain lactone, sacchariferous acrylate and methacrylic ester, polyethylene glycol methacrylate-styrene polymer contains methacrylic ester and the acrylate of nornornane, the oligomeric silsesquioxane methacrylic ester of multiaspect, methacrylic acid 2-trimethylsiloxy ethyl ester, methacrylic acid 1H, 1H, 2H, 2H-fluoro monooctyl ester, penta fluoro benzene ethene, vinyl pyridine, bromstyrol, chloro-styrene, styrene sulfonic acid, fluorobenzene ethene, phenylethyl acetate ester, acrylamide and vinyl cyanide.
In some embodiments, with the monomer that is attached with mentioned reagent directly with the liquid PFPE precursor blend for the treatment of to introduce in the network in crosslinked back.In some embodiments, monomer comprises the segmental group of fluoridizing that is selected from polymerizable groups, required reagent and permission and PFPE Liquid precursor mixing.In some embodiments, monomer does not comprise the fragment of fluoridizing of polymerizable groups, required reagent and permission and PFPE Liquid precursor mixing.
In some embodiments, add monomer to regulate completely crued elastomeric mechanical property.This type of monomer includes but not limited to: perfluor (2,2-dimethyl-1,3-dioxole), and connecing property of the hydrogen bond monomer of hydroxyl, carbamate, urea or other this type of structure division contain the monomer such as the methacrylic tert-butyl acrylate of huge side group.
In some embodiments, functionalized species such as above-mentioned monomer are introduced and mechanically twined when solidifying (, not with the covalent keyed jointing) and in network.For example, in some embodiments, functional group is introduced in the PFPE chain that does not contain polymerisable monomer and with this kind monomer and curable PFPE material blend.In some embodiments, if two kinds of materials are reactive, as: epoxy group(ing)/amine, hydroxyl/acyl chlorides, triol/vulcabond, hydroxyl/isocyanate, amine/isocyanic ester, amine/halogenide, hydroxyl/halogenide, amine/ester and amine/carboxylic acid then can use a plurality of layers that the material of this kind through twining will solidify PFPE to adhere to each other.When heating, this functional group will react and these two layers will be adhered to each other.
In addition, the material of this kind through twining can be used for the PFPE layer is adhered to another kind of material, as glass, silicon, quartz, PDMS, Kratons
TM, Buna rubber, natural rubber, fluoroelastomer, chloroprene, isoprene-isobutylene rubber, paracril, urethane or thermoplastic elastomer layer on.In some embodiments, second polymer materials comprises the rigid thermoplastic, includes but not limited to: polystyrene, poly-(methyl methacrylate), polyester is as poly-(ethylene glycol terephthalate), polycarbonate, polyimide, polymeric amide, polyvinyl chloride, polyolefine, poly-(ketone), poly-(ether ether ketone) and poly-(ether sulfone).
In some embodiments, the material of this kind through twining can be used for the inside of microfluid raceway groove that is used for purpose mentioned above functionalized.
VII. functionality is introduced other method on PFPE surface
In some embodiments, use as
Chen, Y. and Momose, Y.Surf.Interface.Anal.1999,27, the method that will gather (tetrafluoroethylene) functionalisation of surfaces that 1073-1083 describes uses argon plasma that functional group is introduced along completely crued PFPE surface, and document integral body is hereby incorporated by.More particularly, do not wish to be subjected to arbitrary specific theory, the exposure of completely crued PFPE material for some time in argon plasma is added functional group along this fluorizated skeleton.
This kind functional group can be used for a plurality of layers of adhesion of PFPE, completely crued PFPE layer is keyed to by on silane coupling agent treated base material such as glass material or the silicon materials, or completely crued PFPE layer is keyed to second polymer materials, on the PDMS material.In some embodiments, the PDMS material comprises functionalized material.In some embodiments, handle the PDMS material to introduce required functionality with plasma body and silane coupling agent.This kind functional group can also be used to attached protein, oligonucleotide, medicine, catalyzer, dyestuff, transmitter, analyte and can change the charge species of raceway groove wettability.
In some embodiments, second polymer materials comprises the elastomerics except that PDMS, as Kratons
TM, Buna rubber, natural rubber, fluoroelastomer, chloroprene, isoprene-isobutylene rubber, paracril, urethane or thermoplastic elastomer.In some embodiments, second polymer materials comprises the rigid thermoplastic, includes but not limited to: polystyrene, poly-(methyl methacrylate), polyester is as poly-(ethylene glycol terephthalate), polycarbonate, polyimide, polymeric amide, polyvinyl chloride, polyolefine, poly-(ketone), poly-(ether ether ketone) and poly-(ether sulfone).
In some embodiments, completely crued PFPE layer is contacted with solid substrate is conformal.In some embodiments, solid substrate is selected from glass material, quartz material, silicon materials, fused silica material and plastic material.In some embodiments, adopt UV light, for example, this PFPE material of 185nm UV optical radiation, this can extract fluorine atom out and form chemical bond with base material from skeleton, as
Vurens, G. waits the peopleLangmuir 1992,8,1165-1169 is described like that.Therefore, in some embodiments, the PFPE layer covalently is keyed on the solid substrate by the free radical coupling after the extraction of fluorine atom.
VIII. micron order or nanoscale devices are adhered on the base material with polymkeric substance via coating
In some embodiments, following with the micron order device, nanoscale devices or its combination adhere on the base material: with the conformal way of contact completely crued device is placed on this base material and on entire device and topples over " coating with polymkeric substance ".In some embodiments, coating is selected from liquid epoxies precursor and urethane with polymkeric substance.Make this coating fixed by curing or other method then with polymkeric substance.This coating is used for mechanically layer being combined and this layer being attached on the base material.
In some embodiments, the micron order device, nanoscale devices or its combination comprise part II.A. and the described PFPE material of part II.B. as mentioned and a kind of in the described Fluorine containing olefine class of the part II.C. material as mentioned.
In some embodiments, base material is selected from glass material, quartz material, silicon materials, fused silica material and plastic material.In addition, in some embodiments, this base material comprises second polymer materials, as poly-(dimethyl siloxane) (PDMS), or another kind of polymkeric substance.In some embodiments, second polymer materials comprises the elastomerics except that PDMS, as Kratons
TM, Buna rubber, natural rubber, fluoroelastomer, chloroprene, isoprene-isobutylene rubber, paracril, urethane or thermoplastic elastomer.In some embodiments, second polymer materials comprises rigid thermoplastic material, includes but not limited to: polystyrene, poly-(methyl methacrylate), polyester is as poly-(ethylene glycol terephthalate), polycarbonate, polyimide, polymeric amide, polyvinyl chloride, polyolefine, poly-(ketone), poly-(ether ether ketone) and poly-(ether sulfone).In some embodiments, adopt silane coupling agent that the functionalisation of surfaces of this base material so that it will be formed irreversible key with coating with polymer reaction.
IX. use sacrifice layer to form the method for microstructure
Disclosure theme provides by use and comprises that the sacrifice layer of degradable or selectivity soluble material forms as the little raceway groove of microfluidic device or the method for microstructure.In some embodiments, this method comprises: allow liquid precursor material contact with two dimension or three-dimensional sacrificial structure, handle (for example, solidifying) this precursor material, and remove this sacrificial structure to form the microfluid raceway groove.
Therefore, in some embodiments, the PFPE Liquid precursor is arranged on the multidimensional support, wherein this multidimensional support is by the material manufacturing that can degrade after the curing of PFPE network or rinse out.When casting elastomeric another layer thereon, this raceway groove of these material protections is not filled.The example of this type of degradable or the soluble material of selectivity includes but not limited to wax, photo-resist, polysulfones, polylactone, cellulosic fibre, salt or any SOLID ORGANIC or mineral compound.In some embodiments, with the mode of heat, photochemistry mode, or by removing sacrifice layer with solvent wash.Importantly, the consistency of material disclosed herein and device and organic solvent is provided at and uses the ability of sacrificing the property polymer architecture in the microfluidic device.
Useful PFPE material comprises those PFPE and the Fluorine containing olefine class material of describing among the disclosure theme upper section II in the microstructure forming by the use sacrifice layer.
Fig. 6 A-6D and Fig. 7 A-7C show the embodiment that is used for forming by the sacrifice layer that uses degradable or selectivity soluble material microstructure of disclosure method.
Referring now to Fig. 6 A, provide patterned substrate 600.Liquid PFPE precursor material 602 is arranged on the patterned substrate 600.In some embodiments, via spin-coating method liquid PFPE precursor material 602 is arranged on the patterned substrate 600.By treating processes T
R1Treatment liq PFPE precursor material 602 is to form the layer of treated liquid PFPE precursor material 604.
Referring now to Fig. 6 B, remove the layer of treated liquid PFPE precursor material 604 from patterned substrate 600.In some embodiments, allow the layer of treated liquid PFPE precursor material 604 contact with base material 606.In some embodiments, base material 606 comprises planar substrate or planar base material basically.In some embodiments, by treating processes T
R2Handle the layer of treated liquid PFPE precursor material, to form double-layer assembly 608.
Referring now to Fig. 6 C, the degradable or the selectivity soluble material 610 of pre-determined volume is arranged on the double-layer assembly 608.In some embodiments, be arranged on the double-layer assembly 608 via the degradable or the selectivity soluble material 610 of spin coating method pre-determined volume.Referring again to Fig. 6 C, liquid precursor material 602 is arranged in the layer of also being handled on the double-layer assembly 608 with formation PFPE material 612, this layer covers the degradable or the selectivity soluble material 610 of pre-determined volume.
Referring now to Fig. 6 D, by treating processes T
R3Handle the degradable or degradable or the selectivity soluble material 610 of selectivity soluble material 610 of pre-determined volume, thereby form microstructure 616 to remove this pre-determined volume.In some embodiments, microstructure 616 comprises the microfluid raceway groove.In some embodiments, treating processes T
R3Be selected from thermal process, radiative process and dissolution process.
In some embodiments, patterned substrate 600 comprises etched silicon wafer.In some embodiments, this patterned substrate comprises the photo-resist patterned substrate.For the purpose of disclosure theme, this patterned substrate can include but not limited to photoetching, beamwriter lithography and ion milling by any working method manufacturing as known in the art.
In some embodiments, degradable or selectivity soluble material 610 are selected from polyene hydrocarbon sulfones, cellulosic fibre, polylactone and polyelectrolyte.In some embodiments, degradable or selectivity soluble material 610 are selected from the material that can degrade or dissolve.In some embodiments, degradable or selectivity soluble material 610 are selected from salt, water-soluble polymers and solvent soluble polymkeric substance.
Except simple raceway groove, disclosure theme also provides the manufacturing of multiple complex construction, and this complex construction can also be removed in " injection-molded " or manufacturing in advance and the intercalated material as mentioned above.
Fig. 7 A-C shows being used for by using sacrifice layer to form the embodiment of little raceway groove or microstructure of disclosure method.Referring now to Fig. 7 A, provide base material 700.In some embodiments, base material 700 scribbles liquid PFPE precursor material 702.Sacrificial structure 704 is placed on the base material 700.In some embodiments, by treating processes T
R1Treatment liq PFPE precursor material 702.
Referring now to Fig. 7 B, the second liquid PFPE precursor material 706 is arranged on the sacrificial structure 704, make sacrificial structure 704 is coated in second liquid precursor material 706.Then by treating processes T
R2Handle second liquid precursor material 706.Referring now to Fig. 7 C, by treating processes T
R3Handle sacrificial structure 704, so that sacrificial structure degraded and/or remove, thereby microstructure 708 formed.In some embodiments, microstructure 708 comprises the microfluid raceway groove.
In some embodiments, base material 700 comprises silicon wafer.In some embodiments, sacrificial structure 704 comprises degradable or selectivity soluble material.In some embodiments, sacrificial structure 704 is selected from polyene hydrocarbon sulfones, cellulosic fibre, polylactone and polyelectrolyte.In some embodiments, sacrificial structure 704 is selected from the material that can degrade or dissolve.In some embodiments, sacrificial structure 704 is selected from salt, water-soluble polymers and solvent soluble polymkeric substance.
IX.I. use the PTFE powder to improve the method for microfluidic device modulus
In some embodiments, the modulus of the microfluidic device of making by PFPE material or above-described any fluorinated polymer material can by before solidifying with the polytetrafluoroethylene (PTFE) powder, also be called " PTFE filler " herein and be blended in the Liquid precursor and improve.Because PTFE itself has very high modulus, add total modulus that PTFE (in being evenly dispersed in whole low-modulus material of the present invention time) will improve this material with its powder type.This PTFE filler can also be contributed additional chemical stability and solvent resistance for this PFPE material.
IX.II. with the use of microfluidic device bonded material
According to one embodiment of the invention, by micron or the nanoscale devices that method described herein and material are made, the part of device, member, parts etc. can form to introduce microfluidic device.For example, micron or nano level valve or stopper can be formed by material of the present invention and method, and it can seal the raceway groove in the microfluidic device effectively.According to an embodiment, can form valve or stopper by shape that adapts to micro chamber and/or dimensional configuration, and remain on the appropriate location or setting is used in response to move or block the mobile of specific raceway groove by specific direction mobile material.According to another embodiment, can be following in little raceway groove, form valve or stopper: material of the present invention (being in a liquid state) is introduced little raceway groove and according to the present invention in disclosed method this fluent material is solidified.Therefore, valve or stopper present the shape of little raceway groove, thereby form conformal match (conformal fit), because this raceway groove serves as the mould of this valve.In alternate embodiment, by first raceway groove and the adjacent layout of test raceway groove are formed valve, so that when the time to this first raceway groove pressurization, this first raceway groove is applied to pressure on the test raceway groove and reduces the cross-sectional width of test raceway groove, thereby reduces or eliminates the stream in this test raceway groove.
X. microfluidic device
X.A. microfluidic device is functionalized
According to embodiment of the present invention, can microfluidic device is functionalized to improve their chemical compatibility.According to these embodiments, can be by the surface passivation of method of the present invention and material with the raceway groove of microfluidic device.According to these embodiments, can handle PFPE class microfluidic device with the end capped UV curable liquid of vinylbenzene precursor.The curable precursor of the end capped UV of vinylbenzene is dissolved in solvent, such as but not limited to, 3-pentafluorobutane, so that form solution.Then this solution is introduced the raceway groove and the solvent evaporated of microfluidic device.After evaporating solvent, this precursor keeps being coated on the wall of this raceway groove.In one embodiment, handle the microfluidic device that this precursor is coated on this channel walls with UV and handle, this via with the base mateiral that is included in this microfluidic device in potential methacrylate based group reaction and this precursor is adhered on this channel walls.The surface that scribbles the end capped precursor of this vinylbenzene does not comprise acid-unstable group such as carbamate and/or ester bond, thereby produces surface passivation and improve the chemical compatibility of the raceway groove of this microfluidic device.
According to other embodiment, can handle by the medical device of disclosed material of the application and method manufacturing, operation device, medical implant etc. on this device, to produce surface passivation and to improve the chemical compatibility of this device with surface treatment method described herein.This kind surface passivation can improve the unreactiveness of base mateiral, reduces the absorption of surface to material, improves acidproof and alkali resistance, their combination etc.
According to another embodiment, the surface passivation of the device that will make by material described herein by gaseous passivation.According to these embodiments, device is exposed in the mixture of 0.5% fluorine gas in nitrogen.Hydrogen atom generation free radical reaction in this fluorine and this base mateiral, thereby the device surface passivation that the described gas processing of this usefulness is crossed.
X.B. the device that has torque control valve
In some embodiments, microfluidic device is by material described herein and method manufacturing and comprise " torque control valve ", and for example people such as Whitesides is at Anal Chem2005, those that describe in 77,4726.With this type of valve, and below with reference in valve introducing fluoropolymer of describing in the document or the PFPE class micro-fluid chip.Description can be handled by material described herein and method manufacturing, and the reference of the suitable valve of use etc. comprises: (1) Lee, S.; Jeong, W.; Beebe, D.J.Lab Chip 2003,3,164-167; (2) Rich, C.A.; Wise, K.D.J.Microelectromech.Syst.2003,12,201-208; (3) Studer, V.; Hang, G.; Pandolfi, A.; Ortiz, M.; Anderson, W.F.; Quake, S.R; J.Appl.Phys.2004,95,393-398; (4) Sin, A.; Reardon, C.F.; Shuler, M.L.Biotechnol.Bioeng.2004,85,359-363; (5) Gu, W.; Zhu, X.; Futai, N.; Cho, B.S.; Takayama, S.Proc.Natl.Acad.Sci.U.S.A.2004,101,15861-15866; (6) Rohit, P.; Yang, M.; Johnson, B.N.; Burns, D.T.; Burns, M.A.Anal.Chem.2004,76,3740-3748; (7) Liu, R.H.; Bonanno, J.; Yang, J.; Lenigk, R.; Grodzinski, P.Sens.Actuators, B 2004, B98,328-336; (8) Selvaganapathy, P.; Carlen, E.T.; Mastrangelo, C.H.Sens.Actuators, A 2003, A104,275-282; (9) Sethu, P.; Mastrangelo, C.H.Sens.Actuators, A 2003, A104,283-289; (10) Klintberg, L.; Svedberg, M.; Nikolajeff, F.; Thornell, G.Sens.Actuators, A 2003, A103,307-316; (11) Suzuki, H.; Yoneyama, R.Sens.Actuators, B 2003, B96,38-45; (12) Hua, S.Z.; Sachs, F.; Yang, D.X, Chopra, H.D.Anal.Chem.2002,74,6392-6396; (13) Xie, J.; Miao, Y.; Shih, J.; He, Q.; Liu, J.; Tai, Y.-C; Lee, T.D.Anal.Chem.2004,76,3756-3763; (14) Tsai, J.H.; Lin, L.J.Microelectromech.Syst.2002,11,665-671; (15) Munyan, J.W.; Fuentes, H.V.; Draper, M.; Kelly, R.T.; Woolley, A.T.Lab Chip2003,3,217-220; (16) Hartshorne, H.; Backhouse, C.J.; Lee, W.E.Sens.Actuators, B 2004, B99,592-600; (17) Hatch, A.; Kamholz, A.E.; Holman, G.; Yager, P.; Bohringer, K.F.J.Microelectromech.Syst.2001,10,215-221; (18) Jackson, W.C; Tran, H.D.; O ' Brien, M.J.; Rabinovich, E.; Lopez, G.P.J.Vac.Sci.Technol.B 2001,19,596-599; (19) Luo, Q.; Mutlu, S.; Gianchandani, Y.B.; Svec, F.; Frechet, J.M.J.Electrophoresis 2003,24,3694-3702; (20) Yu, C.; Mutlu, S.; Selvaganapathy, P.; Mastrangelo, C.H.; Svec, F.; Frechet, J.M.J.Anal.Chem.2003,75,1958-1961; (21) Griss, P.; Andersson, H.; Stemme, G.Lab Chip 2002,2,117-120; (22) Beebe, D.J.; Moore, J.S.; Bauer, J.M.; Yu, Q.; Liu, R.H.; Devadoss, C; Jo, B.Nature 2000,404,588-590; (23) Beebe, D.J.; Mensing, G.A.; Walker, G.M.Annu.Rev.Biomed.Eng.2002 4,261-286; (24) Jacobson, S.C; Ermakov, S.V.; Ramsey, J.M.Anal.Chem.1999,71,3273-3276; (25) Lazar, I.M.; Karger, B.L.Anal.Chem.2002,74,6259-6268; (26) Gitlin, I.; Stroock, A.D.; Whitesides, G.M.; Ajdari, A.Appl.Phys.Lett.2003,83,1486-1488; (27) Lastochkin, D.; Zhou, R.; Wang, P.; Ben, Y.; Chang, H.-C.J.Appl.Phys.2004,96,1730-1733; (28) Liu, S.; Pu, Q.; Lu, J.J.J.Chromatogr., A 2003,1013,57-64; (29) Takamura, Y.; Onoda, H.; Inokuchi, H.; Adachi, S.; Oki, A.; Horiike, Y.Electrophoresis 2003,24,185-192; (30) McKnight, T.E.; Culbertson, C.T.; Jacobson, S.C; Ramsey, J.M.Anal Chem.2001,73,4045-4049; (31) Culbertson, C.T.; Ramsey, R.S.; Ramsey, M.J.Anal.Chem.2000,72,2285-2291; (32) Salimi-Moosavi, H.; Tang, T.; Harrison, D.J.J.Am.Chem.Soc.1997,119,8716-8717; (33) Johnston, I.D.; Davis, J.B.; Richter, R.; Herbert, G.I.; Tracey, M.C.Analyst 2004,129,829-834; (34) Terray, A.; Oakey, J.; Marr, D.W.M.Science 2002,296,1841-1844; (35) Andersson, H.; Van der Wijngaart, W.; Griss, P.; Niklaus, F.; Stemme, G.Sens.Actuators, B 2001, B75,136-141; (36) Walker, G.M.; Beebe, D.J.Lab Chip 2002,2,131-134; (37) Shoji, S.Top.Curr.Chem.1998,194,163-188; (38) Kovacs, G.T.A.Micromachined Transducers Sourcebook; McGraw-Hill:NewYork, 1998; Each piece of writing in them is incorporated herein by reference in this integral body.
X.C. the device of many kinds of materials
In some embodiments, material described herein only is used for the part of the microfluidic device of manufacturing.In this type of device, some part of this device is made by material disclosed herein, and the other parts of this device are made for example glass or PDMS by other material described herein.The example of these " partly " includes but not limited to: valve, raceway groove, wall, disk, layer, lining, stopper, ball, switch, gear and pillar.In some embodiments, these structures can following on the spot formation: carry out the exposure of UV light so that this PFPE material solidifies by desired shape via the photomask of desired shape in selected zone.Because this mask and the residue PFPE material maintenance that is not exposed to UV light under is untreated, and then can be with solvent for example 1,1,1,3, the 3-3-pentafluorobutane rinses out.Stayed the structure in this mask space (opening) of simulation like this.In other embodiment, adhere to this structure by activating the previously described second curing schedule original place.
X.D. be used to make the caster pattern of device
With reference to Figure 17, in some embodiments, be used for making device, for example the caster pattern of microfluidic device can be transferred on the PDMS plate, and the latter is used for then with device patterning.According to these embodiments, preparation has and will be transferred to the initial caster 1702 of the pattern 1704 of resulting devices.In some embodiments, caster 1702 can be formed by silicon matter, photo-resist material, their combination etc.Next, liquid PFPE precursor 1706 is introduced caster 1702 and/or its pattern 1704, shown in step B-C.In some embodiments, can be by casting, deposition, spin coating, compacting is toppled over, and their combination etc. is incorporated into liquid PFPE 1706 on the caster 1702.Then with liquid PFPE1706 is solidified when caster 1702 contacts, forming fixed liquid PFPE 1708, when when caster 1702 removes, this fixed liquid PFPE 1708 can keep the pattern 1704 of caster 1702.In some embodiments, describe as this paper liquid PFPE 1704 solidified, for example by photocuring, thermofixation, evaporation solidify, their combination etc. is cured.Remove fixed liquid PFPE 1708 from caster 1702 then, shown in step C.Then can be with fixed liquid PFPE 1708 as template, shown in step D-F with PDMS layer 1710 patterning.Liquid PDMS 1710 is contacted with fixed liquid PFPE 1708 and solidify, form fixed liquid PDMS 1712, shown in step e-F.Liquid PDMS 1710 can comprise solidifying agent described herein and can be by method described herein and technology, and for example thermal activation of the photoactivation of light curing agent, thermal curing agents, evaporation are solidified, their combination etc. solidified.Remove fixed liquid PDMS 1712 from fixed liquid PFPE template 1708 then, shown in step F.At last, can use fixed liquid PDMS 1712 as template with following with subsequent P FPE device molding: be incorporated in the fixed liquid PDMS template 1712 the liquid PFPE 1714 of second quantity and solidified liquid PFPE1714, shown in step G-H.Liquid PFPE 1714 can comprise solidifying agent described herein and can be solidified to form PFPE device 1716 by method described herein and technology.Can remove PFPE device 1716 from fixed liquid PDMS template 1710 then.Compare with breaking away from, use liquid PDMS can more easily break away from PFPE devices 1716 from PDMS template 1710 as the template of making PFPE device 1716 from silicon or photo-resist template.When silicon or photo-resist template comprise can be with the potential functional group of end group reaction on the PFPE precursor time, thereby cause PFPE device and this silicon or photo-resist template to adhere to, so the use of PDMS template (PDMS template as described herein) further is better than silicon or photo-resist template.
X.E. by the spin coating stratification
In some embodiments, the layer of material described herein can followingly adhere on other the layer: the thin layer of uncured material is spun on another layer, arrange these layers relative to one another, and adopt for example UV light, photocuring or heat energy to solidify this material to adhere to each other with solidifying agent so that these layers that activates in these layers and/or the spin coating thin layer.In some embodiments, repeat this process repeatedly to form multilayer device.In some embodiments, the thin layer of spin coating can be about 2 microns of about 50nm-.According to other embodiment, this thin layer is about 1 micron of about 100nm-.
X.F. the low permeability layer in device
In some embodiments, make liquid or gas such as oxygen, water vapor, water, their combination etc. are had the layer of material of utmost point low-permeability as the internal layer of multilayer device.This type of device can be, for example, and microfluidic device described herein.This low permeability material can be, for example, acrylic polymers gathers (ethene) or UV curable resin such as Viscoat 295 as poly-(methyl methacrylate), or the material that makes by metathesis polymerization is as poly-(dicyclopentadiene), their combination etc.
X.G. acid and/or alkaline purification
In some embodiments, can consequently any potential functional group that is connected with the surface of this material can be neutralized with the layer of acid and/or alkaline purification material described herein.This type of potential functional group that neutralizes has reduced interaction with the material that in use contacts with this material.According to some embodiments, the surface of treated material is the raceway groove that forms in material, for example the surface of the raceway groove of microfluidic device.According to some embodiments, F-is preferred surface treatment, yet other processing also can be used and may be more suitable in the composition of pending material.
X.H. the microfluidic device that has minimum quencher for the reaction that relates to F-
According to embodiments more of the present invention, microfluidic device comprises the trace-metal that is substantially zero to minimum.In some embodiments, microfluidic device is by comprising the PFPE material manufacturing that is substantially zero to the trace-metal of minimum.
Relate to F-as many reactions of nucleophilic reagent by the metal catalyst of trace, specifically, organotin catalysts such as dibutyltin diacetate, dibutyl tin laurate and stannous octoate quencher.In addition, will to form strong title complex with F-be known for metal catalyst or metal complexes.For example, comprise that the metal complexes of Ru, Rh, Pd, Pt, Cu, Co, Ni, Fe, Cr, Sn, Al and Si is known to form strong association with F-.A kind of like this example of reaction shows below, and is used for Synthetic 2-deoxidation-2-[
18F] fluoro-D-glucose (FDG), be used for the developer of positron emission imaging (PET).
Use many reactions of microfluidic device to relate to the synthetic of PET reagent.In addition, many (even not being great majority) in these reagent relate to the reaction of use F-as nucleophilic reagent.Therefore, for the PET reaction of using F-as nucleophilic reagent, be preferred by the microfluidic device of material manufacturing disclosed herein.
X.I. contain the use of the epoxy functional fluidized polymer of light acid producing agent
In some embodiments, can will contain on the surface that is deposited to device of epoxy functional fluidized polymer of light acid producing agent or a plurality of layers of centre of device.In some embodiments, this epoxy functional fluidized polymer has the Tg of the room temperature of being equal to or greater than, and it is spun to the surface as in the smooth or cured layer of glass, silicon, PFPE material, their combination etc.The layer of device can be sealed to then and also use the UV optical radiation on this polymer layer.This UV light is the activation of the PAG in this epoxy functional fluidized polymer, cause it crosslinked and with the lip-deep potential radical reaction of this PFPE layer, thereby this PFPE layer is adhered on this surface.In some embodiments, this epoxy functional fluidized polymer is made of SU-8 photo-resist, the polymkeric substance that contains following structure, their combination etc.:
II.J. epoxy functional fluidized polymer
In some embodiments, the epoxy functional fluidized polymer can be glycidyl methacrylate and one or more comonomers such as Zonyl TM as described herein
The multipolymer of methacrylic acid fluoroalkyl monomer etc.
II.K. with PFPE bonded ePTFE material
In some embodiments, (ePTFE) form the member (for example, film, valve, raceway groove, reservoir etc.) of microfluidic device or microfluidic device by use to expand poly-(tetrafluoroethylene).EPTFE gathers (tetrafluoroethylene) (PTFE) film by the micropore that the PTFE expansion is formed.Because the surprising low surface energy of PFPE disclosed herein (PFPE) material also makes the hole that is included among this ePTFE wetting so this PFPE can be cast on the ePTFE film effectively, thereby form interpenetrating polymer networks.
PFPE can comprise functional group, as functional group disclosed herein.In some embodiments, PFPE can comprise photocurable functional group and/or thermal curable functional group.In some embodiments, when PFPE comprises photocurable functional group, can by being exposed under the UV light this PFPE be solidified after to ePTFE in that this PFPE is wetting.The gained film of ePTFE and PFPE comprises, for example, and hope flexible, chemical resistant properties and to the ventilation property of solvent vapour and air.The ePTFE of this film partly provides a kind of continuous structure, and this continuous structure itself is compared with flexible body only and is used for greatly making material toughness reinforcing.Some films at United States Patent (USP) 6,673, have carried out general description in 455 by people such as Zumbrum, and the document is incorporated herein by reference in this integral body, comprises all reference of wherein quoting.
In some embodiments, the film of bonded ePTFE and PFPE can be used for microfluidic platforms, especially when wishing via the film evaporating solvent.According to some embodiments, these films can be used for microfluidic platforms, and this microfluidic platforms relates to the synthetic of the radiolabeled biomarker that is used for positron emission (PET) imaging, and wherein the unreactiveness of this film is conclusive.In some embodiments, can with subsequently can UV or the PFPE toluylene material of thermofixation fill this ePTFE film, thereby produce high chemical-resistant.
In other embodiment, " dual cure " described herein PFPE material can be used for the ePTFE film or the microfluidic device member is wetting and activated with other film that this film adhered to this device or the mode on other member.In some embodiments, the manufacture method of microfluidic device (or device in general sense) can comprise and obtains the curable and thermal curable PFPE mixtures of material of UV and they are cast on the ePTFE film, this PFPE UV is solidified, the binding substances of ePTFE/PFPE is sealed on another layer or member of microfluidic device, binding substances with ePTFE/PFPE and device components heats with heat of activation component then, therefore produces this device components to adhering to the adhesion of the PFPE layer on this ePTFE.
XI. microfluid unit operation
In order to develop effective chip lab operation, the microfluidic control device is necessary.The valve mechanism that is in micrometer level with driving, fluid control, mixing, separates and detect must be through designing microminiaturization is had large-scale skew.In order to build this type of device, must develop various members integrated on platform commonly used so that can fully control solvent and solute.
The microfluidic flow controller is usually based on external pump, comprises waterpower, reciprocating type, acoustics and peristaltic pump, and can be simple as syringe (referring to
People such as McbrideU.S. Patent number 6,444,106,
BlakleyU.S.'s publication application number 20040028566 of people such as U.S. Patent number 6,811,385, Ko).Recently, osmosis (not requiring the method for movable part) as the fluid flow driving mechanism obtained success (referring to
MolesU.S. Patent number 6,406,605,
ParseU.S. Patent number 6,568,910).Other fluid flow device that does not require movable part use gravity (referring to
People such as WeiglU.S. Patent number 6,743,399), centrifugal force (referring to
People such as SanaeU.S. Patent number 6,632,388), capillary action (referring to
People such as McNeelyU.S. Patent number 6,591,852) or heat (referring to U.S.'s publication application number 20040257668 of Ito) drive liquid and pass little raceway groove.Other invention is by applying external force, as blade produce liquid-flow (referring to
NeukermansU.S. Patent number 6,068,751).
Valve also is used for liquid flow rate control.Can be by with external force, as blade, cantilever or stopper be applied to drive on the elasticity raceway groove valve (referring to
NeukermansU.S. Patent number 6,068,751).The elasticity raceway groove can also comprise film, and this film can pass through air pressure and/or hydraulic pressure (for example hydraulic pressure), with electrostatic means or magnetic means deflection (referring to
People such as UngerU.S. Patent number 6,408,878).Other two-way valve by light (referring to
People such as HalasU.S.'s publication application number 20030156991), piezoquartz (referring to
People such as DavisOpen PCT international application no WO2003/089,138), particle deflection (referring to
People such as MarrU.S. Patent number 6,802,489) or the bubble that in raceway groove, forms with electrochemical method (referring to
People such as HuaOpen PCT international application no WO 2003/046,256) drive.Unidirectional or " vacuum breaker " can also be in little raceway groove with ball, baffle plate or barrier film form (referring to
People such as CoxU.S. Patent number 6,817,373;
People such as DaiU.S. Patent number 6,554,591;
People such as JeonOpen PCT international application no WO2002/053,290).The rotary-type switch valve be used for complex reaction (referring to
People such as PowellOpen PCT international application no WO 2002/055,188).
In order to promote reaction and estimate product that micron order mixes and separated portion is necessary.In microfluidic device, the most common by have long length scale, crooked, have variable-width or have diffusion in the raceway groove that causes the turbulent feature mix (referring to
People such as O ' ConnerU.S. Patent number 6,729,352,
People such as HansenU.S.'s publication application number 20030096310).Can also osmosis ground (referring to people's such as Yager U.S. Patent number 6,482,306) or ultrasonically (referring to
People such as NorthrupU.S. Patent number 5,639,423) finish mixing.Three kinds of methods are usually used in separation in the micron order raceway groove: electrophoresis, the packed tower in raceway groove or gel or channel walls functionalized.Electrophoresis is used charged molecule usually, carry out as nucleic acid, peptide, protein, enzyme and antibody etc., and be the simplest technology (referring to
Regnier etc. The peopleU.S. Patent number 5,958,202,
People such as ChowU.S. Patent number 6,274,089).The raceway groove post can be filled with pearl that porous or stationary phase apply or gel with promote to separate (referring to
People such as KoehlerOpen PCT international application no WO 2003/068,402,
People such as QuakeU.S.'s publication application number 20020164816,
People such as KoehlerU.S. Patent number 6,814,859).Possible packing material comprises silicate, talcum, Fuller's earth, glass wool, charcoal, gac, diatomite, silica gel, aluminum oxide, paper, Mierocrystalline cellulose, starch, Magnesium Silicate q-agent, calcium sulfate, silicic acid, Florisil (florisil), magnesium oxide, polystyrene, PAB-cellulose, teflon resin, polystyrene resin, SEPHADEX
TM(AmershamBiosciences, Corp., Piscataway, New Jersey, United States ofAmerica), SEPHAROSE
TM(Amersham Biosciences, Corp., Piscataway, New Jersey, United States of America), two or more combination in controlled hole granulated glass sphere, agarose, other solid resin well known by persons skilled in the art and any above-mentioned substance.Magnetisable material can also be embedded, is encapsulated into or introduces in the solid phase packing material as ferric oxide, nickel oxide, barium ferrite or iron protoxide.
Can also with various can be the wall of microfluid chamber is functionalized with interaction and impurities or bonded part in analyte or the analyte solution.This type of part comprises: wetting ability or hydrophobic small molecules, steroid, hormone, lipid acid, polymkeric substance, RNA, DNA, PNA, amino acid, peptide, protein (protein such as the protein G that comprise the antibody keyed jointing), antibody or antibody fragment (FAB etc.), antigen, enzyme, carbohydrate (comprising glycoprotein or glycolipid), phytohemagglutinin, cell surface receptor (or their part), contain material of plus or minus electric charge etc. (referring to
People such as LiuU.S.'s publication application number 20040053237,
People such as AugustineOpen PCT international application no WO2004/007,582,
BlackburnU.S.'s publication application number 20030190608).
Therefore, in some embodiments, the disclosure subject description material is flowed and/or with the method for two or more material mixing.In some embodiments, disclosure subject description carry out the method for chemical reaction, include but not limited to synthesising biological macromole such as DNA.In some embodiments, disclosure subject description according to the method for characteristic screening sample.In some embodiments, the disclosure subject description method of dispensing materials.In some embodiments, the disclosure subject description method of parting material.
Material is flowed and/or with two kinds of material mixing
Method
Referring now to Fig. 8, show the floor map of the microfluidic device of disclosure theme.This microfluidic device is referred to as 800.Microfluidic device 800 comprises patterned layer 802 and a plurality of hole 810A, 810B, 810C and 810D.These holes can further describe and be ingate 810A, ingate 810B and ingate 810C and outlet opening 810D.Among hole 810A, 810B, 810C and the 810D each sealed 820A, 820B, 820C and 820D cover, and they are the reversible sealing member preferably.Sealing member 820A, 820B, 820C and 820D are provided, so that can in microfluidic device 800, store if desired, shipment, or keep material, include but not limited to, solvent, chemical reagent, the component of biochemical system, sample, printing ink and reaction product, and/or component, sample, printing ink, the mixture of reaction product and their combination of solvent, chemical reagent, biochemical system.Sealing member 820A, 820B, 820C and 820D can be reversible, promptly are removable, so that microfluidic device 800 can be implemented chemical reaction or other application then if necessary can be sealed again.
Continuation is with reference to Fig. 8, and in some embodiments, hole 810A, 810B and 810C also comprise pressure activated valve (comprising intersection, overlapping runner), the latter can through drive will be relevant with described hole the microfluid raceway groove seal.
Continuation is with reference to Fig. 8, and the patterned layer 802 of microfluidic device 800 comprises the integrated network 830 of micron order raceway groove.Randomly, patterned layer 802 comprises functionalized surfaces, the surface shown in Fig. 5 A.Integrated network 830 can comprise the micron order raceway groove that a series of fluids of being represented by following reference marks connect: 831,832,833,834,835,836,837,838,839 and 840.Therefore, ingate 810A is communicated with micron order raceway groove 831 fluids and is communicated with micron order raceway groove 832 fluids via elbow, and this micron order raceway groove 831 stretches out from hole 810A.In the integrated network 830 that Fig. 8 describes, for convenience's sake, show a series of 90 ° of elbows.Yet, be noted that the passage that in the raceway groove of integrated network 830, provides and elbow can comprise any required configuration, angle or further feature (as but be not limited to spiral section).In fact, if necessary, can provide fluid reservoir 850A and 850B along micron order raceway groove 831,832,833 and 834 respectively.As shown in Figure 8, fluid reservoir 850A and 850B comprise at least one than with their next-door neighbours' the big size of size of raceway groove.
Then, continue with reference to Fig. 8, micron order raceway groove 832 and 834 is in point of crossing 860A intersection and enter single micron order raceway groove 835.Micron order raceway groove 835 advances to chamber 870, and in the embodiment depicted in fig. 8, the size of this chamber 870 is wideer than micron order raceway groove 835.In some embodiments, chamber 870 comprises reaction chamber.In some embodiments, chamber 870 comprises the mixing zone.In some embodiments, chamber 870 comprises the disengaging zone.In some embodiments, the disengaging zone comprises intended size, and the raceway groove of length for example is wherein by electric charge or quality or its combination or wherein separate any other physical features that can take place with material separation in intended size.In some embodiments, the disengaging zone comprises active material 880.Such as one of ordinary skill understood, term " active material " is to use for convenience's sake and in this article, and does not mean that this material to be activated and be used for the purpose that it is wanted.In some embodiments, active material comprises the stratographic analysis material.In some embodiments, active material comprises target material.
Continue Fig. 8, be noted that chamber 870 not necessarily must have the size wideer than adjacent micron order raceway groove.In fact, chamber 870 can comprise the given fragment of micron order raceway groove simply, and wherein at least two kinds of materials are separated, mixes and/or reaction.Micron order raceway groove 836 extends out from relative with micron order raceway groove 835 basically chamber 870.Micron order raceway groove 836 forms T junctions with micron order raceway groove 837, and this micron order raceway groove 837 stretches out and is communicated with this hole 810C fluid from hole 810C.Therefore, micron order raceway groove 836 and 837 joint form point of crossing 860B.Micron order raceway groove 838 from point of crossing 860B along relative with micron order raceway groove 837 and extend basically towards the direction of fluid reservoir 850C.For predetermined length, the size of fluid reservoir 850C is wideer than micron order raceway groove 838.Yet as mentioned above, the certain portions of giving of micron order raceway groove can be served as fluid reservoir, and needn't change the size of this part of micron order raceway groove.In addition, micron order raceway groove 838 can serve as reaction chamber because from micron order raceway groove 837 flow to point of crossing 860B reaction reagent can with move to point of crossing 860B from micron order raceway groove 836 and go forward side by side into the reaction of the reaction reagent of micron order raceway groove 838.
Continuation is with reference to Fig. 8, and micron order raceway groove 839 extends and passes elbow from relative with microfluid raceway groove 838 basically fluid reservoir 850C and enters micron order raceway groove 840.Micron order raceway groove 840 is connected with outlet opening 810D fluid.Outlet opening 810D can randomly reversibly be sealed via sealing member 820D, and is as discussed above.Equally, reaction product forms in microfluidic device 800 and wishes and is transported in the embodiment of another position in the microfluidic device 800 therein, and the reversible sealing of outlet opening 810D may be wished.
Can the integrated network 830 of micron order raceway groove be passed in the fluid guiding of material by using pressure activated valve as known in the art etc., comprise raceway groove, fluid reservoir and reaction chamber, for example
People such as UngerU.S. Patent number 6,408,878 in describe those, the document is incorporated herein by reference in this integral body.Therefore disclosure theme provides the method that allows material flow through PFPE class microfluidic device.In some embodiments, this method comprises provides microfluidic device, and this microfluidic device comprises that (i) has PFPE (PFPE) material that is selected from following feature: viscosity is greater than about 100 centistokes (cSt); Viscosity is less than about 100cSt, and condition is a viscosity less than the liquid PFPE precursor material of 100cSt is not free radical photocurable PFPE material; (ii) functionalized PFPE material; (iii) Fluorine containing olefine class elastomerics; (iv) their combination, wherein this microfluidic device comprises one or more micron order raceway grooves; With material is flowed in this micron order raceway groove.
The method of mixing two or more materials also is provided.In some embodiments, this method comprises provides the micron order device, and this micron order device comprises that (i) has PFPE (PFPE) material that is selected from following feature: viscosity is greater than about 100 centistokes (cSt); Viscosity is less than about 100cSt, and condition is a viscosity less than the liquid PFPE precursor material of 100cSt is not free radical photocurable PFPE material; (ii) functionalized PFPE material; (iii) Fluorine containing olefine class elastomerics; (iv) their combination; With allow first material and second material in this device, contact to mix this first and second material.Randomly, this micron order device is selected from microfluidic device and micro plate (microtiter plate).
In some embodiments, this method comprises material is placed microfluidic device.In some embodiments, as best illustrate and as more detailed argumentation hereinafter among Figure 10, this method comprises and applies motivating force so that this material moves along this micron order raceway groove.
In some embodiments, the surface of at least one in the one or more micron order raceway grooves of layer covering of PFPE material.Randomly, the layer of PFPE material comprises functionalized surfaces.In some embodiments, microfluidic device comprises one or more patterned layers of PFPE material, and wherein one or more patterned layers of this PFPE material limit one or more micron order raceway grooves.In this case, the patterned layer of PFPE can comprise functionalized surfaces.In some embodiments, microfluidic device can also comprise the patterned layer of second polymer materials, wherein at least one effective connection the in one or more patterned layers of the patterned layer of this second polymer materials and PFPE material.Referring to Fig. 2.
In some embodiments, method comprises at least one valve.In some embodiments, valve is a pressure activated valve, and wherein this pressure activated valve is limited by one of following structure: (a) micron order raceway groove; (b) at least one in a plurality of holes.In some embodiments, the following driving of this pressure activated valve: the impermeable pressure fluid or the gas (for example, sulfur hexafluoride) of this micron order raceway groove of this material of comprising is introduced one of following structure: (a) micron order raceway groove; (b) at least one in a plurality of holes.
In some embodiments, pressure fluid has the pressure of the about 60psi of about 10psi-.In some embodiments, pressure is about 25psi.In some embodiments, described material comprises fluid.In some embodiments, described fluid comprises solvent.In some embodiments, described solvent comprises organic solvent.In some embodiments, described material is pressed pre-determined direction along this micron order channel current flows.
Under the situation of mixing two kinds of materials, this can comprise in some embodiments two kinds of reactants are mixed so that chemical reaction to be provided, then carry out contacting of first material and second material in the mixing zone that limits in one or more micron order raceway grooves.This mixing zone can comprise the geometry that is selected from T junction, coiled pipe, prolongation raceway groove, micron order chamber and compressed pipe.Randomly, first material and second material are placed the independent raceway groove of microfluidic device.In addition, carry out contacting of first material and second material in the mixing zone that can limit in point of crossing by raceway groove.
Continue blending means, this method can comprise makes first material and second material flow in microfluidic device along pre-determined direction, and can comprise this mixing material is flowed in microfluidic device by pre-determined direction.In some embodiments, described mixing material can contact to form second mixing material with the 3rd material.In some embodiments, mixing material comprises that reaction product and this reaction product can react with the 3rd reaction reagent subsequently.The description that the blending means that above just provides is provided of having read disclosure theme is to be used for illustration purpose and unrestricted.Therefore, the method for mixing material of the present disclosure can be used for mixing multiple material and form multiple mixing material and/or multiple reaction product.Described mixing material includes but not limited to reaction product, can flow to the outlet opening of microfluidic device.Motivating force can be applied so that this material moves through this microfluidic device.Referring to Figure 10.In some embodiments, reclaim mixing material.
In an embodiment using micro plate, this micro plate can comprise one or more wells.In some embodiments, the surface of at least one in the one or more wells of layer covering of PFPE material.The layer of PFPE material can comprise functionalized surfaces.Referring to Fig. 5 B.
XI.B. the macromolecular method of synthesising biological in PFPE class microfluidic device
In some embodiments, it is synthetic that PFPE class microfluidic device of the present disclosure can be used for biomacromolecule, for example, is used for synthesis of oligonucleotides Nucleotide, protein, peptide, DNA etc.In some embodiments, these biomacromolecule synthetic systems comprise integration system, comprise row's reservoir, be used for selecting fluidic fluid logic circuit from specific reservoir, one row's raceway groove, reservoir and wherein carry out the synthetic reaction chamber and determine that selected reaction reagent flows into the fluid logic circuit of which raceway groove.
Referring now to Fig. 9, a plurality of reservoirs, for example reservoir 910A, 910B, 910C and 910D have base material A, C, T and the G that is arranged in wherein respectively, as shown.Four runner 920A, 920B, 920C and 920D are connected with reservoir 910A, 910B, 910C and 910D.With four control raceway groove 922A, 922B, 922C and 922D (shown in broken lines) arranged crosswise, wherein when to control raceway groove 922A pressurization, control raceway groove 922A only allows fluid to pass runner 920A (that is, shutoff runner 920B, 920C and 920D).Similarly, when pressurization, control raceway groove 922B only allows fluid to pass runner 920B.Thereby the selectivity pressurization of control raceway groove 922A, 922B, 922C and 922D is sequentially selected required base material A, C, T and G from required reservoir 910A, 910B, 910C or 910D.Fluid passes runner 920E and (for example enters multichannel channel current flows controller 930 then, comprise, any system as shown in Figure 8), this flow governor imports fluid one or more among a plurality of synthetic raceway groove wherein can carry out solid phase synthesis or reaction chamber 940A, 940B, 940C, 940D or the 940E successively.
In some embodiments, replace, arrange the reaction reagent that is selected from one of Nucleotide and polynucleotide at least one in reservoir 910A, 910B, 910C and 910D from required base material A, C, T and G.In some embodiments, reaction product comprises polynucleotide.In some embodiments, polynucleotide are DNA.
Therefore, after reading present disclosure, one of skill in the art will recognize that PFPE class microfluidic device of the present disclosure can be used for the synthesising biological macromole, as
People such as UngerU.S. Patent number 6,408,878 Hes
People such as O ' Conner6,729,352 described, and/or be used to make up synthetic system, as
People such as van DamU.S. Patent number 6,508,988 described, every piece of document is incorporated herein by reference in this integral body.
XI.C. PFPE class microfluidic device is introduced the method in the integrated fluid flow system
In some embodiments, in PFPE class microfluidic device, carry out chemical reaction or material mobile method is comprised this microfluidic device is introduced the integrated fluid flow system.Referring now to Figure 10, schematically described according to disclosure theme and be implemented in the system that makes material mobile method in the microfluidic device and/or carry out the method for chemical reaction.Itself generally is called 1000 this system.System 1000 can comprise central processing unit 1002, one or more motivating force actuator 1010A, 1010B, 1010C and 1010D, collector 1020 and detector 1030.In some embodiments, detector 1030 is communicated with (illustrating with shade) with this microfluidic device fluid.System's microfluidic device 1000 of Fig. 8 and these Ref. No.s of Fig. 8 are used for Figure 10.For example, central processing unit (CPU) 1002 can be the universal personal computer with dependent surveillance device, keyboard or other required user interface.Motivating force actuator 1010A, 1010B, 1010C and 1010D can be any suitable motivating force actuators, and this is conspicuous to the those of ordinary skills that read disclosure theme.For example, motivating force actuator 1010A, 1010B, 1010C and 1010D can be that pump, electrode, injector, syringe or other can be used for promoting those devices that material passes microfluidic device.Therefore, representational motivating force itself comprises fluid flow, electrophoresis class fluid flow, the fluid flow of pH value gradient-driven or the fluid flow of other gradient-driven that capillary action, pump drive.
In the synoptic diagram of Figure 10, motivating force actuator 1010D demonstration is connected (this will be described below) with outlet opening 810D, shows that at least a portion of motivating force can be provided in the required mobile destination county of solution, reaction reagent etc.Also provide collector 1020 with the expression can be in system flow destination county collecting reaction product 1048 (as following discussion).In some embodiments, collector 1020 comprises fluid reservoir.In some embodiments, collector 1020 comprises base material.In some embodiments, collector 1020 comprises detector.In some embodiments, collector 1020 comprises the object that the needs treatment is handled.For convenience's sake, system flow is generally represented by direction arrow F1, F2 and F3 in Figure 10.
Continuation in some embodiments, is carried out chemical reaction with reference to Figure 10 in integrated flow system 1000.In some embodiments, with material 1040, for example chemical reagent is introduced microfluidic device 1000 via hole 810A, simultaneously via ingate 810B with second material 1042 for example second chemical reagent introduce microfluidic device 1000.Randomly, microfluidic device 1000 comprises functionalized surfaces (referring to Fig. 5 A).Motivating force actuator 1010A and 1010B are pushed to chemical reagent 1040 and 1042 respectively in microfluid raceway groove 831 and 833.Chemical reagent 1040 and 1042 fluid proceed to fluid reservoir 850A and 850B, there, collect the reserve of reaction reagent 1040 and 1042.Chemical reagent 1040 and 1042 fluid continue to enter microfluid raceway groove 832 and 834, arrive point of crossing 860A, and therein, chemical reagent 1040 and 1042 takes place initially to contact.Then, chemical reagent 1040 and 1042 fluid proceed to reaction chamber 870, and there, the chemical reaction between the chemical reagent 1040 and 1042 is proceeded.
Continuation is with reference to Figure 10, and reaction product 1044 flows to micron order raceway groove 836 and reaches point of crossing 860B.Then, chemical reagent 1046 and reaction product 1044 reactions, 860B begins in the point of crossing, passes reaction chamber 838 and arrives fluid reservoir 850C.Formed second reaction product 1048.The fluid of second reaction product 1048 continues across micron order raceway groove 840 and arrives hole 810D and enter collector 1020 at last.Therefore, be noted that CPU 1002 drives motivating force actuator 1010C, so that discharge chemical reagent 1046 with at point of crossing 860B place contact reacts product 1044 in the suitable time.
XI.D. the representative applications of microfluidic device
In some embodiments, disclosure theme discloses the method according to the characteristic screening sample.In some embodiments, disclosure theme discloses the method for dispensing materials.In some embodiments, disclosure theme discloses the method for parting material.Therefore, one of skill in the art will recognize that, microfluidic device described herein can be applied to many application, include but not limited to gene order-checking, sharp separation, transmitter, the nano level reaction, ink jet printing, medicine is defeated far away, chip lab, in-vitro diagnosis, injection nozzle, biological study, the high flux screening technology, for example be used for drug discovery and Materials science, diagnosis and treatment tool, the biochemical watch-dog of research tool and food and natural resources (for example with soil, water and/or air portable or fixedly monitoring device collection).In some embodiments, disclosure theme discloses via the microfluidic device screening material.Some useful microfluidic devices that are suitable for ultraviolet detection are described in International Patent Publication No. WO 02/29397 A2, and the document is incorporated herein by reference in this integral body.
XI.D.1. according to the method for characteristic screening sample
In some embodiments, disclosure theme discloses the method according to the characteristic screening sample.In some embodiments, this method comprises:
(a) provide the micron order device, this micron order device comprises:
(i) have PFPE (PFPE) material that is selected from following feature: less than about 100cSt, condition is a viscosity less than the liquid PFPE precursor material of 100cSt is not free radical photocurable PFPE material to viscosity greater than about 100 centistokes (cSt) and viscosity;
(ii) functionalized PFPE material;
(iii) Fluorine containing olefine class elastomerics; With
(iv) their combination;
(b) provide target material;
(c) with sample arrangement in this micron order device;
(d) this sample is contacted with target material; With
(e) detect interaction between this sample and the target material, wherein existing or do not have this interaction is the indication of this sample characteristics of for example.
Referring again to Figure 10, at least a sample that comprises in the material 1040 and 1042.In some embodiments, at least a target material that comprises in the material 1040 and 1042.Therefore, " sample " generally is meant any material of waiting to obtain its information relevant with characteristic.In addition, " target material " can be meant any material that can be used to provide the information relevant with sample characteristics of for example based on the interaction between target material and the sample.For example, in some embodiments, when sample 1040 contact target materials 1042, interact.In some embodiments, interaction produces reaction product 1044.In some embodiments, interaction comprises fixation phenomenon.In some embodiments, fixation phenomenon for example comprises, antibody and antigen, and enzyme and substrate, or more particularly, acceptor and part, or the interaction between catalyzer and one or more chemical reagent.In some embodiments, reaction product is detected by detector 1030.
In some embodiments, method comprises target material is arranged in in a plurality of raceway grooves at least one.Referring again to Figure 10, in some embodiments, target material comprises active material 880.In some embodiments, target material, sample or target and sample and functionalized surfaces keyed jointing.In some embodiments, target material comprises substrate, for example non-patterned layer.In some embodiments, this substrate comprises semiconductor material.In some embodiments, at least one in a plurality of raceway grooves of microfluidic device and substrate, for example non-patterned layer fluid is communicated with.In some embodiments, target material is arranged in substrate, on for example non-patterned layer.In some embodiments, at least one in one or more raceway grooves of microfluidic device is communicated with target material fluid on being arranged in substrate.
In some embodiments, method comprises at least one in a plurality of raceway grooves of many sample arrangement.In some embodiments, sample is selected from therapeutical agent, diagnostic reagent, research reagent, catalyzer, metal ligand, abiology organic materials, inorganic materials, food, soil, water and air.In some embodiments, sample comprises one or more in one or more chemistry or biological compound or the component pool.In some embodiments, sample comprises in nucleic acid-templated, order reagent, primer, primer extension product, restriction enzyme, PCR reagent, PCR reaction product or its combination one or more.In some embodiments, sample comprises in antibody, cell receptor, antigen, receptors ligand, enzyme, substrate, immune chemical, virus, viral bound component, protein, cellular factor, somatomedin, inhibitor or its combination one or more.
In some embodiments, target material comprises in antigen, antibody, enzyme, restriction enzyme, dyestuff, fluorescence dye, order reagent, PCR reagent, primer, acceptor, part, chemical reagent or its combination one or more.
In some embodiments, interaction comprises fixation phenomenon.In some embodiments, carry out this interactional detection by at least a or multiple following device: spectrophotometer, photofluorometer, photodiode, photomultiplier, microscope, scintillometer, pick up camera, ccd video camera, film, optical detection system, temperature sensor, electrical conductivity meter, potentiometer, amperometer, pH meter or its combination.
Therefore, after reading present disclosure, those skilled in the art will also recognize that PFPE class microfluidic device of the present disclosure can be used for various triage techniqueses, as
People such as BerghU.S. Patent number 6,749,814,
People such as Bergh6,737,026,
People such as Parce6,630,353,
Wolk Deng the people6,620,625,
People such as Parce6,558,944,
People such as Kopf-Sill6,547,941,
People such as Wada6,529,835,
People such as Kercso6,495,369 Hes
Parce Deng the people6,150,180 in describe those, in these documents each piece whole introduce for reference.In addition, after reading present disclosure, those skilled in the art will also recognize that PFPE class microfluidic device of the present disclosure can for example be used for detecting with. DNA, protein or other molecule that specific biochemical system is relevant, as
People such as QuakeU.S. Patent number 6,767,706 described, the document is incorporated herein by reference in this integral body.
XI.D.2. the method for dispensing materials
In addition, the disclosure subject description method of dispensing materials.In some embodiments, this method comprises:
(a) provide microfluidic device, comprising:
(i) have PFPE (PFPE) material that is selected from following feature: less than about 100cSt, condition is a viscosity less than the liquid PFPE precursor material of 100cSt is not free radical photocurable PFPE material to viscosity greater than about 100 centistokes (cSt) and viscosity;
(ii) functionalized PFPE material;
(iii) Fluorine containing olefine class elastomerics; With
(iv) their combination; And wherein this microfluidic device comprises one or more micron order raceway grooves, and wherein at least one comprises outlet opening in these one or more micron order raceway grooves;
(b) provide at least a material;
(c) arrange at least a material at least one in these one or more micron order raceway grooves; With
(d) distribute at least a material by this outlet opening.
In some embodiments, the surface of at least one in the one or more micron order raceway grooves of layer covering of PFPE material.
Referring again to Figure 10, in some embodiments, material, for example material 1040, second material 1042, chemical reagent 1046, reaction product 1044 and/or reaction product 1048 flow through outlet opening 810D and be assigned among the collector 1020 or on.In some embodiments, target material, sample or target and sample combine with functionalized surfaces.
In some embodiments, described material comprises medicine.In some embodiments, this method comprises the predetermined dose that measures this medicine.In some embodiments, this method comprises the predetermined dose that distributes this medicine.
In some embodiments, this material comprises ink composite.In some embodiments, this method is included in and distributes this ink composite on the base material.In some embodiments, the distribution of this ink composite on base material forms printed images.
Therefore, after reading present disclosure, those skilled in the art will also recognize that PFPE class microfluidic device of the present disclosure can be used for the microfluid printing, as U.S. Patent number
Kaszczuk etc. The people6,334,676,
People such as DeBoer6,128,022 He
Wen6,091, described in 433, in these documents each a piece of writing be incorporated herein by reference in this integral body.
The method of XI.D.3 parting material
In some embodiments, the disclosure subject description method of parting material, this method comprises:
(a) provide microfluidic device, comprising:
(i) have PFPE (PFPE) material that is selected from following feature: less than about 100cSt, condition is a viscosity less than the liquid PFPE precursor material of 100cSt is not free radical photocurable PFPE material to viscosity greater than about 100 centistokes (cSt) and viscosity;
(ii) functionalized PFPE material;
(iii) Fluorine containing olefine class elastomerics; With
(iv) their combination; And wherein this microfluidic device comprises one or more micron order raceway grooves, and wherein at least one in these one or more micron order raceway grooves comprises the disengaging zone;
(b) first material will be comprised at least and second mixtures of material is arranged in the microfluidic device;
(c) allow this mixture flow through this disengaging zone; With
(d) in this disengaging zone with this first material and second material separation to form at least a isolating material.
Referring again to Figure 10, in some embodiments, at least a mixture that comprises in the material 1040 and second material 1042.For example, material 1040 for example mixture flows through microfluid system to chamber 870, and this chamber 870 comprises the disengaging zone in some embodiments.In some embodiments, this disengaging zone comprises active material 880, for example the stratographic analysis material.Material 1040 for example mixture at chamber 870 separated formation the 3rd material 1044 in the separate chamber for example, for example isolating material.In some embodiments, isolating material 1044 is detected by detector 1030.
In some embodiments, the disengaging zone comprises the stratographic analysis material.In some embodiments, the stratographic analysis material is selected from size-matrix separation, avidity-matrix separation and gel-exclusion matrix or their combination.
In some embodiments, first or second material comprises one or more in one or more chemistry or biological compound or the component pool.In some embodiments, first or second material comprises in nucleic acid-templated, order reagent, primer, primer extension product, restriction enzyme, PCR reagent, PCR reaction product or its combination one or more.In some embodiments, first or second material comprises in antibody, cell receptor, antigen, receptors ligand, enzyme, substrate, immune chemical, virus, viral bound component, protein, cellular factor, somatomedin, inhibitor or its combination one or more.
In some embodiments, method comprises the isolating material of detection.In some embodiments, carry out this isolating material tests by at least a or multiple following device: spectrophotometer, photofluorometer, photodiode, photomultiplier, microscope, scintillometer, pick up camera, ccd video camera, film, optical detection system, temperature sensor, electrical conductivity meter, potentiometer, amperometer, pH meter or its combination.
Therefore, after reading present disclosure, those skilled in the art will also recognize that PFPE class microfluidic device of the present disclosure can be used for parting material, as U.S. Patent number
People such as Huang6,752,922,
People such as Chow6,274,089 He
People such as Knapp6,444, described in 461, in these documents each a piece of writing be incorporated herein by reference in this integral body.
XII. the application of functionalized microfluidic device
The fluidity microchip technology is substituting as traditional chemical and biology laboratory function day by day.Made the microchip that on individual devices, carries out complex chemical reaction, separation and detection.These " chip labs " are used and are promoted fluid and analyte transportation, and have minimizing time and chemical depletion and the easy advantage of operation automatically.
Many biochemical analysises, reaction and separate and in little channel system, carry out.The high throughput screening assay of synthetic molecules and natural product has significant interests.Based on the interactional ability of molecules in inhibiting enzyme and fluorescent mark substrate and the microfluidic device that screens various molecules obtained description (
People such as ParseU.S. Patent number 6,046,056).As
People such as ParseDescribed, these devices allow the pro-drug in or synthetic storehouse natural by the anti-or short effect performance screening of pro-drug.The molecule type that can screen includes but not limited to, little organic or inorganic molecule, polysaccharide, peptide, protein, the extract of nucleic acid or biomaterial such as bacterium, fungi, yeast, plant and animal cell.Analysis of compounds can dissociate in solution or be attached on the carrier, as agarose, Mierocrystalline cellulose, dextran, polystyrene, carboxymethyl cellulose, polyoxyethylene glycol (PEG), filter paper, soluble cotton, ion exchange resin, plastics film, granulated glass sphere, polyamine methylvinylether maleic acid, amino acid copolymer, ethene-maleic acid, nylon, silk etc.Compound can be used as pure compound or tests to converge the thing form.For example,
People such as NelsonU.S. Patent number 6,007,690 relate to the microfluid molecular diagnosis of purify DNA from whole blood sample.This device uses the enrichment raceway groove of cleaning or concentrated analytic sample.For example, this enrichment raceway groove may hold the pearl of antibody coating to remove various cells parts via their anti-gene element or may hold the stratographic analysis component, as ion exchange resin or hydrophobicity or hydrophilic film.This device can also comprise chamber of the reactor, wherein can carry out various reactions to analyte, as labeled reactant or under the situation of protein analyte, carries out the lixiviate reaction.In addition,
People such as BeebeU.S.'s publication application number 20040256570 a kind of device has been described, but wherein when antibody and the anti-genetic analysis thing material that applies interact the dissipation that causes liposome and its release detection molecules, detect this interaction on the liposome outside.U.S.'s publication application number 20040132166 of people such as Miller provides a kind of microfluidic device, and this microfluidic device can be responded to pair cell and increase important environmental factors, as pH value, humidity and O
2Level.Reaction chamber in these devices can play the bio-reactor effect that can make the cell growth, allows them to be used for and DNA exchange cell and generation protein, or crosses over the possible bioavailability of the absorption rate testing medicine of CACO-2 cellular layer by measuring medicine.
Except making the cell growth, microfluidic device also is used for cell divide.
People such as WadaU.S. Patent number 6,592,821 described and concentrated on cell and daughter cell component, comprise independent molecule, as nucleic acid, polypeptide or other organic molecule, or than the hydrokinetics of maxicell component such as cell organelle classification.This method can be with cells survival or other cell expressing functional classification.
Nucleic acid with proteinic expansion, separate, ordering and evaluation be that the microfluidic device of using always is used.For example,
LoewyU.S. Patent number 5,939,291 for example understand to use electrostatic technique to wait the microfluidic device of isothermal nucleic acid expansion.This device and many expansion response strategies commonly used are used simultaneously, comprise PCR (polymerase chain reaction), LCR (ligase chain reaction), SDA (tow displacement expansion), NASBA (expansion of nucleotide sequence base) and TMA (transcribe to reconcile and enlarge).
Moroney etc. The peopleU.S. Patent number 5,993,611 device that uses the electric capacity charging to analyze, amplify or handle nucleic acid has been described.Device has designed by size classes DNA, analysis restriction fragment length polymorphism (referring to
People such as QuakeU.S. Patent number 6,833,242).This device can also be used in particular for court and use, as dna fingerprint.
People such as JensenU.S. Patent number 6,447,724 microfluid of identifying the component of mixtures based on the different fluorescence lifetimes of the mark that adheres to the member of mixture has been described.This kind device can be used for analysis of nucleic acids, protein or oligose ordering reaction or check or the member of inquiry organic molecule combinatorial libraries.
Relate to the device that other microfluidic device that specific proteins uses comprises the crystallization of protein growth that promotes in the microfluid raceway groove (referring to
People such as WeiglU.S. Patent number 6,409832).In this device, protein example and solvent are sent to the raceway groove with laminar flow characteristic that forms the spreading area, this provides the crystallization that the division is clearly demarcated.
People such as PugiaU.S.'s publication application number 2004/0121449 for example understand the device that uses minimum centrifugal force separate red hemocyte from plasma to the sample size of 5 microlitres to little.This device can be particularly useful for clinical diagnosis and can also be used to separating any particulate matter in addition from liquid.
As described in the part, microfluidic device is with acting on the microreactor that many chemistry and biologies are used as mentioned.Chamber in these devices can be used for that ordering, restriction enzyme lixiviate, restriction fragment length polymorphism (RFLP) are analyzed, nucleic acid enlarges or gel electrophoresis (referring to
People such as HandiqueU.S. Patent number 6,130,098).The reaction of many chemistry titrations can move (referring to U.S.'s publication application number 20040258571 of people such as Lee) in this device, comprise the acidic group titration or based on sedimentary titration (for example, Ag (I) and Cl
-, Br
-, I
-Or SCN
-), complex compound forms (for example, Ag (I) and CN
-) or redox reaction (as Fe (II)/Fe (III) and Ce (III)/Ce (IV)).In addition, the transmitter that is used for potentiometry, amperometry, spectrophotometry, turbidometry, fluorometry or calorimetry can be connected with this device.Protein (referring to
People such as GilbertU.S.'s publication application number 20040245102) classification of basic physics or biology performance is used for protein expressioning analysis (find the molecule marker, measure the molecular basis or the profile of morbid state or describe protein structure/functional relationship).Many electrophoretic techniques (comprising the kapillary isoelectric focusing, zone of capillarity electrophoresis and capillary gel electrophoresis) be used for the proteinic microfluidic device of classification (referring to
People such as SchneiderU.S. Patent number 6,818,112).The use of can connecting of different electrophoretic techniques has or does not help quantitative markers step and use (as the mobilization of ydrodynamics salt, the mobilization of pH value or osmosis fluid) with further isolated protein simultaneously with many elution techniques.Many other materials are with helping sepn process in the microfluidic device.These materials can be connected with the channel walls in the device or as matrix independently be present in the raceway groove (referring to
PaulU.S. Patent number 6,581,441
People such as WadaU.S. Patent number 6,613,581).Can exist the raceway groove that separates in parallel to separate many samples simultaneously.The solid separating medium can be used as discrete particle or exists as the porous integral solid.Possible material comprises silica gel, agar glycosyl gel, polyacrylamide gel, colloidal solution such as gelatin, starch, and the big netted and macroporous resin of non-ionic type is (as AMBERCHROM
TM(Rohm and Haas Co, Philadelphia, Pennsylvania, United States of America), AMBERLITE
TM(Rohm andHaas Co, Philadelphia, Pennsylvania, United States ofAmerica), DOWEX
TM(The Dow Chemical Company, Midland, Michigan, United States of America), DUOLITE
(Rohm and HaasCo, Philadelphia, Pennsylvania, United States of America), etc.) or the material (glass, metal, silicon-dioxide, acrylic resin, the SEPHAROSE that exist as pearl
TM, Mierocrystalline cellulose, pottery, polymkeric substance etc.).These materials can also exist various biologically-based molecules to help separation (for example, the phytohemagglutinin with carbohydrate and antibodies can will resist the gene group to be strapped on the different proteins) on their surface.Film in little raceway groove be used for osmosis separate (referring to
MolesU.S. Patent number 6,406,605).The film that is fit to can comprise material, as the polycarbonate or the polyimide of track etching.
Temperature, concentration and fluid gradient are also with helping separating in the microfluidic device.
Kirk Deng the peopleU.S.'s publication application number 20040142411 use chemotaxi (motion of cell is caused by the concentration gradient of solvable chemotaxis stimulator) is disclosed, hapatotaxis (motion response of cell is in the concentration gradient of the stimulator of substrate constraint) and chemoinvasion (cell enter and/or the motion response by obstruct or gel-in-matrix in stimulator).The chemotactic stimulator comprises chemical expellent (chemorepellants) and chemoattractant.Chemoattractant is any material that attracts cell.Example includes but not limited to, hormone such as suprarenin and vassopressin; Immunizing agent such as interleukein-2; Somatomedin, chemokine, cytokine and various peptide, small molecules and cell.The chemistry expellent comprises stimulator such as benzalkonium chloride, propylene glycol, methyl alcohol, acetone, sodium lauryl sulphate, hydrogen peroxide, 1-butanols, ethanol and dimethyl sulfoxide (DMSO); Toxin such as prussiate, carbonyl cyanide, chloro-phenyl-hydrazone; Intracellular toxin and bacteria lipopolysaccharide; Virus; Pathogenic agent and pyrogene.The limiting examples of the cell that can handle by these technology comprise lymphocyte, monocyte, white cell, scavenger cell, mastocyte, T cell, B cell, neutrophil leucocyte, basophil, inoblast, tumour cell and many other.
Microfluidic device as transmitter came on the scene in recent years.These microfluid sensors can comprise the dye-based detection system, avidity base detection system, little manufacturing gravity analyser, ccd video camera, fluorescence detector, optical microscope system, electrical system, thermopair, hot resistance and pressure transmitter.These devices be used for by they with can provide electrochemical signals the interaction detection of biological molecule of detecting molecule (referring to
People such as AlthausThe open international application no WO 2004/094,986 of PCT), comprise polynucleotide, protein and virus.For example, nucleic acid samples and the insertion of detecting molecule such as adriamycin can reduce the amount of the free adriamycin that contacts with electrode; And obtain the change of electrical signal.Described in the device reaction chamber, to comprise and be used for detecting and control environment factor such as humidity, pH value, dissolved O
2With dissolved CO
2Transmitter device (referring to
People such as RodgersThe open international application no WO2004/069 of PCT, 983).These devices are used in particular for making the cell growth and keep.Can be in device measure sample carbon content (referring to
People such as ThomasU.S. Patent number 6,444,474), wherein the UV radiation becomes CO with oxidation operation
2, measure this CO by conductivity measurement or infrared method then
2Amount.Be used for microfluidic device capacity transducer (referring to
People such as XieThe open international application no WO 2004/085,063 of PCT) can be used for measuring stress, flow, liquid level and ionic concn.
The Another application that is used for microfluid system comprise cell the high-throughput injection (referring to
People such as GarmanThe open international application no WO 00/20554 of PCT).In this kind device, advance cell to nozzle needle, there, they can with various materials, comprise molecule and macromole, gene, karyomit(e) or cell organelle are injected together.This device can also be used to from the cell extraction material and will be used for many fields, as gene therapy, and medicine or agrochemicals research and diagnosis.Microfluidic device also as the device of in ink jet printing, carrying printing ink (referring to
Anderson Deng the peopleU.S. Patent number 6,575,562), and be used for sample solution deliver to the electropaining ionization tip that is used for mass spectroscopy (referring to
People such as BousseU.S. Patent number 6,803,568).Also reported administration through skin system (referring to
People such as CormierThe open international application no WO2002/094 of PCT, 368), and be used for that spectroscopy uses comprise the device that light changes element (referring to
People such as NagleU.S. Patent number 6,498,353).
XIII. the application of functionalized micro plate
Material of the present disclosure and method can also be applied to treat the design and the manufacturing of the device that uses by the micro plate mode.Micro plate is at the high flux screening of protein groups, genome and drug discovery, and environmental chemistry is tested, and parallel synthetic, cell cultures has many purposes in molecular biology and the immunity test field.The base mateiral commonly used that is used for micro plate comprises hydrophobic material such as polystyrene and polypropylene and hydrophilic material such as glass.Silicon, metal, polyester, polyolefine and ptfe surface also have been used for micro plate.
The molecule that can test or handle for application-specific (based on their solvent and temperature consistency) and their influence or the ability (or lacking ability) of biomolecules are selected the surface.The chemical modification of base mateiral can be used for the following micro plate that makes usually and adapts to its required function: change surface characteristic or provide the position for the covalent attachment of molecule or biomolecules.The functionalisable character of disclosure material is suitable for these purposes very much.
Some application requiring have weak surface in conjunction with feature.Protein and many other biomolecules (as eukaryotic cell and microorganism cells) can be adsorbed with polystyrene passively by hydrophobic interaction or ionic interaction.The base mateiral of having developed some surface modifications solves this problem.CORNING
Ultra Low Attachment (CorningIncorporated-Life Sciences, Acton, Massachusetts, UnitedStates of America) is the polystyrene that hydrogel applies.This hydrogel coating is given surperficial neutrality and wetting ability, prevents adhering to of nearly all cell.The container of being made by this surface is used to prevent that serum protein from absorbing, prevent grappling dependent cell (MDCK, VERO, C6 etc.) division, optionally cultivate tumour or virus and change independently colony of cell conduct, prevent that stem cell from adhering to the differentiation of conciliation and the activation and the PASSIVATION MECHANISM of research scavenger cell.NUNC MINISORP (Nalgene Nunc International, Naperville, Illinois, UnitedStates of America) be to have the polyvinyl product of low albumen avidity and be used for DNA to detect and the serum-based test, wherein non-specific binding is a problem.
For other application, the base mateiral modification is improved the ability that they are attached to cell and other biomolecules.The NUNCLON Δ
TM(Nalgene Nunc International) to add surperficial carboxyl, given this material wetting ability and electronegativity by the polystyrene surface of corona or plasma discharge processing.This material has been used for the cell cultures of many cells.Polyolefine and polyester material also processed with the wetting ability that improves them and the adhesion of the pair cell that therefore becomes and growth be excellent surface (PERMANOX for example
TMAnd THERMANOX
TM, also derive from NalgeneNunc International).Base mateiral can scribble poly--D-Methionin, collagen or Fibronectin are to produce the surface of positively charged, and this also can improve cell attachment, growth and differentiation.
In addition, other molecule can absorb on the micro-shape plate.Nunc MAXISORP
TM(Nalgene Nunc) is the modified polystyrene basis, and it has high avidity and recommendation to polar molecule and is used for the surface, and wherein antibody must absorb this surface, as under many ELISA test situation.The surface also can be through modification to interact by more specific mode and analyte.The example of these functionalization and modifications comprises that surface that the surface of nickel-inner complex modification is used for the quantification of fused protein of histidine mark and detection and gsh modification is used for the capturing of fused protein of GST mark.When handling biotinyl protein, the surface that can use streptavidin to apply.
The surface of some modifications provides the position for the covalent attachment of various molecules or biomolecules.COVALINK
TMNH secondary amine surface (Nalgene Nunc International) is the polystyrene surface that covers with secondary amine, this secondary amine can be by their carboxyl via carbodiimide Chemical bond protein and peptide or the formation by 5 ' phosporamidiate key (reusing the carbodiimide chemistry) in conjunction with DNA.Other molecule, carbohydrate, hormone, small molecules etc. that comprises or comprise the carboxylate group through modification also can with this surface bonding.Epoxide is the another kind of useful structure division that is used for being connected with the covalent linkage on surface base.The surface of having used the epoxide modification is via the oligonucleotide of amino-modification and the reaction generation DNA chip on surface.Surface with fixed oligonucleotide can be used for high-throughput DNA and RNA detection system and automatic DNA broadened application.
Other purposes of micro plate relates to surface modification so that its hydrophobicity more, thereby makes it more perhaps reduce the absorption of medicine (common little organic molecule) mutually with organic solvent.For example, total pharmaceutical analysis test relies on usually and uses acetonitrile to make protein and salt from plasma or serum sample precipitation.The medicine of testing must remain in the solution so that quantification subsequently.The compatible micro plate of organic solvent also prepares device and is used as combinatorial chemistry or parallel building-up reactions container (being used for solution-based or solid state chemistry process) as high speed liquid chromatography (HPLC) or liquid chromatography/mass spectrum/mass spectrum (LC/MS/MS).The example on the surface of the purposes of these types comprises MULTICHEM
TMMicroplate (Whatman, Inc., Florham Park, New Jersey, United States ofAmerica) and MULTISCREEN
Solvinert (Millipore, Billerica, Massachusetts, United States of America).
XIV. use the method for functionalized PFPE network as gas separation membrane
Disclosure theme provides the purposes of functionalized PFPE (PFPE) network as gas separation membrane.In some embodiments, functionalized PFPE network separates and is selected from CO as gas separation membrane
2, methane, hydrogen, CO, CFC, CFC alternative, organism, nitrogen, methane, H
2S, amine, fluorohydrocarbon, Fluorine containing olefine and O
2Gas.In some embodiments, use functionalized PFPE network to be separated in gas in the desalt process.In some embodiments, gas separation membrane comprises independence (stand-alone) film.In some embodiments, gas separation membrane comprises laminated film.
In some embodiments, gas separation membrane comprises comonomer.In some embodiments, the penetrating quality of comonomer adjustments of gas separatory membrane.In addition, the physical strength of this type of film and weather resistance can be finely tuned by compounded mix such as silica dioxide granule and other are added in this film.Therefore, in some embodiments, film also comprises compounded mix.In some embodiments, compounded mix comprises silica dioxide granule.
XV. the application of the low-surface-energy material of anti-the solvent
According to alternate embodiment, one or more that material of the present disclosure and method can be with following material and in using combine and/or replace them.
According to an embodiment, material of the present invention and method can replace the silicone component in the adhesive material.In another embodiment, material of the present invention and method can combine the bonding and the alternate that provide stronger with adhesive material and adhere to pattern.The example that can use material of the present invention comprises tackiness agent, as the time being solidified to form flexible rapidly when heating and elastomeric two components of the high tear tackiness agent that can flow.Tackiness agent such as this be suitable for the fabric of silicone coated is bonded to one another and be bonded on the various base materials.A kind of like this example of tackiness agent is DOWCORNING
Q5-8401 ADHESIVE KIT (Dow Corning Corp., Midland, Michigan, United States of America).
According to another embodiment, material of the present invention and method can replace the silicone component in the colour batch.In another embodiment, material of the present invention and method can combine bonding and the alternate bonding pattern that provides stronger with the component of colour batch.The example that is suitable for the colour batch that uses with the present invention include but not limited to for liquid silicones rubber (LSR ' s) use a series of pigment masterbatch that design, for example, SILASTIC
LPX RED IRON OXIDE5 (Dow Corning Corp., Midland, Michigan, United States ofAmerica).
According to another embodiment, material of the present invention and method can replace the liquid silicones elastomeric material.In another embodiment, material of the present invention and method can combine with the liquid silicones elastomeric material provides stronger bonding of the present invention and alternate bonding technology for this liquid silicones elastomeric material.Be suitable for using or the example of the liquid silicones rubber replaced with the present invention includes but not limited to the present invention, the liquid silicones rubber coating is as not only firmly but also the solvent-free liquid silicones rubber of heat-staple two components.Similar liquid silicone rubber coating shows the especially good adhesion of polymeric amide and glass and has the low friction of flexible and non-inaccessible surperficial, and this kind product is by for example, DOW CORNING
3625 A﹠amp; B KIT representative.Other this type of liquid silicones rubber comprises, for example, and DOW CORNING
3629 PART A; DOW CORNING
3631 PARTA﹠amp; B (two portions, solvent-free, thermofixation liquid silicones rubber); DOW CORNING
3715BASE (be cured to two portions solvent-less silicone finish paint stone and very low-friction surface, this surface is anti-soil and dust-proofing agent); DOW CORNING
3730 A﹠amp; B KIT (polymeric amide and glass fabric are had the especially good solvent-free and colourless liquid silicone rubber of adherent two components); SILASTIC
590 LSR PART A﹠amp; B (the solvent-free liquid silicones rubber of two components) with good thermal stability; SILASTIC
9252/250P KIT PARTS A﹠amp; B (two components, solvent-free, the liquid silicones rubber of thermofixation; The universal lacquer of glass and polyamide fabric; Usually can obtain three kinds of ranks, halogen, low smoke and non-toxic and food grade); SILASTIC
9252/500PKIT PARTS A﹠amp; B; SILASTIC
9252/900P KIT PARTS A﹠amp; B; SILASTIC
9280/30 KIT PARTS A﹠amp; B; SILASTIC
9280/60E KIT PARTS A﹠amp; B; SILASTIC
9280/70E KIT PARTS A﹠amp; B; SILASTIC
9280/75E KITPARTS A﹠amp; B; SILASTIC
LSR 9151-200P PART A; SILASTIC
LSR9451-1000P; RTV Elastomers (Dow Corning Corp., Midland, Michigan, United States of America); DOW CORNING
734 FLOWABLESEALANT, CLEAR (be used for the single-component solvent-free silicone elastomer that general sealing and bonding are used, this silicone elastomer is a flowable liquids, this liquid be easy to use and when being exposed to the curing of following time of airborne moisture); DOW CORNING
Q3-3445 RED FLOWABLEELASTOMER; (be used for the redness of high temperature anti-stick coating, the single-component solvent-free silicone elastomer that can flow, usually, this product is used for coated fabric, discharge food and to stable) up to 260 ℃; With DOW CORNING
Q3-3559 SEMIFLOWABLE TEXTILE ELASTOMER (the single-component solvent-free silicone elastomer partly can flow).
According to another embodiment, material of the present invention and method can replace water base Procuring silicone elastomer.In another embodiment, material of the present invention and method can combine with water base silicone elastomer provides improved physics described herein and chemical property for this material.Be suitable for using or the example of the water base silicone elastomer replaced with the present invention includes but not limited to that the present invention typically is applied to its water base auxiliary agent, comprises DOW CORNING with the present invention
84 ADDITIVE (water base Procuring silicone elastomer); DOW CORNING
85 ADDITIVE (water base Procuring silicone elastomer); DOW CORNING
ET-4327 EMULSION (for the glass fabric fibre provides that dimension is lubricated, wear resistance, waterproof and the functionalized silicone emulsion of flexible methyl/phenyl, usually as the glass fibre pre-treatment of PTFE coating); With Dow Corning 7-9120Dimethicone NF Fluid (by the new rank polydimethylsiloxane fluid that is used for over-the-counter (OTC) part and skin care product of Dow Corning introduction).
According to another embodiment, material of the present invention and method can replace other silicone material.In another embodiment, material of the present invention and method can combine with these other silicone material and think that these other silicone material gives improved physics and chemical property.Be suitable for using or the example of other silicone material of replacing with the present invention includes but not limited to the present invention, for example, United Chemical Technologies RTVsilicone (United Chemical Technologies, Inc., Bristol, Pennsylvania, United States of America) (the flexible transparent elastomer that is suitable for the electrical/electronic cast and seals); Methyl silicone closes sodium (this product is given siliceous surface waterproofing and increased green strength and the original storage life); Silicone emulsion (can be used as nontoxic sprayable releasing agent and be dried to the transparent silicone film); PDMS/ alpha-methyl styrene (when must with temporary transient silicone coating when base material dissolves, being useful); GLASSCLAD
6C (United ChemicalTechnologies, Inc., Bristol, Pennsylvania, United States ofAmerica) (hydrophobic coating that has the glass wares that is used for fibre optics, clinical analysis, electron device); GLASSCLAD
18 (hydrophobic coatings that are used for labware, porcelain, optical fiber, clinical analysis and bulb); GLASSCLAD
The HT protectiveness hard film coating of 350 ℃ of stability (have＞); GLASSCLAD
PSA (the temporary transient bonded high purity pressure sensitive adhesive strong) with glass, insulator member, metal and polymer formation; GLASSCLAD
SO (being used for) with the protectiveness hard coat of silica deposit on silicon; GLASSCLAD
EG (flexible heat stable resin is for resistor and circuit card are given oxidation and mechanical barrier); GLASSCLAD
RC (have＞methyl silicone of 250 ℃ stability, be commonly used for electric and coating circuit board member); GLASSCLAD
CR (being solidified into flexible thin film's silicone lacquer preparaton, anti-290 ℃); GLASSCLAD
TF (the source material of the thick film of silicon-dioxide (0.2-0.4 micron) coating is transformed into 36% silicon-dioxide and is generally used for dielectric layer, wear-resistant coating and semitransparent thin film); GLASSCLAD
FF (the wet activation flexibility elastomerics that is used for bio-medical instrument and optics); With UV SILICONE (refractive index (R.I.) and the UV curable silicone that silicon-dioxide mates are solidified in thin cross section with conventional UV source).
According to another embodiment of the invention, material of the present invention and method can replace containing the material of other silicone and/or combine with it.Some examples that contain the material of other silicone include but not limited to TUFSIL
(Specialty Silicone Products, Inc., BallstonSpa, New York, United States of America) (makes breathing mask, pipe arrangement and other and skin contact by being mainly used in of Specialty Silicones exploitation, or be used to keep healthy and the member of the parts of food-processing industry); Baysilone Paint Additive TP3738 (LANXESS Corp., Pittsburgh, Pennsylvania, United States ofAmerica) (slip additive of hydrolysis); Baysilone Paint Additive TP3739 (reduces surface tension and improves the moistening composition of base material, three kinds of acrylic resin thickening materials that are used for negatively charged ion, positively charged ion, nonionic and both sexes solution, the APK of powder polymethacrylate, APN and APA and liquid propene acid are the resin thickening material in this way); Tego Protect5000 (Tego Chemie Service GmbH, Essen Germany) (is generally used for the modified dimethyl polysiloxane of matte finish, clear-cut finish and paint system); Tego Protect5001 (contain the silicone polyacrylate resin of water-resisting agent, use with the transparent varnish system usually); The Tego Protect 5002 silicone polyacrylate resin of recoat (can after gentle surface treatment); (what can be used for preparing the emulsion, powder and the excellent goods that are used for facial processing, bight, lipstick, moistening agent and sunscreen holds back the system of technology based on the microsponge dimethyl silicone oil to Microsponge 5700 Dimethicone, in the matrix of the complex cross-linked of polymethacrylate copolymer dimethyl silicone oil is pressed in the vacuum zone usually; The 350cST polydimethylsiloxane constitutes 78% and the 1000cST polydimethylsiloxane hold back the dimethyl-silicon oil ingredient and constitutes in addition 22%, and this system promotes the provide protection of dimethyl silicone oil to be transported in the skin usually); MB50 high molecular polydimethylsiloxane additive series (can be in the surface friction that reduces and better process under the running speed faster, usually the preparaton that can be used for PE, PS, PP, thermoplastic polyester elastomer, nylon 6 and 66, acetal and ABS, this silicone component is tasteless and colourless and can be used to relate to the application of Food Contact that this product can be used as substituting of silicone fluid and PTFE); Slytherm XLT (derives from the novel polydimethylsiloxane low temperature heat-transfer fluid of Dow Corning, different with traditional organic conducting fluid, it be nonpoisonous and tasteless and not with system in the reaction of other material, it has non-scaling and does not form the attendant advantages of sludge under the high temperature); With 561
Silicone conversion fluid (this material has 300 ℃ flash-point and 343 ℃ burning-point, and this single component fluid is 100%PDMS, does not comprise additive, but in soil and settling natural degradation, do not cause that the oxygen in the water is exhausted).
XVI. be applied to device
Dual curable components material of the present invention can be used for various medical applications and include but not limited to medical device or medical implant.According to an embodiment, the material that comprises the photocuring of one or more blend and/or one or more thermofixation components can be used for making medical device, the part of device components, device, operation device, instrument, implantable member etc.The material of this blend is meant photocurable and/or the thermal curable mixture of ingredients in the polymkeric substance that will form device.Use this kind system to allow to form discrete objects, then in some embodiments, these discrete objects are adhered on other object, surface or the material by activating second curing system by activation semicure system.In some embodiments, this dual cure material can be used for solidifying medical device or the implant that is manufactured on the main body outside by first of this material, and second curing can be used for after implanting main body this device being adhered to tissue then.In other embodiment, the dual cure material can be used for making by stages medical device or the implant formation implant that member can be solidified togather then.Medical device made from dual cure material of the present invention or implant can be but be not limited to orthopedic device, cardiovascular device, device in the tube chamber, dermatology device, oral devices, optics, auditory organ's device is organized device, the organ device, the neuroscience device, the vascular device, regeneration device, their combination etc.Other device and the member that can scribble material disclosed herein and method comprise: pipe, pipeline; Bottle, glass wares, holder, transfer container, valve, volumetric pipette; Nozzle; Labware, eye-protection glasses, glass, gloves, washtub, groove (as tank for gaseous or liquid substances), cylindrical shell, ceramic component, metal device, polymer device, glass, their combination etc.This material can prevent to pollute as the coating of this type of device or liner to prevent fouling, prevents the reaction between the material in container and the container, cleaning easily, their combination etc.In some embodiments, material of the present invention adheres to by the hydroxyl on this device surface and these devices and material and forms strong interaction, and this interaction is kept this coating and liner in situ.
XVI.A. form device or implant and they are attached on another device or the implant
According to some embodiments, object is as the member of medical device or implant, or entire device can followingly be made: form Liquid precursor in mould, the activation curing mechanism so that this precursor is fixed or partly fixed, and takes out solid object as photocuring or thermofixation from mould.Then can be with another member of this object and medical device or implant, the surface, contacts such as coating contact is placed and is activated second curing mechanism, as thermofixation or photocuring, so that these two objects are adhered to each other.For example, this object can be but be not limited to, artificial joint member, artificial bone member, artificial tooth or tooth member, artificial facet joint, artificial lens etc.
The example of this program for example is illustrated among Figure 13 steps A-C.According to Figure 13, can (for example, PFPE) material be introduced in the mould and behind activation first curing mechanism (for example, thermofixation), the fixed formation pipe 1300 of this PFPE material with the liquid fluoropolymer.Pipe 1300 can be inserted in second pipe 1310 then, this second pipe 1310 is formed by identical or different material, and for example different polymkeric substance or natural materials or structure are as tissue or blood vessel.Next, activate second curing mechanism (for example, photocuring) so that this PFPE pipe 1300 adheres on second pipe 1310.
Relate to the embodiment of orthopedic application according to some, dual curable materials of the present invention promotes to be used for the new unit of placement in vivo and the reconstruction and/or the construction of structure.Other embodiment comprises biological or artificial device, tissue and the structure of rebuilding and repairing existence on the spot.For example, dual curable materials can be external or be used to build novel joint on the spot and repair existing joint.
According to some embodiments, the biological member of damage can be injured tissues such as osseous tissue (for example, spine member such as plate-like and the main body that is made of vertebra, and the bone of other skeleton).In some embodiments, dual cure material of the present invention can be used to increase the biological member of damage on the spot.According to these embodiments, this method comprises that surgery ground inserts mould structure the position of damage or prepares surgical site to serve as the reception mould of liquid dual cure material.This mould structure set be used for receiving the dual curable materials of liquid and geometrically to wait to substitute or set the similar setting of impaired biological member that is used for producing required result.Next, liquid dual cure material is introduced in the mould and carried out curing first time.This solidifies for the first time for example can be, uses up or thermal treatment.In some embodiments, this to solidify for the first time can be not exclusively to solidify so that allow this replacement structure comply with.The conformability of replacing structure can promote mould structure from the taking-up of damage location or replace the location of member at required surgery/implant position.After the removing of mould structure, this replaces structure to satisfy the required mechanical property for application-specific with further curing can to replace structure with solidification treatment first solidified for the second time.
In other embodiment, replacing member can increase, perhaps external or on the spot.According to these embodiments, can do forr a short time to the opening of surgical site, because this implant can once increase a part (for example, substituting hip joint by arthroscope type program) than the implant of this position requirement.In these embodiments, dual cure fluent material described herein can be introduced in mould or the surgical site and use first solidification treatment.This first first part so that this member that solidifies this fluent material formation replacement member of activation can keep desired shape.This first part can set and be used for solidifying post-hardening or keeping conformability first.Next, in some embodiments, the fluent material of second amount can be introduced second part of replacing member to form.With the material processing of first solidification treatment with second section.Being used for disposing this member second first solidification treatment partly can be that constructed so that each member maintenance that first part is used is that available second solidifies member.Therefore because each part of this device to keep be that available second solidifies member, so behind the device that first cured portion finishing of this device is finished with formation, can be with this part of second solidification treatment.After second curing, second curing component and the stratiform part that activates the stratiform part of this device will be bonded together the formation integral device.As described herein, can form a plurality of parts of replacing member, replace device to make as required.According to some embodiments, each part can have different functionalization and/or mechanical property to give required machinery and/or chemical results to the replacement member of finishing.
According to other embodiment, part can form and be attached on the natural joint on the spot as the articulum in joint with dual cure material of the present invention.According to these embodiments, artificial facet joint can be solidified (for example, thermofixation) manufacturing by first of dual cure material of the present invention.Artificial facet joint can be implanted to then on the articulum of preexist and solidify (for example, photocuring) and handle so that the articulum of this artificial facet joint and preexist bonds with second.
XVI.B. form device or implant and they are attached to tissue
According to other embodiment, dual cure material of the present invention can be used for substituting or increase natural biological tissue or structure and can be directly and tissue apposition.
According to some embodiments, dual cure material described herein can be introduced the repairing or the patchery of various types, as shown in figure 14.In one embodiment, this kind patchery can be used for the pneumochirurgia program.Patchery comprises, for example, but is not limited to, set be used for second curing mechanism by this dual cure material activation and directly adhere to thin slice with fixed dual cure material with living tissue.According to some embodiments, destroy or material, device or the surface of damage can be with materials repairing of the present invention (for example, patcheries).Shown in Figure 14 steps A-C, patchery can followingly be made: the dual cure material is molded as desired shape and activates first curing (for example, thermofixation) and formation patchery 1400.Next, patchery 1400 is placed on is damaged or damages the devices of (for example, crackle, hole, surgery change tissue) 1412 influences or organize on 1410.Patchery 1400 is placed on destroy on 1412 after, activate second curing mechanism (for example, photocuring) and this patchery adhered to the surface of device 1410.The intensity of patchery depends on a plurality of variablees, as patchery 1400 with organize the size of the bonded areas between 1410, give the state of cure of patchery/tissue combination, be used for chemical substance, amount, concentration of second solidification process etc., the composition of patchery 1400, the composition of tissue or device 1410, their combination etc.According to alternate embodiment, patchery 1400 can be experienced second curing (for example, heat or photocuring) and patchery 1400 is attached on compound, material or the material of known and tissue bond.For example, patchery 1400 can seal that component or cementing agent are handled or attached to it with fribrin, and this fribrin sealant compositions or cementing agent are known and are widely used for various clinical settings and are used for tissue is adhered to each other.In other embodiment, this patchery can be attached to second cured article on the biocompatible material and this biocompatible material then with tissue apposition, thereby implant this patchery.
In other embodiment, material of the present invention can be used for mfg. moulding die and duplicate another object.In some embodiments, treat that molding and the object that duplicates can be medical device or tissue, as joint component, organ, organ support, joint, frame member, tooth member, eyes member, vascular member etc.
According to these embodiments, shown in Figure 15 steps A-E, following mfg. moulding die: obtain object such as bone 1500 and this object is encapsulated in curable matrix 1502 as in the liquid PDMS precursor.Next, this curable matrix 1502 is solidified.Take out bone 1500 then, stay the mould 1504 that has with molding object 1500 corresponding shape.In some embodiments, curing mold is oppositely expanded to help to take out object.Next, can be with dual cure material of the present invention, for example dual cure liquid PFPE precursor 1510 is filled moulds 1502.Make this dual cure material 1510 stand first then and solidify (for example, thermofixation) is bone 1500 shapes with formation duplicate object 1512.Next, can with duplicate object 1512 as an alternative member implant in the main body.During implanting, can following duplicate object 1512 be attached to natural tissues, as joint cartilage, the part of remaining natural bone, ligament, tendon, on other artificial joint member etc.: with respect to duplicate object 1512 with tissue positioned and make this binding substances experience second solidify (for example, photocuring).
According to other embodiment, dual cure material of the present invention can be used for using in various cardiovascular application and other tube chamber.In some of these embodiments, this material can be used for making and/or increase the main body inner chamber and form artificial inner chamber (for example, artificial blood vessel).Dual cure material of the present invention can be as shown in figure 15 molding in addition, replace blood vessel and be used for substituting main intravital damage and/or interlock vascular to form.Material disclosed herein not only can serve as the conduit of blood flow, and they can also allow oxygen and nutrient substance to be diffused in the surrounding tissue by tube wall, thereby works as the normal health blood vessel very much.
According to embodiment of the present invention, the method that substitutes a blood vessel part on the spot comprises: oxygen is permeable, and the inner chamber of the part of the impermeable dual cure liquid of bacterium PFPE material injection blood vessel so that the surface, chamber that this dual cure liquid PFPE covers this blood vessel.Make this dual cure liquid PFPE experience first curing technology then in natural blood vessel, to form artificial blood vessel.Can from this first solidified PFPE material, take out biological blood vessel then and this material experience second is solidified maybe and can and can make this binding substances stand second with this material of another layer processing of dual curable liquid PFPE to solidify.In addition, when being bonded to this material on the natural blood vessel, can use second curing when artificial blood vessel being arranged in the research object and activate.Thereby produced the work quid pro quo of vasculature part.
With regard to the repairing and/or replacement of blood vessel, embodiment of the present invention are especially favourable.Because their high oxygen carrying capability and perviousness, the artificial blood vessel that is formed by the PFPE material has high functional and synthetic vasavasorum characteristic.The PFPE material allows oxygen via the wall diffusion and in the related tissue around entering, and allows the lasting nutrient substance diffusion and the diffusion of metabolite.The PFPE material mechanically imitates vascular basically, because they are flexible and conformability.In addition, embodiment of the present invention especially are suitable for the heart bypass surgery and as artificial arteriovenous shunt device.The PFPE material also can be used for the natural or synthetic arteriovenous shunt device of following repairing: the internal surface and as described herein being cured that cover damage or wearing and tearing vascular.According to other embodiment, the position that endoluminal prosthesis can be used for main body for example but is not limited to, and carries the bile tree, oesophagus, intestines, tracheobronchial tree, urinary tract etc.
In another embodiment, dual cure material of the present invention can be used for making the fixed mould of repairing vascular tissue.In some embodiments, this dual cure fluent material can be implanted and solidify in processes such as balloon angioplasty program partly, and in the curing of back, location experience or second curing partly.In these embodiments, can at first solidify the dual cure fluent material to form the steerable thin slice or the pipe of material.The manipulative capability of thin slice promotes the implantation of fixed mould precursor material.Can for example this fixed mould precursor material be located then by the angioplasty program.After with this fixed mould precursor location, this implant devices can make this fixed mould precursor material carry out second curing, thereby, produce mechanical available fixed mould.
According to embodiment of the present invention, dual cure PFPE material can use by device in all cardiovascular and tube chambers described herein.The PFPE material can be used for the material of these devices and/or the coating that can be used as on these devices provides.
According to other embodiment with shown in Figure 16 A-16C, the biological structure with inner chamber (for example, blood vessel) can be replaced with the medical device of dual cure material molding disclosed herein.Figure 16 shows the vertical view or the end view of the biological structure 1602 with inner chamber 1604.At first, replace in the vascular at molding, with temporary filling 1603 inner cavity filled 1604.Temporary filling 1603 can be PDMS, and foam maybe can insert the material that the another kind in the vascular 1602 is fit to.Filler 1603 can be applied in the inner chamber 1604, so that required pressure is applied on the wall of vascular 1602.The pressure that is applied on the wall of vascular 1602 can be the pressure of mimic biology condition, less than the pressure of normal biotic condition, greater than the pressure of normal biotic condition, the pressure of hope etc.Then vascular 1602 is encapsulated into curable outside matrix 1600, for example among the liquid PDMS.Next, solidified outer matrix 1600 so that vascular 1602 are clipped between outside matrix 1600 and the filler 1603.
Referring now to Figure 16 B,, produce reception space 1606 from taking out vascular 1602 between outside matrix 1600 and the filler 1603.Next, the replacement material (for example, liquid PFPE etc.) with dual cure ability described herein is transported to and receives in the space 1606.Replacement material can be injected, pour into, spraying or similar fashion be to receiving space 1606.Next, make replacement material experience first solidify (for example, light or thermofixation), so that its fixed (at least in part) and formation replacement device 1620.After first solidifies, remove outside matrix 1600 and filler 1603, replace device 1620 (Figure 16 C) thereby stay.Replace device 1620 and have outside surface 1610, internal surface 1612 and comprise its molding from the feature of natural biological structure.In addition, replace the inner chamber 1608 that device 1620 comprises the mimic biology structure inner chamber, this replaces device 1620 from this biological structure molding.
Next, in the position that natural therein member is removed or any implant place that other is fit to will be replaced device 1620 and will be arranged in the research object.To replace that device 1620 aligns with biological structure so that its is set and is used for adhering to and together playing a role and solidify (for example, heat or photocuring) with second with biological structure handling replacement device 1620.Second solidifies the component that device (described herein) is replaced in activation, this component again with on every side biological tissue's bonding, thereby will replace device 1620 implantation and paste with research object.In other embodiment, replacing device 1620 can combine with the known bioactive polymer that is attached to tissue in second curing schedule, so that should can combine with biological tissue via bioactive polymer by replacement device 1620.
According to another embodiment, this dual cure material can be used for forming rigid structure, and this rigid structure increases the skeleton part of supporting structure to research object.For example, the damage of increase can be other defective in crackle or the bone.In some embodiments, molding or at external formation dual cure fluent material and be solidified to form for the first time structure at first with required configuration.Next, can implant and locate this first consolidated structures with respect to damage biological structure to be increased.In case in position, just can be with this first solidify material of second solidification treatment with further fixed and/or be bonded on this biological structure.Dual cure mechanism of the present invention promotes the implantation of structure, reason be first solidify after, but this structure can keep specified shape be unusual conformability.The wound that when first conformability of solidifying the back structure can be reduced in implant infrastructure, patient is born.Second solidify after, this structure combines sealing crackle, and the biology member provide the structural support for damaging with adjacent tissue or biological member.Can change the composition of embedded material and degree of cure to obtain to have similar desired function, for example intensity, snappiness, rigidity, elasticity, their structure of combination etc.Therefore, the flexible material of dual cure can the interior ligament of substitution studies objective subject, tendon, cartilage, muscle etc. and tissue (for example, flexible tissue).
In another embodiment, dual cure material of the present invention can be used for forming other medical device, medical implant, and biology is replaced device, medical procedure instrument, surface treatment, their combination etc.Other useful application that the dual cure material can be applied to discloses in laid-open U.S. Patents application number 2005/0142315, comprises the publication of wherein quoting, and they all integrally are hereby incorporated by.
In another embodiment, the dual cure material of this paper disclosure and description can be used for forming the patterned surface feature on the surface of medical device.This patterned surface feature can provide the performance of usefulness and as the medical device coating for medical device.The surface patterning of medical device and medical implant can provide the coating of super-hydrophobicity, and this super-hydrophobic coating can be a not wettability of the convection cell utmost point.This patterned surface also can be highly anti-biofouling.The dual cure material can following composition: the Liquid precursor of dual cure material (is for example poured into the patterning template, silicon wafer) goes up or pass through photolithography, and handle this precursor to the first and solidify, this material is fixed or partly fixed and become the shape of pattern on patterned wafers by this.In some embodiments, this pattern can have the structure of the about 500nm of about 1nm-.In other embodiment, this pattern can have the structure of about 1 μ m-10 μ m.In one embodiment, this pattern is the multiple argyle design.
Next, take off first solidify material and produce patterned layer from this wafer.This kind layer then can be directly maybe can solidify via second by previously described quadrature curing as medical device and adhere on other object, thus the surface of coating medical device and implant and cause the wettability of reduction of this medical device or implant and the biological fouling possibility of reduction.
In other embodiment, the dual cure material can be used for dermatological applications, for example comprises band, dressing, wound healing applications, burn nursing product, reconstructive surgery, surgical glue mixture, suture etc.Because to be oxygen permeable and bacterium is impermeable for the PFPE material, be positioned at tissue under the PFPE band and can receive oxygen and prevent dust simultaneously, microbial organisms, pathogenic agent, and other pollutes and the toxic forms infiltration.In addition, the oxygen permeability of PFPE material and supporting capacity also can help prevent under band and dressing, or the health tissues necrosis under the zone for the treatment of.
According to one embodiment of the invention, " instantaneous skin " method on the research object main body of being applied to is comprised oxygen permeable, the impermeable liquid dual cure of bacterium PFPE material is coated on the part of research object main body.Can be with this dual cure of first solidification treatment PFPE material to form layer near predetermined size and/or shape.After first curing, the damage that this stratiform PFPE dual cure material is placed on patient is with.Make this dual cure PFPE stand second then and solidify so that this dual cure PFPE is attached to patient and provides oxygen permeable, microorganism is impermeable, and waterproof is flexible, elasticity, biocompatible artificial skin layer.
According to other embodiment, can form ocular implant and contact lens by dual cure material of the present invention.These devices are favourable with respect to the ocular implant and the contact lens of routine, because this PFPE material is can saturating and anti-biological fouling to oxygen.In addition, because lower surface energy, the result of the low friction that produces as this PFPE, more comfortable to the wearer.In addition, the refractive index of PFPE material can be regulated according to the optimum performance of ocular implant and contact lens.Other embodiment comprises the volute implant that uses dual cure PFPE material.Use dual cure PFPE material, the tissue in the growth is minimized, thereby make the safer and wound of removing of this device still less.
XVII. has material of nano level hole and forming method thereof
According to other embodiments of the present invention, the material of present disclosure has formed the nano level hole.This nano level hole can provide porous material and/or increase the perviousness of material.According to these embodiments, with the precursor that lower concentration will be fluoridized or fluorinated fluids is not incorporated herein description.This material of curing as described herein then includes but not limited to that UV solidifies, thermofixation, evaporation, their combination etc.Next, evaporation or remove this fluid from this solidify material.After from this solidify material, removing fluid, stay the nano level hole.These nano level holes can be given this material porousness, increase the perviousness of this material, they can be the interconnection or independently, their combination etc.According to an embodiment, concentration of fluid is less than about 15%.According to another embodiment, concentration of fluid is less than about 10%.In another embodiment, concentration of fluid is less than about 5%.According to these embodiments, fluid serves as pore generating agent (porogen), stays the nano level hole in curing elastomer, thereby increases the ventilation property of material, produces nanometer porous property in material, increases Test Liquid Permeability of Core, their combination etc.Other method of making the nano level hole in material of the present invention exists
People such as ChaoukUnited States Patent (USP) 6,160,030 in disclose, the document is incorporated herein by reference in this integral body, comprises all reference of wherein quoting.
XVIII. other application
According to other embodiments of the present invention, the tradition that adopts material of the present invention and method can improve silicone is used and according to other embodiment, and this application can be with material disclosed herein and method replacement.The silicone that material of the present invention and method are applicable to is used and is comprised releasing agent, release layer, and breathing mask resists to scratch the lacquer system; Water paint, sealing agent, the individual layer of mechanical assembly, microplate and cover, pipe arrangement, water-resisting agent and organic solvent protective agent.
Little extraction is that the another kind that material of the present invention and method can be applied to is used.For example, material of the present invention and method can be applied to substitute or improve prior art and the chemical substance of using in little extraction.An example of little extraction is at analytical chemistry [69 (6), 1197-1210,1997] describe in detail in the article in, wherein author's 80 microlitre fragments that OV-1 is extracted medium [poly-(dimethyl siloxane)] are placed on 50ml and have in the flask of 49ml aqueous specimen, shake this flask 45-100 minute, and took out this fragment, and place them in Shimadzu UV-260 spectrophotometer (Shimadzu Corp., Kyoto composes to obtain UV in separate slot Japan).What further described is pre-concentration by SPME, this SPME makes the UV absorption spectrum identify benzene under the investigative range of 97ppb, under 0.40ppb, identify naphthalene, under 0.41ppb, identify the 1-methylnaphthalene and under 5.5-12ppb, identify 8 kinds of other aromatic substance.Using white gasoline, in the test of the sample that JP4 rocket engine fuel and Numberl diesel fuel fuel are strengthened, pre-concentration allows the direct quantitative of the dilution level of aromatic substances in the aqueous specimen, and can not be subjected to the interference that matter is planted in corruption in the solution.
According to other embodiment, application of the present invention can replace traditional chromatographic separation material with material of the present invention and method.According to another embodiment of the present invention, material of the present invention and method can combine with typical chromatographic separation material.Can in following research, be described with the chromatographic separation that the present invention uses, be hereby incorporated by, this research has been described based on the natural enantiomerism distribution of the terpenol of various natural substrates and has been determined that though every kind of matrix is had any different, this distribution is distinguished widely.Though there is data available in the free bonded Linaool content in the Muscatel, the enantiomerism of the same terpenol in these wine is distributed does not have data available.DIFCA (di Chimica AnaliticaArgoali-mentare ed.Ambientale, Universita degli Studi diMilano, Via Celoria 2,20133 Milan, Italy; Tel:39 2 26607227, and Fax:39 2 2663057) the researchist used gas-chromatography (GC) chiral analysis to characterize Muscatel.In order to measure the aromatic fractions of Muscatel, must measure excessive Linaool and the alpha-terpineol of enantiomerism.F.Tateo uses two kinds of different fibers to be used for solid phase micro extraction (SPME) with M.Bononi, and a kind of is nonpolar (100 microns unconjugated polydimethylsiloxanes), and a kind of is polar (65 microns partial cross-linked polyoxyethylene glycol/Vinylstyrenes).Use pole filter to have the bigger absorption of Linaool.The enantiomerism of Linaool and alpha-terpineol is distributed in the limited field that is rather narrow and is the merit index of considering.In order to evaluate the selectivity of pole filter, use the data that obtain by direct injection to make contrast with respect to the SPME absorption of many molecules.Use this technology to obtain the bigger susceptibility of molecule.
In other application, material of the present invention and method can replace the PDMS material that uses in the outdoor electric capacity, for example are used for covering the PDMS porcelain patticoat material of pressurizing chamber outer insulator.According to other embodiment, material of the present disclosure and method can with outdoor electric capacity, the PDMS material combination of using in the outer insulator porcelain patticoat of for example above-mentioned pressurizing chamber.Importantly, the surface of the porcelain patticoat of isolator keeps hydrophobicity in its whole length of life.Yet, be known that discharge causes the oxidation and the hydrophobic temporary transient loss on traditional surface.Research according to traditional material, to comprise Irganox 1076, Tinuvin 770 or Irganox 565 (Ciba SpecialtyChemicals Corp., Tarrytown, New York, United States of America) crosslinked polydimethylsiloxane (PDMS) (by make the preparation of PDMS swelling in the solution of one of these stablizers in normal hexane) is exposed in the corona discharge and measures the corona exposure duration (t-crit) that forms fragility, silicon-dioxide shape layer by optical microscopy.This critical corona exposure duration shows that the linearity that increases with stabilizer concentration increases; Tinuvin 770 shows top efficiency, and Irganox 1076 shows minimum efficiency.According to the value of unstable PDMS, the increase of the t-crit that exposes based on the corona of stablize sample with previously for the sample of air plasma exposure report similar.The efficient of the surface oxidation of the PDMS that stablizer causes for corona is also confirmed by x-ray photoelectron spectroscopy.Yet what those of ordinary skills will understand is to use the traditional material of PDMS to be improved significantly by addition or the increase with material of the present invention and method.
Proposed the little valve by the paraffinic hydrocarbons driving, for example the little valve that contains silicone-rubber seal that drives by the heating and cooling paraffinic hydrocarbons is used to be developed as the integrated member of microfluid system.According to one embodiment of the invention, material of the present invention and method can replace, or combine with silicone-rubber seal as these devices of disclosed little valve material, thereby increase this physics and chemical property of valve slightly.
Not having the scratch surface is another application that material of the present invention and method can be applied to.Material of the present invention and method can replace or be used for increasing traditional nothing abrading physics and the chemical property of material to improve them.For example, Dow Corning of Freeland, the research of MI has shown adds the scratch resistance of masterbatch to the middle TPO of improvement of thermoplastic olefin (TPO) member.The MB50 series masterbatch of the said firm is the vector resin pattern that contains 50% ultra-high molecular weight polydimethylsiloxane, anti-scratch liniment and slip additive.This additive reduces the frictional coefficient of molded parts surface.Use surface modification to be used for various application with masterbatch and exploitation now, for example be used for automotive field, wherein it is being used for supervisory control desk, air bag, door skin and external member.Replace this type of no scratch-off surface material with material of the present invention and method, or with material of the present invention and method with it in conjunction with the scratch resistance that can improve this material.
Material of the present invention and method also can be applied to material and the method used in the manufacturing of transmitter.Material of the present invention and method be applied to be used for making transmitter, for example example those of ordinary skills of polymeric film paste composition will understand from following.Poly-(vinylchlorid) compound of urethane/hydroxylation and silicone-based compounds that favourable polymeric film paste composition is included in the proper solvent system have suitable viscosity and the printable paste of thixotropic silk screen to provide.For will be at commercial acceptable ionization sensor, it must have the quality that exceeds aspect chemical property.For with the cost effective sensor, it must use mass production system to reproduce.In mass-producted group member, must there be total electrochemical response characteristic.If this transmitter is all not substantially the same, then they separately with outstanding behaviours in different life-spans and response characteristic, produce the difficulty in this area, the inferior limit in them be not when changing transmitter with the interpolation of calibration cost related again of device.Polymeric film is usually as the transmodulator in the solid state chemistry transmitter, especially because this type of film has high to the ionic selectivity considered and can use a kind of perhaps many ionophores that can obtain easily to make many ions are selectivity.A kind of known technology that is used to form film is a solvent casting; The technology of following the ion specific electrode technology to take place.Except quite tediously long operation, particularly consider the small size of transmitter, this preparation method also produces very high loss.The thickness of this film and shape can not Be Controlled, cause the unacceptable shortage of transmitter reproducibility.The research purpose of University of Michigan is for the simple and economical system that provides is provided the intermittence of solid ionic selective sensor.Their method constitutes by mask is installed on semiconductor substrate, and this mask has at least one hole, and this hole has and the required corresponding predetermined configuration of film configuration.The polymeric film paste is applied on the mask, and on whole mask, is communicated with to force this paste to enter this Kong Bingyu semiconductor substrate with the rubber roll calendering.In one form, mask has metallic substance, and this metallic substance can be the stainless steel sieve aperture that scribbles the photoreactivity emulsion.In another form, this mask is the tinsel template.The final film that produces has the thickness corresponding with this mask, the 25-250 micron.This film paste can be formed by following material: the urethane with poly-(vinylchlorid) multipolymer of effective ratio hydroxylation; The polyimide based compound; Silicone-based compounds, as have the end capped polydimethylsiloxane of silanol that resistance reduces additive, CN deutero-silicone rubber; Or any polymer materials that other is fit to.Therefore, should be appreciated that material of the present invention and method can be applied to form transmitter, as polymer film composition, polyimide based compound, the material of polydimethylsiloxane and silicone rubber and method.
In another embodiment, material of the present invention and method can replace maybe can being used for expanding material and the method for using in the little extraction of collosol and gel kapillary.Usually, sol-gel technique relates in micron and nano level matrix, silicon-dioxide based substrate, and encapsulated active ingredients in the nanometer spheroid usually.For example, the little extraction of collosol and gel kapillary (collosol and gel CME) is the solvent-free extractive technique of available that is used for pre-concentration trace analysis thing.The kapillary that collosol and gel applies is generally used for extracting and various polarity of pre-concentration and nonpolar analyte.Two kinds of dissimilar sol-gel coatings are used for extracting: collosol and gel poly-(dimethyl siloxane) (PDMS) gathers (ethylene glycol) (PEG) with collosol and gel.Gravity feeding sample distribution device can be used for carrying out this extraction.The analysis of the analyte that extracts can be undertaken by vapor-phase chromatography (GC).Via thermal desorption the analyte that extracts is transferred to the GC post.For this reason, the kapillary with analyte of extraction can use two-way press-fit fused silica junctor to be connected with the inlet end of GC post, and this junctor is encapsulated in the GC injection port.Analyte with extract desorb capillaceous can be program control by the fast temperature of GC injection port (100 ℃/min) carry out.The analyte of desorb is further concentrated along this system's transportation and at the inlet end place of GC post by helium flow, and this GC post maintains under 30 ℃.Collosol and gel PDMS kapillary be usually used in extracting nonpolar and middle polarity compound (such as but not limited to, polycyclic aromatic hydrocarbons, aldehyde, ketone), and collosol and gel PEG kapillary is used to extract polar compound (for example, but being not limited to alcohol, phenol, amine).For polarity and nonpolar analyte, the round of GC peak area remains on respectively under 6% and 4% kapillary relative standard deviation (RSD) value usually to round and kapillary.By collosol and gel CME and gas-chromatography/flame ionization are surveyed the detection limit that (GC-FID) coupling has obtained part/quadrillion level.Use the more long capillary fragment (or kapillary) of thicker sol-gel coating and larger diameter to cause the further raising of extracting sensitivity usually with collosol and gel integral bed.What those of ordinary skills will understand is, substitutes or in conjunction with being usually used in efficient and the validity that matrix that collosol and gel uses and nanometer spheroid can improve sol-gel method with material of the present invention and method.
In alternate embodiment, material of the present invention and method can be applied to technology, for example the processing aid of plastics and membrane separation process.The example of the membrane separation process that can use with the present invention is at Membrane ﹠amp; Separation Technology News, v.15:no.6, February 1,1997 (ISSN-0737-8483)) is described in.
Method of the present invention includes but not limited to the article that material can expand or other silicone of alternate is relevant, U.S. Patent number 6,887,911; 6,846,479; 6,808,814; 6,806,311; 6,804,062; 6,803,103; Disclosure in 6,797,740; Application No. 2005/0147768; 2005/0112385; 2005/0111776; 2005/0091836; Disclosure in 2005/0052754; With the disclosure among the EP1533339A1, each piece of writing in them integrally is hereby incorporated by data.
XIX. the sacrifice layer device is made
According to embodiments more of the present invention, material described herein is used for forming the device of making according to the sacrifice layer method, for example microfluidic device.Via controlled exposure, for example make and concentrate light source through grating, via mask flood exposure, Zu Zhi precision light source highly, their combination etc., the specific photoetching composition of curable materials disclosed herein provides the manufacturing of polymers micro-devices.In addition, according to embodiment of the present invention, the living radical photopolymerization of material disclosed herein provides the parallel manufacturing of multilayer device.Specific initiator chemical process is used in the living radical photopolymerization, and they are at the process that is exposed to the UV light that is used for synthesizing linear polymkeric substance reactivate continuously.According to some embodiments, not end-blocking or the passivation for good and all and combine of the polymkeric substance end of the chain with cross-linking monomer, the living radical photopolymerization can make new polymer chain or film cause and covalency adheres on the surface of photopolymerisable structure before this.
According to some embodiments, polymkeric substance can be used to produce the three-dimensional design with high complexity, the micro element of extremely general surface and a lot of physics and chemical property, for example microfluidic device as the light pattern polymeric method of polymkeric substance disclosed herein.In alternative method, material disclosed herein can with material, as filtering medium, different polymerisable monomer preparatons, photocurable agent, thermal curable agent, combination such as their combination and form the layer bonded that can be used as one-piece construction or device and solidify member.After the initial solidification of this material, adjacent layers or device can adhere to each other with covalent via second solidification process described herein or program, to form complicated multilayer device.
According to some embodiments, material property can initial following selection: change the composition of base mateiral and/or the monomer prescription in the base mateiral according to material described herein and method, so that the gained layer of device or this device itself will play a role for predetermined the application.
According to Figure 18, provide reaction chamber 1800.Reaction chamber 1800 usually and cup similarly be shaped, have side 1802, so that it can enclosing liquid 1804, and does not allow this liquid overflow from chamber 1800.That chamber 1800 can have is smooth, crooked or similar bottom chamber or can have and comprise section bar or groove 1806 therein.Chamber 1800 preferably has side 1802, and its height that has is equal to or greater than the height of required device.In some embodiments, side 1802 is arrived between about 100mm at about 1nm.According to other embodiment, side 1802 is between about 1 micron to about 500 microns.According to other embodiment, side 1802 is arrived between about 50mm at about 50nm.With fluent material 1804, material for example disclosed herein, for example, the derivative of PFPE disclosed herein or PFPE is introduced chamber 1800 and is filled into predetermined depth.This desired depth can be determined by the desired thickness of obtained device for the treatment of to make in first manufacturing step or layer.
According to some embodiments, with mask 1810, the optical mask that for example has required mask design or pattern aligns system 1812 and is placed on above the liquid polymers material 1810 or contact with it.In some embodiments, mask 1810 is made by commercially available emulsion film with high resolving power plotting apparatus.According to these embodiments, mask 1810 is made by rapid prototyping production and device optimization.For example these produce about 10 microns resolving power usually to use mask manufacture method.According to other embodiment, higher resolving power, promptly less than about 1 micron and/or more durable mask can by with chromium deposition on etched silica glass or the alternate printing process make.Mask 1810 can the service recorder marking or the optical orientation arranging system align.In some embodiments, use up or UV curing 1830, for example described herein those are handled the mask 1810 and the fluent material 1804 of pattern 1812 exposures of passing through mask 1810.In some embodiments, curing 1830 activates the photocurable monomer component in the fluent material 1804 so that press the pattern cured fluent material 1804 according to the pattern 1812 of mask 1810.According to other embodiment, after fluent material 1804 is introduced chambers 1800, with the light source treatment liq material of highly organizing 1804 consequently the predetermined zone originally of fluent material 1804 be solidified into solid form or solid form basically.If use mask 1810, then then it is removed and by removing any uncured fluent material 1804 with the uncured fluent material 1804 of solvent treatment.
According to some embodiments, form and the second layer or second device are adhered on the initial solidified fluent material 1804 and may be wished.According to these embodiments, removing hole 1818 usefulness sacrifice layers 1820 fillings that stay behind the uncured fluent material 1804.In some embodiments, sacrifice layer 1820 can be a wax, for example paraffin etc.Sacrifice layer 1820 preferably liquid or molten solids so that its filling pore 1818 with the open space in the reserved materials, for example raceway groove in the solidify material, valve port or opening, groove etc.According to some embodiments, filling pore 1818 so that with the flush of initial solidified fluent material 1826 or link up.In some embodiments, come out in the surface of removing excessive sacrifice layer so that initial solidified fluent material 1826.
Next, second fluent material 1824 is incorporated on the surface and sacrifice layer 1820 of initial solidified fluent material 1826.As mentioned above, will have pattern 1812, the second patterns 1814 then, the mask 1810 of precision light source etc. is transported on second fluent material 1824 so that the predetermined portion of second fluent material 1824 becomes photoactivation and curing.The height of the space domination second layer between photomask and the previous layer.In photoactivation and solidification process, second fluent material 1824 also can chemical bonding to initial solidified fluent material 1804, thereby these two layers adhered to each other and form individual devices.Above-mentioned technology can repeat and form a plurality of stratiform predetermined three-dimensional structures.After the manufacturing of desired structure, remove any sacrifice layer 1820 from this structure, for example by heating or with this structure of solvent treatment.This sacrifice layer 1820 is removed method can be similar to the negative type photoresist chemical process in some embodiments; Behind solvent washing, remove unexposed zone and keep exposed areas.In some embodiments, according to the required purposes of device, layer subsequently can have identical or different physical configuration and/or identical or different material is formed and/or performance.In some embodiments, section bar or groove 1806 can be included in the chamber 1800.Therefore, when when solidifying first fluent material 1804 around the section bar 1806, remove solidified first fluent material 1826 from chamber 1800 after, section bar will stay space 1816 in solidified first fluent material 1826.In some embodiments, section bar 1806 can be a chamber common and that microfluidic device is got in touch, passage, the system of chamber, valve port etc.
According to other embodiment, the base mateiral of device can comprise thermal curable components disclosed herein.According to these embodiments,, as mentioned above, can handle this device with thermofixation by after building up a plurality of layers of this device of manufacturing.Thermofixation activates the thermal curable components of base mateiral and further a plurality of layers is adhered to each other and maybe this device can be adhered on second device.
According to some embodiments, the material 1804 of this device can comprise structure division structure division for example disclosed herein, for example top structure division with respect to the 4th preceding volume description.According to these embodiments, this structure division precursor keeps utilizing the sample that consequently passes through on this surface to react with this structure division in the surface of solidifying device.Many functions of carrying out in the microfluidic device depend on the chemical substance of fluid and transportation or the interaction between the biological compound, therefore, manufacturing has the microfluidic device of functionalized structure part precursor, and this structure division precursor keeps after the manufacturing of device can promote micro fluid reaction and can utilize.According to some embodiments, the structure division that is included in the material 1804 can be selected and changes according to the required function of making device.Usually, the space controlled surface performance that is different from the block materials performance is wished in microfluidic device.For example, in some embodiments, the living radical initiator is introduced monomer formulation and can be made it possible to via grafting or the modification of photolithography with the surperficial living radical photopolymerization implementation space resolution of reconciling.
All reference that this paper quotes integrally are incorporated herein by reference at this, comprise all reference of wherein quoting.
Embodiment
Following examples have comprised and have been used for providing for those of ordinary skills the guidance of the representative embodiment of putting into practice disclosure theme.According to present disclosure and those skilled in the art's common level, it only is to be used for illustrating that the technician can understand following examples, and can use many changes, modifications and variations under the situation of the scope that does not break away from disclosure theme.
Overall consideration
The PFPE microfluidic device before this by
Rolland, J.Deng people's JACS2004,126,2322-2323 carried out report, and the document is incorporated herein by reference in this integral body.
Rolland, J.Deng the disclosed specific PFPE material of people be non-chain extension and therefore do not have a plurality of hydrogen bonds, described hydrogen bond basicly exists during with the PFPE chain extension when adopting vulcabond to connect.This material does not have the mechanical property of improvement such as modulus and the necessary higher molecular weight of tear strength yet between cross-linking set, these mechanical propertys are critical to various microfluidic applications.In addition, this material does not functionalised to introduce various structure divisions, as charge species, biomacromolecule or catalyzer.
This paper has described the whole bag of tricks that addresses these problems.Being included in these in improving is to have described chain extension, to a plurality of PFPE layers and to other base material as the improved adhesion of glass, silicon, quartz and other polymkeric substance and the method that can introduce functionalized monomer's (as described in functionalized monomer can change wettability or attached catalyst, biomolecules or other material).What also described is PFPE elastomerics solidified is improved one's methods, and this method comprises that hot radical solidifies, two-pack curing chemistry and make photocuring with the light acid producing agent.
Embodiment 1
The liquid PFPE precursor (wherein n=2) of structure and the blend of 1wt% free radical photo-initiation shown in below will having also are poured on the microfluid main body (master), and this microfluid main body comprises the 100 μ m features that are channel shape.Use the PDMS mould in desired zone, to hold the thickness of this liquid to about 3mm.Then this wafer (wafer) is put into the UV chamber and under nitrogen purging, be exposed to following 10 minutes of UV light (λ=365).Individually, with the small droplets of this liquid PFPE precursor under the 3700rpm on the top of second main body 1 minute thickness of this second main body of spin coating to about 20 μ m, this second main body comprises the 100 μ m features that are channel shape.Then this wafer is put into the UV chamber and under nitrogen purging, be exposed to following 10 minutes of UV light (λ=365).The 3rd, by the small droplets blade coating of liquid PFPE precursor having been formed smooth, smooth PFPE layer on slide glass with scraper plate.Then slide glass is put into the UV chamber and under nitrogen purging, be exposed to following 10 minutes of UV light (λ=365).Remove, repair this then than thick-layer, and use luer stub to allow the ingate punching press pass this layer.Then this layer is placed on above the thick layer of this 20 μ m and in required zone, aligns to form sealing member.Then this layer is put into baking oven and descended heating 2 hours at 120 ℃.Repair this thin layer then and mention this adherent layer from this main body.Use luer stub punching press fluid provider and outlet opening.Then the layer of this keyed jointing is placed on the completely crued PFPE smooth layer on the slide glass and 120 ℃ of heating 15 hours down.Little nozzle needle can be put into this inlet then with introducing fluid and drive membrane valve, as
Unger.M.Deng people's Science.2000,288,113-6 reports.
Embodiment 2
Hot radical
Glass
Will be by methacrylate based group end capped liquid PFPE precursor and 1wt%2, the blend of 2-Diisopropyl azodicarboxylate also is poured on the microfluid main body, and this microfluid main body comprises the 100 μ m features that are channel shape.Use the PDMS mould in desired zone, to hold the thickness of this liquid to about 3mm.The baking oven of this wafer being put into 65 ℃ then under nitrogen purging kept 20 hours.Remove, repair this cured layer then, and use luer stub to allow the ingate punching press pass this layer.Then this layer is placed on above the slide glass of cleaning and can introduces fluid via this ingate.
Embodiment 3
Hot radical-partly solidified
Layer adheres to layer
Will be by methacrylate based group end capped liquid PFPE precursor and 1wt% 2, the blend of 2-Diisopropyl azodicarboxylate also is poured on the microfluid main body, and this microfluid main body comprises the 100 μ m features that are channel shape.Use the PDMS mould in desired zone, to hold the thickness of this liquid to about 3mm.The baking oven of this wafer being put into 65 ℃ then under nitrogen purging kept 2-3 hour.Individually, with the small droplets of this liquid PFPE precursor under the 3700rpm on the top of second main body 1 minute thickness of this second main body of spin coating to about 20 μ m, this second main body comprises the 100 μ m features that are channel shape.The baking oven of this wafer being put into 65 ℃ then under nitrogen purging kept 2-3 hour.The 3rd, by the small droplets blade coating of liquid PFPE precursor having been formed smooth, smooth PFPE layer on slide glass with scraper plate.The baking oven of this wafer being put into 65 ℃ then under nitrogen purging kept 2-3 hour.Remove, repair this then than thick-layer, and use luer stub to allow the ingate punching press pass this layer.Then this layer is placed on above the thick layer of this 20 μ m and in required zone, aligns to form sealing member.Then this layer is put into baking oven and descended heating 10 hours at 65 ℃.Repair this thin layer then and mention this adherent layer from this main body.Use luerstub punching press fluid provider and outlet opening.Then the layer of this keyed jointing is placed on the partly solidified PFPE smooth layer on the slide glass and 65 ℃ of heating 10 hours down.Little nozzle needle can be put into this inlet then with introducing fluid and drive membrane valve, as
Unger.M.Deng people's Science.2000,288,113-6 reports.
Hot radical-partly solidified
Adhesion with urethane
The photocurable liquid polyurethane precursor and the 1wt%2 that will comprise methacrylate based group, the blend of 2-Diisopropyl azodicarboxylate also is poured on the microfluid main body, and this microfluid main body comprises the 100 μ m features that are channel shape.Use the PDMS mould in desired zone, to hold the extremely roughly thickness of 3mm of this liquid.The baking oven of this wafer being put into 65 ℃ then under nitrogen purging kept 2-3 hour.Individually, in that this second main body of spin coating 1 minute is to the thickness of 20 μ m roughly on the top of second main body under the 3700rpm, this second main body comprises the 100 μ m features that are channel shape with the small droplets of this liquid PFPE precursor.The baking oven of this wafer being put into 65 ℃ then under nitrogen purging kept 2-3 hour.The 3rd, by the small droplets blade coating of liquid PFPE precursor having been formed smooth, smooth PFPE layer on slide glass with scraper plate.The baking oven of this wafer being put into 65 ℃ then under nitrogen purging kept 2-3 hour.Remove, repair this thicker layer then, and use luerstub to allow the ingate punching press pass this layer.Then this layer is placed on above the thick layer of this 20 μ m and in required zone, aligns to form sealing member.Then this layer is put into baking oven and descended heating 10 hours at 65 ℃.Repair this thin layer then and mention this adherent layer from this main body.Use luer stub punching press fluid provider and outlet opening.Then the layer of this keyed jointing is placed on the partly solidified PFPE smooth layer on the slide glass and 65 ℃ of heating 10 hours down.Little nozzle needle can be put into this inlet then with introducing fluid and drive membrane valve, as
Unger.M.Deng people's Science.2000,288,113-6 reports.
Embodiment 5
Hot radical-partly solidified
Adhesion to the urethane that contains silicone
The photocurable liquid polyurethane precursor and the 1wt% 2 that will comprise PDMS block and methacrylate based group, the blend of 2-Diisopropyl azodicarboxylate also is poured on the microfluid main body, and this microfluid main body comprises the 100 μ m features that are channel shape.Use the PDMS mould in desired zone, to hold the extremely roughly thickness of 3mm of this liquid.The baking oven of this wafer being put into 65 ℃ then under nitrogen purging kept 2-3 hour.Individually, in that this second main body of spin coating 1 minute is to the thickness of 20 μ m roughly on the top of second main body under the 3700rpm, this second main body comprises the 100 μ m features that are channel shape with the small droplets of this liquid PFPE precursor.The baking oven of this wafer being put into 65 ℃ then under nitrogen purging kept 2-3 hour.The 3rd, by the small droplets blade coating of liquid PFPE precursor having been formed smooth, smooth PFPE layer on slide glass with scraper plate.The baking oven of this wafer being put into 65 ℃ then under nitrogen purging kept 2-3 hour.Remove, repair this then than thick-layer, and use luer stub to allow the ingate punching press pass this layer.Then this layer is placed on above the thick layer of this 20 μ m and in required zone, aligns to form sealing member.Then this layer is put into baking oven and descended heating 10 hours at 65 ℃.Repair this thin layer then and mention this adherent layer from this main body.Use luer stub punching press fluid provider and outlet opening.Then the layer of this keyed jointing is placed on the partly solidified PFPE smooth layer on the slide glass and 65 ℃ of heating 10 hours down.Little nozzle needle can be put into this inlet then with introducing fluid and drive membrane valve, as
Unger.M.Deng people's Science.2000,288,113-6 reports.
Embodiment 6
Hot radical-partly solidified
Adhesion to the PFPE-PDMS segmented copolymer
To comprise simultaneously by the Liquid precursor of end capped PFPE of methacrylate based group and PDMS block and 1wt% 2, the blend of 2-Diisopropyl azodicarboxylate also is poured on the microfluid main body, and this microfluid main body comprises the 100 μ m features that are channel shape.Use the PDMS mould in desired zone, to hold the extremely roughly thickness of 3mm of this liquid.The baking oven of this wafer being put into 65 ℃ then under nitrogen purging kept 2-3 hour.Individually, in that this second main body of spin coating 1 minute is to the thickness of 20 μ m roughly on the top of second main body under the 3700rpm, this second main body comprises the 100 μ m features that are channel shape with the small droplets of this liquid PFPE precursor.The baking oven of this wafer being put into 65 ℃ then under nitrogen purging kept 2-3 hour.The 3rd, by the small droplets blade coating of liquid PFPE precursor having been formed smooth, smooth PFPE layer on slide glass with scraper plate.The baking oven of this wafer being put into 65 ℃ then under nitrogen purging kept 2-3 hour.Remove, repair this then than thick-layer, and use luer stub to allow the ingate punching press pass this layer.Then this layer is placed on above the thick layer of this 20 μ m and in required zone, aligns to form sealing member.Then this layer is put into baking oven and descended heating 10 hours at 65 ℃.Repair this thin layer then and mention this adherent layer from this main body.Use luer stub punching press fluid provider and outlet opening.Then the layer of this keyed jointing is placed on the partly solidified PFPE smooth layer on the slide glass and 65 ℃ of heating 10 hours down.Little nozzle needle can be put into this inlet then with introducing fluid and drive membrane valve, as
Unger.M.Deng people's Science.2000,288,113-6 reports.
Embodiment 7
Hot radical-partly solidified
Glass adheres to
Will be by methacrylate based group end capped liquid PFPE precursor and 1wt% 2, the blend of 2-Diisopropyl azodicarboxylate also is poured on the microfluid main body, and this microfluid main body comprises the 100 μ m features that are channel shape.Use the PDMS mould in desired zone, to hold the thickness of this liquid to about 3mm.The baking oven of this wafer being put into 65 ℃ then under nitrogen purging kept 2-3 hour.Remove this partly solidified layer from this wafer, and use luer stub to be stamped into oral pore.Then this layer is placed on above the slide glass of handling with silane coupling agent (methacrylic acid trimethoxysilyl propyl ester).Then this layer is put into baking oven and descended heating 20 hours, thereby this PFPE layer for good and all is keyed on the slide glass at 65 ℃.Little nozzle needle can be put into this inlet then to introduce fluid.
Embodiment 8
Hot radical-partly solidified
PDMS adheres to
Poly-(dimethyl siloxane) precursor of liquid is poured on the microfluid main body that comprises the 100 μ m features that are channel shape.The baking oven of then this wafer being put into 80 ℃ kept 3 hours.Individually, use by the small droplets of the end capped liquid PFPE of methacrylate unit precursor 1 minute thickness to about 20 μ m of spin coating second main body under 3700rpm, this second main body comprises the 100 μ m features that are channel shape.The baking oven of this wafer being put into 65 ℃ then under nitrogen purging kept 2-3 hour.Remove, repair this PDMS layer then, and use luer stub to allow the ingate punching press pass this layer.With this layer of oxygen plasma treatment 20 minutes, then handle then with silane coupling agent (methacrylic acid trimethoxysilyl propyl ester).Then treated PDMS layer is placed on above the partly solidified PFPE thin layer and and heated 10 hours down at 65 ℃.Repair this thin layer then and mention this adherent layer from this main body.Use luer stub punching press fluid provider and outlet opening.Then the layer of this keyed jointing is placed on the partly solidified PFPE smooth layer on the slide glass and 65 ℃ of heating 10 hours down.Little nozzle needle can be put into this inlet then with introducing fluid and drive membrane valve, as
Unger.M.Deng people's Science.2000,288,113-6 reports.
Hot radical
Poly-(dimethyl siloxane) precursor of liquid can be SYLGARD 184 through design so that it
Base-material or the part of curing component.This precursor comprises potential functional group such as epoxy group(ing), methacrylic ester or amine and mixes with the standard solidifying agent, and is poured on the microfluid main body that comprises the 100 μ m features that are channel shape.The baking oven of then this wafer being put into 80 ℃ kept 3 hours.Individually, use that spin coating second main body 1 minute is to the thickness of 20 μ m roughly under 3700rpm by the small droplets of the end capped liquid PFPE of methacrylate unit precursor, this second main body comprises the 100 μ m features that are channel shape.The baking oven of this wafer being put into 65 ℃ then under nitrogen purging kept 2-3 hour.Remove, repair this PDMS layer then, and use luer stub to allow the ingate punching press pass this layer.Then the PDMS layer is placed on above the partly solidified PFPE thin layer and and heated 10 hours down at 65 ℃.Repair this thin layer then and mention this adherent layer from this main body.Use luerstub punching press fluid provider and outlet opening.Then the layer of this keyed jointing is placed on the partly solidified PFPE smooth layer on the slide glass and 65 ℃ of heating 10 hours down.Little nozzle needle can be put into this inlet then with introducing fluid and drive membrane valve, as
Unger.M.Deng people's Science.2000,288,113-6 reports.
Embodiment 10
Resins, epoxy/amine
The two ingredient liquids PFPE precursor systems of the PFPE of comprising diepoxy resin as shown below and PFPE diamines is in the same place by the stoichiometric ratio blend, and is poured on the microfluid main body that comprises the 100 μ m features that are channel shape.Use the PDMS mould in desired zone, to hold the thickness of this liquid to about 3mm.The baking oven of then this wafer being put into 65 ℃ kept 5 hours.Remove, repair this cured layer then, and use luer stub to allow the ingate punching press pass this layer.Then this layer is placed on above the slide glass of cleaning and can introduces fluid via this ingate.
Embodiment 11
Resins, epoxy/amine-excessive
Adhesion to glass
With the two ingredient liquids PFPE precursor systems of the PFPE of comprising diepoxy resin as shown below and PFPE diamines in 4: 1 epoxy group(ing): the ratio blend of amine and is poured on the microfluid main body that comprises the 100 μ m features that are channel shape together so that have excessive epoxy group(ing).Use the PDMS mould in desired zone, to hold the thickness of this liquid to about 3mm.The baking oven of then this wafer being put into 65 ℃ kept 5 hours.Remove, repair this cured layer then, and use luer stub to allow the ingate punching press pass this layer.Then this layer is placed on above the cleaning slide glass of using silane coupling agent (aminopropyltriethoxywerene werene) processing.Then 65 ℃ down these slide glasss of heating 5 hours so that this device for good and all is keyed on the slide glass.Can introduce fluid via this ingate then.
Embodiment 12
Resins, epoxy/amine-excessive
Adhesion to the PFPE layer
With the two ingredient liquids PFPE precursor systems of the PFPE of comprising diepoxy resin as shown below and PFPE diamines in 1: 4 epoxy group(ing): the ratio blend of amine and is poured on the microfluid main body that comprises the 100 μ m features that are channel shape together so that have excessive amine.Use the PDMS mould in desired zone, to hold the thickness of this liquid to about 3mm.Individually, with in 4: 1 epoxy group(ing): the small droplets of the liquid PFPE precursor of the ratio blend of amine (so that having excessive epoxy group(ing) unit) applies second main body and spin coating 1 minute is to the thickness of 20 μ m roughly under 3700rpm, and this second main body comprises the 100 μ m features that are channel shape.The baking oven of then this wafer being put into 65 ℃ kept 5 hours.Remove, repair this thick-layer then, and use luer stub to allow the ingate punching press pass this layer.Then this thick-layer is placed on above the solidified PFPE thin layer and and heated 5 hours down at 65 ℃.Repair this thin layer then and mention this adherent layer from this main body.Use luer stub punching press fluid provider and outlet opening.Layer with this keyed jointing is placed on the slide glass of handling with silane coupling agent (aminopropyltriethoxywerene werene) then, and heats 5 hours so that this device adheres on this slide glass in 65 ℃ baking oven.Little nozzle needle can be put into this inlet then with introducing fluid and drive membrane valve, as
Unger.M.Deng people's Science.2000,288,113-6 reports.
Embodiment 13
Resins, epoxy/amine-excessive
Adhesion to the PDMS layer
Poly-(dimethyl siloxane) precursor of liquid is poured on the microfluid main body that comprises the 100 μ m features that are channel shape.The baking oven of then this wafer being put into 80 ℃ kept 3 hours.Individually, with in 4: 1 epoxy group(ing): the small droplets of the liquid PFPE precursor of the ratio blend of amine (so that having excessive epoxy group(ing) unit) applies second main body and spin coating 1 minute is to the thickness of 20 μ m roughly under 3700rpm, and this second main body comprises the 100 μ m features that are channel shape.The baking oven of then this wafer being put into 65 ℃ kept 5 hours.Remove, repair this PDMS layer then, and use luerstub to allow the ingate punching press pass this layer.Then handled in 20 minutes with this layer of oxygen plasma treatment then with silane coupling agent (aminopropyltriethoxywerene werene).Then treated PDMS layer is placed on above the PFPE thin layer and and heated 10 hours down so that this two layers adhere at 65 ℃.Repair this thin layer then and mention this adherent layer from this main body.Use luer stub punching press fluid provider and outlet opening.Layer with this keyed jointing is placed on heating 10 hours down on the slide glass of aminopropyltriethoxywerene werene processing and at 65 ℃ then.Little nozzle needle can be put into this inlet then with introducing fluid and drive membrane valve, as
Unger.M.Deng people's Science.2000,288,113-6 reports.
Embodiment 14
Resins, epoxy/amine-excessive
To the adhesion of PFPE layer, the adhering to of biomolecules
With the two ingredient liquids PFPE precursor systems of the PFPE of comprising diepoxy resin as shown below and PFPE diamines in 1: 4 epoxy group(ing): the ratio blend of amine and is poured on the microfluid main body that comprises the 100 μ m features that are channel shape together so that have excessive amine.Use the PDMS mould in desired zone, to hold the thickness of this liquid to about 3mm.Individually, with in 4: 1 epoxy group(ing): the small droplets of the liquid PFPE precursor of the ratio blend of amine (so that having excessive epoxy group(ing) unit) applies second main body and spin coating 1 minute is to the thickness of 20 μ m roughly under 3700rpm, and this second main body comprises the 100 μ m features that are channel shape.The baking oven of then this wafer being put into 65 ℃ kept 5 hours.Remove, repair this thick-layer then, and use luer stub to allow the ingate punching press pass this layer.Then this thick-layer is placed on above the solidified PFPE thin layer and and heated 5 hours down at 65 ℃.Repair this thin layer then and mention this adherent layer from this main body.Use luer stub punching press fluid provider and outlet opening.Layer with this keyed jointing is placed on heating 5 hours so that this device adheres on this slide glass on the slide glass of silane coupling agent (aminopropyltriethoxywerene werene) processing and in 65 ℃ baking oven then.Little nozzle needle can be put into this inlet then with introducing fluid and drive membrane valve, as
Unger.M.Deng people's Science.2000,288,113-6 reports.Allow then comprise and flow through the raceway groove that is lined with the unreacted epoxy groups structure division, so that this raceway groove is functionalized by this protein then by the functionalized proteinic aqueous solution of unhindered amina.
Embodiment 15
Resins, epoxy/amine-excessive
To the adhesion of PFPE layer, the adhering to of charge species
With the two ingredient liquids PFPE precursor systems of the PFPE of comprising diepoxy resin as shown below and PFPE diamines in 1: 4 epoxy group(ing): the ratio blend of amine and is poured on the microfluid main body that comprises the 100 μ m features that are channel shape together so that have excessive amine.Use the PDMS mould in desired zone, to hold the thickness of this liquid to about 3mm.Individually, with in 4: 1 epoxy group(ing): the small droplets of the liquid PFPE precursor of the ratio blend of amine (so that having excessive epoxy group(ing) unit) applies second main body and spin coating 1 minute is to the thickness of 20 μ m roughly under 3700rpm, and this second main body comprises the 100 μ m features that are channel shape.The baking oven of then this wafer being put into 65 ℃ kept 5 hours.Remove, repair this thick-layer then, and use luer stub to allow the ingate punching press pass this layer.Then this thick-layer is placed on above the solidified PFPE thin layer and and heated 5 hours down at 65 ℃.Repair this thin layer then and mention this adherent layer from this main body.Use luer stub punching press fluid provider and outlet opening.Layer with this keyed jointing is placed on heating 5 hours so that this device adheres on this slide glass on the slide glass of silane coupling agent (aminopropyltriethoxywerene werene) processing and in 65 ℃ baking oven then.Little nozzle needle can be put into this inlet then with introducing fluid and drive membrane valve, as
Unger.M.Deng people's Science.2000,288,113-6 reports.Allow the aqueous solution that comprises by the functionalized charged molecule of unhindered amina flow through the raceway groove that is lined with the unreacted epoxy groups structure division then, so that this raceway groove is functionalized by this charged molecule then.
Embodiment 16
Resins, epoxy/amine-partly solidified
Adhesion to glass
The two ingredient liquids PFPE precursor systems of the PFPE of comprising diepoxy resin as shown below and PFPE diamines is in the same place by the stoichiometric ratio blend, and is poured on the microfluid main body that comprises the 100 μ m features that are channel shape.Use the PDMS mould in desired zone, to hold the thickness of this liquid to about 3mm.Then this wafer is put into that 65 ℃ baking oven kept 0.5 hour so that it is by partly solidified.Remove, repair this partly solidified layer then, and use luer stub to allow the ingate punching press pass this layer.Then this layer is placed on the slide glass of handling with silane coupling agent (aminopropyltriethoxywerene werene) and and adheres on this slide glass in 65 ℃ of following heating 5 hours so that it.Little nozzle needle can be put into this inlet then to introduce fluid.
Embodiment 17
Resins, epoxy/amine-partly solidified
Layer adheres to layer
The two ingredient liquids PFPE precursor systems of the PFPE of comprising diepoxy resin as shown below and PFPE diamines is in the same place by the stoichiometric ratio blend, and is poured on the microfluid main body that comprises the 100 μ m features that are channel shape.Use the PDMS mould in desired zone, to hold the thickness of this liquid to about 3mm.Then this wafer is put into that 65 ℃ baking oven kept 0.5 hour so that it is by partly solidified.Remove, repair this partly solidified layer then, and use luer stub to allow the ingate punching press pass this layer.Individually, with the small droplets of this liquid PFPE precursor under the 3700rpm on the top of second main body 1 minute thickness of this second main body of spin coating to about 20 μ m, this second main body comprises the 100 μ m features that are channel shape.Then this wafer is put into that 65 ℃ baking oven kept 0.5 hour so that it is by partly solidified.Then this thick-layer is placed on above the thick layer of this 20 μ m and in required zone, aligns to form sealing member.Then this layer is put into baking oven and descended heating 1 hour so that this two layers adhere at 65 ℃.Repair this thin layer then and mention this adherent layer from this main body.Use luer stub punching press fluid provider and outlet opening.Layer with this keyed jointing is placed on heating 10 hours down on the slide glass of silane coupling agent (aminopropyltriethoxywerene werene) processing and at 65 ℃ then.Little nozzle needle can be put into this inlet then with introducing fluid and drive membrane valve, as
Unger.M.Deng people's Science.2000,288,113-6 reports.
Embodiment 18
Resins, epoxy/amine-partly solidified
PDMS adheres to
Poly-(dimethyl siloxane) precursor of liquid is poured on the microfluid main body that comprises the 100 μ m features that are channel shape.The baking oven of then this wafer being put into 80 ℃ kept 3 hours.Remove, repair this solidified PDMS layer then, and use luer stub to allow the ingate punching press pass this layer.Then handled in 20 minutes with this layer of oxygen plasma treatment then with silane coupling agent (aminopropyltriethoxywerene werene).Individually, with spin coating second main body 1 minute is to the thickness of 20 μ m roughly under 3700rpm by the small droplets of stoichiometric ratio blended liquid PFPE precursor, this second main body comprises the 100 μ m features that are channel shape.The baking oven of then this wafer being put into 65 ℃ kept 0.5 hour.Then treated PDMS layer is placed on above the partly solidified PFPE thin layer and and heated 1 hour down at 65 ℃.Repair this thin layer then and mention this adherent layer from this main body.Use luer stub punching press fluid provider and outlet opening.Layer with this keyed jointing is placed on heating 10 hours down on the slide glass of aminopropyltriethoxywerene werene processing and at 65 ℃ then.Little nozzle needle can be put into this inlet then with introducing fluid and drive membrane valve, as
Unger.M.Deng people's Science.2000,288,113-6 reports.
Embodiment 19
Photocuring with the available potential functional group of after fixing
Adhesion to glass
(wherein R is an epoxy group(ing) to the liquid PFPE precursor of structure shown in below will having, curve is the PFPE chain, circle is a link molecule) with 1wt% free radical photo-initiation blend and being poured on the microfluid main body, this microfluid main body comprises the 100 μ m features that are channel shape.Use the PDMS mould in desired zone, to hold the thickness of this liquid to about 3mm.Then this wafer is put into the UV chamber and under nitrogen purging, be exposed to following 10 minutes of UV light (λ=365).Remove this completely crued layer from this main body then, and use luer stub to be stamped into oral pore.This device is placed on the slide glass of handling with silane coupling agent (aminopropyltriethoxywerene werene) and 65 ℃ of heating 15 hours down, thereby this device for good and all is keyed on this slide glass.Little nozzle needle can be put into this inlet then to introduce fluid.
Embodiment 20
Photocuring with the available potential functional group of after fixing
Adhesion to PFPE
(wherein R is an epoxy group(ing) to the liquid PFPE precursor of structure shown in below will having, curve is the PFPE chain, circle is a link molecule) with 1wt% free radical photo-initiation blend and being poured on the microfluid main body, this microfluid main body comprises the 100 μ m features that are channel shape.Use the PDMS mould in desired zone, to hold the thickness of this liquid to about 3mm.Then this wafer is put into the UV chamber and under nitrogen purging, be exposed to following 10 minutes of UV light (λ=365).Remove this completely crued layer from this main body then, and use luer stub to be stamped into oral pore.Individually, with the small droplets of this liquid PFPE precursor (wherein R is an amido) under the 3700rpm on the top of second main body 1 minute thickness of this second main body of spin coating to about 20 μ m, this second main body comprises the 100 μ m features that are channel shape.Then this wafer is put into the UV chamber and under nitrogen purging, be exposed to following 10 minutes of UV light (λ=365).To be somebody's turn to do then than thick-layer and be placed on above the thick layer of this 20 μ m and in required zone, align to form sealing member.Then this layer is put into baking oven and descended heating 2 hours at 65 ℃.Repair this thin layer then and mention this adherent layer from this main body.Use luer stub punching press fluid provider and outlet opening.Then this agglutinating layer is placed on the slide glass of handling with silane coupling agent (aminopropyltriethoxywerene werene) and and heated 15 hours down, thereby this device for good and all is keyed on this slide glass at 65 ℃.Little nozzle needle can be put into this inlet then with introducing fluid and drive membrane valve, as
Unger.M.Deng people's Science.2000,288,113-6 reports.
Embodiment 21
Photocuring with the available potential functional group of after fixing
Adhesion to PDMS
Poly-(dimethyl siloxane) precursor of liquid is poured on the microfluid main body that comprises the 100 μ m features that are channel shape.The baking oven of then this wafer being put into 80 ℃ kept 3 hours.Remove, repair this solidified PDMS layer then, and use luer stub to allow the ingate punching press pass this layer.Then handled in 20 minutes with this layer of oxygen plasma treatment then with silane coupling agent (aminopropyltriethoxywerene werene).Individually, with the small droplets of this liquid PFPE precursor (wherein R is an epoxy group(ing)) under the 3700rpm on the top of second main body 1 minute thickness of this second main body of spin coating to about 20 μ m, this second main body comprises the 100 μ m features that are channel shape.Then this wafer is put into the UV chamber and under nitrogen purging, be exposed to following 10 minutes of UV light (λ=365).Then that this is thicker PDMS layer is placed on above the thick layer of this 20 μ m and aligns in required zone to form sealing member.Then this layer is put into baking oven and descended heating 2 hours at 65 ℃.Repair this thin layer then and mention this adherent layer from this main body.Use luer stub punching press fluid provider and outlet opening.Then the layer of this keyed jointing is placed on the slide glass of handling with silane coupling agent (aminopropyltriethoxywerene werene) and 65 ℃ of heating 15 hours down, thereby this device for good and all is keyed on this slide glass.Little nozzle needle can be put into this inlet then with introducing fluid and drive membrane valve, as
Unger.M.Deng people's Science.2000,288,113-6 reports.
Embodiment 22
The available potential functional group of after fixing: attaching biomolecules
The liquid PFPE precursor (wherein R is an amido, and curve is the PFPE chain, and circle is a link molecule) of structure and the blend of 1wt% free radical photo-initiation shown in below will having also are poured on the microfluid main body, and this microfluid main body comprises the 100 μ m features that are channel shape.Use the PDMS mould in desired zone, to hold the thickness of this liquid to about 3mm.Then this wafer is put into the UV chamber and under nitrogen purging, be exposed to following 10 minutes of UV light (λ=365).Remove this completely crued layer from this main body then, and use luer stub to be stamped into oral pore.Individually, with the small droplets of this liquid PFPE precursor (wherein R is an epoxy group(ing)) under the 3700rpm on the top of second main body 1 minute thickness of this second main body of spin coating to about 20 μ m, this second main body comprises the 100 μ m features that are channel shape.Then this wafer is put into the UV chamber and under nitrogen purging, be exposed to following 10 minutes of UV light (λ=365).To be placed on above the thick layer of this 20 μ m and in required zone, align than thick-layer then to form sealing member.Then this layer is put into baking oven and descended heating 2 hours at 65 ℃.Repair this thin layer then and mention this adherent layer from this main body.Use luer stub punching press fluid provider and outlet opening.Then the layer of this keyed jointing is placed on the slide glass of handling with silane coupling agent (aminopropyltriethoxywerene werene) and 65 ℃ of heating 15 hours down, thereby this device for good and all is keyed on this slide glass.Little nozzle needle can be put into this inlet then with introducing fluid and drive membrane valve, as
Unger.M.Deng people's Science.2000,288,113-6 reports.Allow then comprise and flow through the raceway groove that is lined with the unreacted epoxy groups structure division, so that this raceway groove is functionalized by this protein then by the functionalized proteinic aqueous solution of unhindered amina.
Embodiment 23
The available potential functional group of after fixing: sclerozone isoelectric substance
The liquid PFPE precursor (wherein R is an amido, and curve is the PFPE chain, and circle is a link molecule) of structure and the blend of 1wt% free radical photo-initiation shown in below will having also are poured on the microfluid main body, and this microfluid main body comprises the 100 μ m features that are channel shape.Use the PDMS mould in desired zone, to hold the thickness of this liquid to about 3mm.Then this wafer is put into the UV chamber and under nitrogen purging, be exposed to following 10 minutes of UV light (λ=365).Remove this completely crued layer from this main body then, and use luer stub to be stamped into oral pore.Individually, with the small droplets of this liquid PFPE precursor (wherein R is an epoxy group(ing)) under the 3700rpm on the top of second main body 1 minute thickness of this second main body of spin coating to about 20 μ m, this second main body comprises the 100 μ m features that are channel shape.Then this wafer is put into the UV chamber and under nitrogen purging, be exposed to following 10 minutes of UV light (λ=365).To be somebody's turn to do then than thick-layer and be placed on above the thick layer of this 20 μ m and in required zone, align to form sealing member.Then this layer is put into baking oven and descended heating 2 hours at 65 ℃.Repair this thin layer then and mention this adherent layer from this main body.Use luer stub punching press fluid provider and outlet opening.Then the layer of this keyed jointing is placed on the slide glass of handling with silane coupling agent (aminopropyltriethoxywerene werene) and 65 ℃ of heating 15 hours down, thereby this device for good and all is keyed on this slide glass.Little nozzle needle can be put into this inlet then with introducing fluid and drive membrane valve, as
Unger.M.Deng people's Science.2000,288,113-6 reports.Allow the aqueous solution that comprises by the functionalized charged molecule of unhindered amina flow through the raceway groove that is lined with the unreacted epoxy groups structure division then, so that this raceway groove is functionalized by this charged molecule then.
Embodiment 24
With the available functionalized monomer's photocuring of after fixing
Adhesion to glass
With monomer (wherein R the is an epoxy group(ing)) blend of structure shown in liquid PFPE dimethacrylate precursor or the big monomer of monomethacrylates PFPE are below having and with the blend of 1wt% free radical photo-initiation, and be poured on the microfluid main body, this microfluid main body comprises the 100 μ m features that are channel shape.Use the PDMS mould in desired zone, to hold the thickness of this liquid to about 3mm.Then this wafer is put into the UV chamber and under nitrogen purging, be exposed to following 10 minutes of UV light (λ=365).Remove this completely crued layer from this main body then, and use luer stub to be stamped into oral pore.This device is placed on the slide glass of handling with silane coupling agent (aminopropyltriethoxywerene werene) and 65 ℃ of heating 15 hours down, thereby this device for good and all is keyed on this slide glass.Little nozzle needle can be put into this inlet then to introduce fluid.
Embodiment 25
With the available functionalized monomer's photocuring of after fixing
Adhesion to PFPE
With monomer (wherein R the is an epoxy group(ing)) blend of structure shown in liquid PFPE dimethacrylate precursor is below having and with the blend of 1wt% free radical photo-initiation, and be poured on the microfluid main body, this microfluid main body comprises the 100 μ m features that are channel shape.Use the PDMS mould in desired zone, to hold the thickness of this liquid to about 3mm.Then this wafer is put into the UV chamber and under nitrogen purging, be exposed to following 10 minutes of UV light (λ=365).Remove this completely crued layer from this main body then, and use luer stub to be stamped into oral pore.Individually, the small droplets that adds functionalized monomer's (wherein R is an amido) with this liquid PFPE precursor under the 3700rpm on the top of second main body 1 minute thickness of this second main body of spin coating to about 20 μ m, this second main body comprises the 100 μ m features that are channel shape.Then this wafer is put into the UV chamber and under nitrogen purging, be exposed to following 10 minutes of UV light (λ=365).To be somebody's turn to do then than thick-layer and be placed on above the thick layer of this 20 μ m and in required zone, align to form sealing member.Then this layer is put into baking oven and descended heating 2 hours at 65 ℃.Repair then this thin layer and from this main body mention this keyed jointing the layer.Use luer stub punching press fluid provider and outlet opening.Then this agglutinating layer is placed on the slide glass of handling with silane coupling agent (aminopropyltriethoxywerene werene) and and heated 15 hours down, thereby this device for good and all is keyed on this slide glass at 65 ℃.Little nozzle needle can be put into this inlet then with introducing fluid and drive membrane valve, as
Unger.M.Deng people's Science.2000,288,113-6 reports.
Embodiment 26
With the available functionalized monomer's photocuring of after fixing
Adhesion to PDMS
Poly-(dimethyl siloxane) precursor of liquid is poured on the microfluid main body that comprises the 100 μ m features that are channel shape.The baking oven of then this wafer being put into 80 ℃ kept 3 hours.Remove, repair this solidified PDMS layer then, and use luer stub to allow the ingate punching press pass this layer.Then handled in 20 minutes with this layer of oxygen plasma treatment then with silane coupling agent (aminopropyltriethoxywerene werene).Individually, with this liquid PFPE dimethacrylate precursor add small droplets that functionalized monomer's (wherein R is an epoxy group(ing)) adds light trigger under the 3700rpm on the top of second main body 1 minute thickness of this second main body of spin coating to about 20 μ m, this second main body comprises the 100 μ m features that are channel shape.Then this wafer is put into the UV chamber and under nitrogen purging, be exposed to following 10 minutes of UV light (λ=365).Then that this is thicker PDMS layer is placed on above the thick layer of this 20 μ m and aligns in required zone to form sealing member.Then this layer is put into baking oven and descended heating 2 hours at 65 ℃.Repair this thin layer then and mention this adherent layer from this main body.Use luer stub punching press fluid provider and outlet opening.Then the layer of this keyed jointing is placed on the slide glass of handling with silane coupling agent (aminopropyltriethoxywerene werene) and 65 ℃ of heating 15 hours down, thereby this device for good and all is keyed on this slide glass.Little nozzle needle can be put into this inlet then with introducing fluid and drive membrane valve, as
Unger.M.Deng people's Science.2000,288,113-6 reports.
Embodiment 27
With the available functionalized monomer's photocuring of after fixing
Adhering to of biomolecules
With monomer (wherein R the is an amido) blend of structure shown in liquid PFPE dimethacrylate precursor is below having and with the blend of 1wt% free radical photo-initiation, and be poured on the microfluid main body, this microfluid main body comprises the 100 μ m features that are channel shape.Use the PDMS mould in desired zone, to hold the thickness of this liquid to about 3mm.Then this wafer is put into the UV chamber and under nitrogen purging, be exposed to following 10 minutes of UV light (λ=365).Remove this completely crued layer from this main body then, and use luer stub to be stamped into oral pore.Individually, the small droplets that adds functionalized monomer's (wherein R is an epoxy group(ing)) with this liquid PFPE precursor under the 3700rpm on the top of second main body 1 minute thickness of this second main body of spin coating to about 20 μ m, this second main body comprises the 100 μ m features that are channel shape.Then this wafer is put into the UV chamber and under nitrogen purging, be exposed to following 10 minutes of UV light (λ=365).To be somebody's turn to do then than thick-layer and be placed on above the thick layer of this 20 μ m and in required zone, align to form sealing member.Then this layer is put into baking oven and descended heating 2 hours at 65 ℃.Repair this thin layer then and mention this adherent layer from this main body.Use luer stub punching press fluid provider and outlet opening.Then the layer of this keyed jointing is placed on the slide glass of handling with silane coupling agent (aminopropyltriethoxywerene werene) and 65 ℃ of heating 15 hours down, thereby this device for good and all is keyed on this slide glass.Little nozzle needle can be put into this inlet then with introducing fluid and drive membrane valve, as
Unger.M.Deng people's Science.2000,288,113-6 reports.Allow then comprise and flow through the raceway groove that is lined with the unreacted epoxy groups structure division, so that this raceway groove is functionalized by this protein then by the functionalized proteinic aqueous solution of unhindered amina.
Embodiment 28
Photocuring with the available potential functional group of after fixing
Adhering to of charge species
With monomer (wherein R the is an amido) blend of structure shown in liquid PFPE dimethacrylate precursor is below having and with the blend of 1wt% free radical photo-initiation, and be poured on the microfluid main body, this microfluid main body comprises the 100 μ m features that are channel shape.Use the PDMS mould in desired zone, to hold the thickness of this liquid to about 3mm.Then this wafer is put into the UV chamber and under nitrogen purging, be exposed to following 10 minutes of UV light (λ=365).Remove this completely crued layer from this main body then, and use luer stub to be stamped into oral pore.Individually, the small droplets that adds functionalized monomer's (wherein R is an epoxy group(ing)) with this liquid PFPE precursor under the 3700rpm on the top of second main body 1 minute thickness of this second main body of spin coating to about 20 μ m, this second main body comprises the 100 μ m features that are channel shape.Then this wafer is put into the UV chamber and under nitrogen purging, be exposed to following 10 minutes of UV light (λ=365).To be somebody's turn to do then than thick-layer and be placed on above the thick layer of this 20 μ m and in required zone, align to form sealing member.Then this layer is put into baking oven and descended heating 2 hours at 65 ℃.Repair this thin layer then and mention this adherent layer from this main body.Use luer stub punching press fluid provider and outlet opening.Then the layer of this keyed jointing is placed on the slide glass of handling with silane coupling agent (aminopropyltriethoxywerene werene) and 65 ℃ of heating 15 hours down, thereby this device for good and all is keyed on this slide glass.Little nozzle needle can be put into this inlet then with introducing fluid and drive membrane valve, as
Unger.M.Deng people's Science.2000,288,113-6 reports.Allow the aqueous solution that comprises by the functionalized charged molecule of unhindered amina flow through the raceway groove that is lined with the unreacted epoxy groups structure division then, so that this raceway groove is functionalized by this charged molecule then.
Embodiment 29
Use and sacrifice raceway groove manufacturing PFPE microfluidic device
By the small droplets blade coating of liquid PFPE dimethacrylate precursor having been formed smooth, smooth PFPE layer on slide glass with scraper plate.Then this slide glass is put into the UV chamber and under nitrogen purging, be exposed to following 10 minutes of UV light (λ=365).This that will be laid on PFPE by the support that is channel shape that poly-(lactic acid) constitutes be smooth, above the smooth layer.With liquid PFPE dimethacrylate precursor and the blend of 1wt% free radical photo-initiation and be poured on this support.Use the PDMS mould in desired zone, to hold the thickness of this liquid to about 3mm.Then this device is put into the UV chamber and under nitrogen purging, be exposed to following 10 minutes of UV light (λ=365).Can heat this device 24 hours down so that poly-(lactic acid) degrades at 150 ℃ then, thereby expose the hole that stays by channel shape.
Embodiment 30
Use 185nm light that PFPE device and glass are adhered to
With liquid PFPE dimethacrylate precursor and the blend of 1wt% free radical photo-initiation and be poured on the microfluid main body, this microfluid main body comprises the 100 μ m features that are channel shape.Use the PDMS mould in desired zone, to hold the thickness of this liquid to about 3mm.Then this wafer is put into the UV chamber and under nitrogen purging, be exposed to following 10 minutes of UV light (λ=365).Individually, with the small droplets of this liquid PFPE precursor under the 3700rpm on the top of second main body 1 minute thickness of this second main body of spin coating to about 20 μ m, this second main body comprises the 100 μ m features that are channel shape.Then this wafer is put into the UV chamber and under nitrogen purging, be exposed to following 10 minutes of UV light (λ=365).Remove, repair this then than thick-layer, and use luer stub to allow the ingate punching press pass this layer.Then this layer is placed on above the thick layer of this 20 μ m and in required zone, aligns to form sealing member.Then this layer is put into baking oven and descended heating 2 hours at 120 ℃.Repair this thin layer then and mention this adherent layer from this main body.Use luerstub punching press fluid provider and outlet opening.Then the layer of this keyed jointing is placed on the slide glass of cleaning so that it forms sealing member.This device is exposed to 185nm UV light following 20 minutes, thereby between this device and glass, forms persistent keyed jointing.Little nozzle needle can be put into this inlet then with introducing fluid and drive membrane valve, as
Unger.M.Deng people's Science.2000,288,113-6 reports.
Embodiment 31
" Resins, epoxy coating " method of encapsulated device
With liquid PFPE dimethacrylate precursor and the blend of 1wt% free radical photo-initiation and be poured on the microfluid main body, this microfluid main body comprises the 100 μ m features that are channel shape.Use the PDMS mould in desired zone, to hold the thickness of this liquid to about 3mm.Then this wafer is put into the UV chamber and under nitrogen purging, be exposed to following 10 minutes of UV light (λ=365).Individually, with the small droplets of this liquid PFPE precursor under the 3700rpm on the top of second main body 1 minute thickness of this second main body of spin coating to about 20 μ m, this second main body comprises the 100 μ m features that are channel shape.Then this wafer is put into the UV chamber and under nitrogen purging, be exposed to following 10 minutes of UV light (λ=365).Remove, repair this then than thick-layer, and use luer stub to allow the ingate punching press pass this layer.Then this layer is placed on above the thick layer of this 20 μ m and in required zone, aligns to form sealing member.Then this layer is put into baking oven and descended heating 2 hours at 120 ℃.Repair this thin layer then and mention this adherent layer from this main body.Use luerstub punching press fluid provider and outlet opening.Then the layer of this keyed jointing is placed on the slide glass of cleaning so that it forms sealing member.Little nozzle needle can be put into this inlet then with introducing fluid and drive membrane valve, as
Unger.M.Deng people's Science.2000,288,113-6 reports.Whole device can be coated in the liquid epoxies precursor then, this liquid epoxies precursor is poured on this and makes on its solidified device.This coating is used for mechanically with this device and base material bonding.
Embodiment 32
Make the PFPE device by three arm PFPE precursors
The liquid PFPE precursor (wherein circle is represented link molecule) of structure and the blend of 1wt% free radical photo-initiation shown in below will having also are poured on the microfluid main body, and this microfluid main body comprises the 100 μ m features that are channel shape.Use the PDMS mould in desired zone, to hold the thickness of this liquid to about 3mm.Then this wafer is put into the UV chamber and under nitrogen purging, be exposed to following 10 minutes of UV light (λ=365).Individually, with the small droplets of this liquid PFPE precursor under the 3700rpm on the top of second main body 1 minute thickness of this second main body of spin coating to about 20 μ m, this second main body comprises the 100 μ m features that are channel shape.Then this wafer is put into the UV chamber and under nitrogen purging, be exposed to following 10 minutes of UV light (λ=365).The 3rd, by the small droplets blade coating of liquid PFPE precursor having been formed smooth, smooth PFPE layer on slide glass with scraper plate.Then this slide glass is put into the UV chamber and under nitrogen purging, be exposed to following 10 minutes of UV light (λ=365).Remove, repair this then than thick-layer, and use luer stub to allow the ingate punching press pass this layer.Then this layer is placed on above the thick layer of this 20 μ m and in required zone, aligns to form sealing member.Then this layer is put into baking oven and descended heating 2 hours at 120 ℃.Repair this thin layer then and mention this adherent layer from this main body.Use luer stub punching press fluid provider and outlet opening.Then the layer of this keyed jointing is placed on the completely crued PFPE smooth layer on the slide glass and 120 ℃ of heating 15 hours down.Little nozzle needle can be put into this inlet then with introducing fluid and drive membrane valve, as
Unger.M.Deng people's Science.2000,288,113-6 reports.
Embodiment 33
The PFPE/PDMS hybrid of photocuring
With small droplets 1 minute thickness to about 20 μ m of this main body of spin coating on the top in main body under the 3700rpm of the liquid PFPE dimethacrylate precursor that comprises light trigger, this main body comprises the 100 μ m features that are channel shape.The PDMS dimethacrylate that will comprise light trigger then is poured on the top of this thin PFPE layer the thickness to 3mm.Then this wafer is put into the UV chamber and under nitrogen purging, be exposed to following 10 minutes of UV light (λ=365).Remove, repair this layer then, and use luer stub to allow the ingate punching press pass this layer.Be placed on this hydridization device on the slide glass then and formed sealing member.Little nozzle needle can be put into this inlet then to introduce fluid.
Embodiment 34
The microfluidic device that forms by the thermal curable and the photocurable materials of blend
At first, what measure predetermined amount (for example 5 gram) comprises a little light initiator, as the PFPE dimethacrylate of the chain extension of hydroxycyclohexylphenylketone.Next, add 1: 1 weight ratio (for example 5 grams) the PFPE vulcabond of chain extension.Next, add then a certain amount of (for example 0.3mL) PFPE tetrol (Mn～2000g/mol) thus exist stoichiometric-N (C=O)-and-the OH structure division.Mix these three kinds of components then up hill and dale and under vacuum, outgas.
Use photolithography formation caster and use argon plasma body and function metal, for example the thin layer of gold/palladium applies.The thin layer of device is spun on the patterned substrate under 1500rpm by this PFPE blend.Thin, smooth (non-patterning) layer of spin coating also.Individually, thicker layer is cast on the caster of this washing, usually by material is for example converged in, in the PDMS packing ring.Then all layers are put into the UV chamber, with nitrogen purging 10 minutes, and under comprehensive nitrogen purging photocuring ten minutes, become solid rubber shape test specimen.Can repair this layer and punching press inlet/outlet opening then.Next, layer is piled up and by record position align so that they form conformal sealing member.Heated this stack layer 10 minutes down at 105 ℃ then.This heating steps causes the thermofixation of this thermal curable material, is wrapped in the matrix of photocuring to this thermal curable Material Physics.Because this layer is by conformal contact, so obtained strong adhesion.Can peel off these two adherent layers or use solvent from the patterning main body then, as dimethyl formamide it is broken away from, and the 3rd base material smooth, photocuring under making it and also not being exposed to heat contact.Under 110 ℃, cured this three layer device 15 hours then so that whole three layers adhere to fully.
According to another embodiment, about 20 degrees centigrade (℃)-about 200 ℃ temperature under this thermofixation of activation.According to another embodiment, about 50 degrees centigrade (℃)-about 150 ℃ temperature under this thermofixation of activation.Additionally, this thermofixation through select to satisfy it about 75 degrees centigrade (℃)-be activated under the about 200 ℃ temperature.
According to another embodiment, the photocuring amount of substance that adds in this material is substantially equal to the thermofixation amount of substance.In another embodiment, the thermofixation amount of substance that adds in this material is about 10% of a photocuring amount of substance.According to another embodiment, the thermofixation amount of substance is about 50% of a photocuring amount of substance.
Embodiment 35
Be used to make the multi-component material of microfluidic device
The chemical structure of every kind of component will be described below.In following examples, first component (component 1) be chain extension, photocurable PFPE Liquid precursor.Should syntheticly use classical carbamate chemical and organotin catalysts, with vulcabond commonly used, isophorone diisocyanate (IPDI) is with commercially available PFPE glycol (ZDOL) chain extension.After chain extension, with containing the diisocyanate monomer (EIM) of methacrylic ester with this chain end-blocking.
Second component is the PFPE vulcabond of chain extension.It makes (component 2a) by ZDOL and IPDI by making the polymer chain of gained be reacted by isocyanate-terminated mol ratio.Same classical carbamate chemical and the organotin catalysts of using of this reaction.
The second section of thermal curable components is that commercially available molecular weight is 2, the PFPE tetrol of 000g/mol (component 2b).
Should be appreciated that under the situation of the scope that does not break away from disclosure theme the various details of disclosure theme can change.In addition, top description only is to be used for explanation, rather than is used for restriction.
Embodiment 36
The microfluidic device that forms by the thermal curable and the photocurable materials of blend: UV diamino
Manthanoate methacrylic ester and PFPE triol+PFPE vulcabond system
At first, what measure predetermined amount (for example 10 gram) comprises a little light initiator, as the PFPE dimethacrylate of the chain extension of diethoxy phenyl ketone.Next, add about 7 gram PFPE vulcabond.Next, add then a certain amount of (for example 3.0g) PFPE triol (Mn～5000g/mol) thus exist stoichiometric-N (C=O)-and-the OH structure division.Mix these three kinds of components then up hill and dale and under vacuum, outgas.
Use photolithography formation caster and use argon plasma body and function metal, for example the thin layer of gold/palladium applies.Perhaps, handle this main body with silane or other release layer.The thin layer of device is spun on the patterned substrate under 1500rpm by this PFPE blend.Thin, smooth (non-patterning) layer of spin coating also.Individually, thicker layer is cast on the caster of this washing, usually by material is for example converged in, in the PDMS packing ring.Then all layers are put into the UV chamber, use nitrogen purging 10 minutes, and photocuring became solid rubber shape test specimen in ten minutes under comprehensive nitrogen purging.Can repair this layer and punching press inlet/outlet opening then.Next, layer is piled up and by record position align so that they form conformal sealing member.Heated this stack layer 10 minutes down at 115 ℃ then.This heating steps causes the thermofixation of this thermal curable material, is wrapped in the matrix of photocuring to this thermal curable Material Physics.Because this layer is by conformal contact, so obtained strong adhesion.Can peel off these two adherent layers or use solvent from the patterning main body then, as dimethyl formamide it is broken away from, and the 3rd base material smooth, photocuring under making it and also not being exposed to heat contact.Under 150 ℃, cured this three layer device 2 hours then so that whole three layers adhere to fully.
Embodiment 37
The microfluidic device that forms by the thermal curable and the photocurable materials of blend: UV diamino
Manthanoate methacrylic ester and PFPE diepoxy resin+PFPE diamines
At first, what measure predetermined amount (for example 20 gram) comprises a little light initiator, as the PFPE dimethacrylate of the chain extension of diethoxy phenyl ketone.Next, add about 10 gram PFPE diepoxy resins.Next, add a certain amount of (for example 3.6g) PFPE diamines then and consequently have stoichiometric epoxy group(ing) and amine structure part.Mix these three kinds of components then up hill and dale and under vacuum, outgas.
Use photolithography formation caster and use argon plasma body and function metal, for example the thin layer of gold/palladium applies.Perhaps, handle this main body with silane or other release layer.Thin, smooth (non-patterning) layer of spin coating under 1500rpm also.Individually, thicker layer is cast on this patterning caster, usually by material is for example converged in, in the PDMS packing ring.Then all layers are put into the UV chamber, use nitrogen purging 10 minutes, and photocuring became solid rubber shape test specimen in ten minutes under comprehensive nitrogen purging.Can repair this layer and punching press inlet/outlet opening then.Next, layer is piled up and by record position align so that they form conformal sealing member.Heated this stack layer 20 minutes down at 120 ℃ then.This heating steps causes the thermofixation of this thermal curable material, is wrapped in the matrix of photocuring to this thermal curable Material Physics.Because this layer is by conformal contact, so obtained strong adhesion.
Embodiment 38
The microfluidic device that forms by the photocurable materials of two kinds of blend: UV diurethanes
Methacrylic ester and UV Resins, epoxy
At first, what measure predetermined amount (for example 10 gram) comprises a little light initiator, as the PFPE dimethacrylate of the chain extension of diethoxy phenyl ketone.Next, add 10 gram PFPE diepoxy resin preparatons, this preparaton comprises 5 gram ZDOL TX and 0.2g light acid producing agents, as Rhodorsil 2079.Mix these two kinds of components then up hill and dale and under vacuum, outgas.
Use photolithography formation caster and use argon plasma body and function metal, for example the thin layer of gold/palladium applies.Perhaps, handle this main body with silane or other release layer.Thin, smooth (non-patterning) layer of spin coating under 1500rpm also.Individually, thicker layer is cast on this patterning caster, usually by material is for example converged in, in the PDMS packing ring.Then all layers are put into the UV chamber, use nitrogen purging 5 minutes, and photocuring became solid rubber shape test specimen in 5 minutes under comprehensive nitrogen purging.Can repair this layer and punching press inlet/outlet opening then.Next, layer is piled up and by record position align so that they form conformal sealing member.For the second time this stack layer is exposed under the UV light then, continues 10 minutes.The 2nd UV step has further promoted the curing of this PFPE diepoxy resin material, is wrapped in this PFPE diurethanes methacrylic ester to this PFPE diepoxy resin Material Physics.Because this layer is by conformal contact, so obtained strong adhesion.
Embodiment 39
The microfluidic device that forms by the thermal curable and the photocurable materials of blend: UV diamino
Manthanoate methacrylic ester and PFPE vulcabond system
At first, can measure about 10 grams and comprise a little light initiator, as the PFPE dimethacrylate of the chain extension of diethoxy phenyl ketone.Next, should add about 7 gram PFPE vulcabond.To mix these three kinds of components then up hill and dale and under vacuum, outgas.
To use photolithography formation caster then and use argon plasma body and function metal, for example the thin layer of gold/palladium applies.Perhaps, can handle this main body with silane or other release layer.To under 1500rpm, the thin layer of device be spun on the patterned substrate by this PFPE blend then.Also that spin coating is thin, smooth (non-patterning) layer.Individually, thicker layer can be cast on the caster of this washing, usually by material is for example converged in, in the PDMS packing ring.Then all layers are put into the UV chamber, use nitrogen purging 10 minutes, and photocuring became solid rubber shape test specimen in ten minutes under comprehensive nitrogen purging.As required, can repair this layer and punching press inlet/outlet opening then.Next, layer is piled up and align so that form conformal sealing member by record position.Then this stack layer was heated 30 minutes down at 130 ℃.This heating steps causes the thermofixation component of this thermal curable material, is wrapped in the matrix of photocuring to this thermal curable Material Physics.Because of pressing conformal contact by layer, so will obtain strong adhesion.Can peel off these two adherent layers or use solvent from the patterning main body then, as dimethyl formamide it is broken away from, and the 3rd base material smooth, photocuring under making it and also not being exposed to heat contact.Can under 130 ℃, cure this three layer device 4 hours then so that whole three layers adhere to fully.
Embodiment 40
Be used to make the multi-component material of microfluidic device.But thermal curable and light by blend are solid
The microfluidic device that formed material forms: UV diurethanes methacrylic ester and PFPE two are different
The cyanate system
At first, should measure about 10 grams and comprise a little light initiator, as the PFPE dimethacrylate of the chain extension of diethoxy phenyl ketone.Next, should add 7 gram PFPE vulcabond.To mix this three component then up hill and dale and under vacuum, outgas.
To use photolithography formation caster and use argon plasma body and function metal, for example the thin layer of gold/palladium applies.Perhaps, can handle this main body with silane or other release layer.To under 1500rpm, the thin layer of device be spun on the patterned substrate by this PFPE blend then.Also that spin coating is thin, smooth (non-patterning) layer.Individually, thicker layer is cast on the caster of this washing, usually by material is for example converged in, in the PDMS packing ring.All layers should be put into the UV chamber then, use nitrogen purging 10 minutes, and photocuring became solid rubber shape test specimen in ten minutes under comprehensive nitrogen purging.As required, can repair this layer and punching press inlet/outlet opening then.Next, layer should be piled up and by record position align so that they form conformal sealing member.To in having, heat this stack layer down 30 minutes then (wet and cause curing) at 90 ℃ greater than the humidity chamber of 50% relative humidity.This heating steps causes the thermofixation of this thermal curable material, is wrapped in the matrix of photocuring to this thermal curable Material Physics.Because of pressing conformal contact by layer, so will obtain strong adhesion.Can peel off these two adherent layers or use solvent from the patterning main body then, as dimethyl formamide it is broken away from, and the 3rd base material smooth, photocuring under making it and also not being exposed to heat contact.Can in having, under 90 ℃, cure this three layer device 4 hours then greater than the humidity chamber of 50% relative humidity.
Claims (261)
1. polymer composition comprises:
First component that comprises the fluoropolymer that contains first curable functional group; With
Second component that comprises the fluoropolymer that contains second curable functional group.
2. the composition of claim 1 also comprises the 3rd component, and the 3rd component comprises the fluoropolymer that contains the 3rd curable functional group.
3. the composition of claim 1 wherein saidly contains the fluoropolymer of first curable functional group or contains at least a PFPE that comprises in the fluoropolymer of second curable functional group.
4. the composition of claim 2, contains the fluoropolymer of second curable functional group or contains at least a low surface energy polymeric material that comprises in the fluoropolymer of the 3rd curable functional group the wherein said fluoropolymer that contains first curable functional group.
5. the composition of claim 1, wherein this first curable functional group comprises the first photocurable functional group.
6. the composition of claim 5, wherein this second curable functional group comprises the second photocurable functional group.
7. the composition of claim 1, wherein this second curable functional group comprises the first thermal curable functional group.
8. the composition of claim 5, wherein this first photocurable functional group comprises photo curable diurethanes methacrylic ester.
9. the composition of claim 7, wherein this first thermal curable functional group comprises vulcabond.
10. the composition of claim 7, wherein this first thermal curable functional group comprises the diepoxy group.
11. the composition of claim 7, wherein this first thermal curable functional group comprises diamines.
12. the composition of claim 6, wherein this second photocurable functional group comprises photo curable diepoxy group.
13. the composition of claim 2, wherein the 3rd curable functional group comprises the second thermal curable functional group.
14. the composition of claim 13, wherein this second thermal curable functional group comprises triol.
15. the composition of claim 13, wherein this second thermal curable functional group comprises tetrol.
16. the composition of claim 2, wherein this first curable functional group comprises photo curable diurethanes methacrylic ester, and second curable functional group comprises vulcabond, and the 3rd curable functional group comprises triol.
17. the composition of claim 2, wherein this first curable functional group comprises photo curable diurethanes methacrylic ester, and second curable functional group comprises vulcabond, and the 3rd curable functional group comprises tetrol.
18. the composition of claim 2, wherein this first curable functional group comprises photo curable diurethanes methacrylic ester, and second curable functional group comprises the diepoxy group, and the 3rd curable functional group comprises diamines.
19. the composition of claim 1, wherein this first curable functional group comprises photo curable diurethanes methacrylic ester, and second curable functional group comprises photo curable diepoxy group.
20. the composition of claim 1, wherein this first curable functional group comprises photo curable diurethanes methacrylic ester, and second curable functional group comprises vulcabond.
21. the composition of claim 6, wherein this first photocurable functional group reacts under first wavelength, and the second photocurable functional group reacts under second wavelength.
22. the composition of claim 13, wherein this first thermal curable functional group reacted in first period, and the second thermal curable functional group reacted in second period.
23. the composition of claim 13, wherein this first thermal curable functional group reacts under first temperature, and the second thermal curable functional group reacts under second temperature.
24. the composition of claim 2, contains the fluoropolymer of second curable functional group and contains at least a PFPE that comprises in the fluoropolymer of the 3rd curable functional group the wherein said fluoropolymer that contains first curable functional group.
25. the composition of claim 2, the wherein said fluoropolymer that contains first curable functional group, the fluoropolymer that contains the fluoropolymer of second curable functional group and contain the 3rd curable functional group comprise PFPE.
26. the composition of claim 24, wherein this PFPE has structure: C
3F
7O[CF (CF
3) CF
2O]
xC
2F
5
27. the composition of claim 24, wherein this PFPE has structure: C
3F
7O[CF (CF
3) CF
2O]
x(CF
2O)
yC
2F
5
28. the composition of claim 24, wherein this PFPE has structure: CF
3O (CF
2CF
2O)
x(CF
2O)
yCF
3
29. the composition of claim 1, the wherein said fluoropolymer that contains first curable functional group comprise the methacrylate functionalized PFPE of photocurable diurethanes with following structure:
30. the composition of claim 1, the wherein said fluoropolymer that contains first curable functional group comprise the methacrylate functionalized PFPE of photocurable diurethanes with following structure:
31. the composition of claim 1, the wherein said fluoropolymer that contains second curable functional group comprises the functionalized PFPE of the vulcabond with following structure:
32. the composition of claim 1, the wherein said fluoropolymer that contains second curable functional group comprises the functionalized PFPE of the vulcabond with following structure:
33. the composition of claim 1, the wherein said fluoropolymer that contains second curable functional group comprise the functionalized PFPE of photocurable bicyclic oxygen with following structure:
34. the composition of claim 1, the wherein said fluoropolymer that contains second curable functional group comprises the functionalized PFPE of the bicyclic oxygen with following structure:
35. the composition of claim 2, the wherein said fluoropolymer that contains the 3rd curable functional group comprises the functionalized PFPE of the tetrol with following structure:
36. the composition of claim 2, the wherein said fluoropolymer that contains the 3rd curable functional group comprises the functionalized PFPE of the triol with following structure:
37. the composition of claim 1, the wherein said fluoropolymer that contains second curable functional group comprise two amine-functionalized PFPE with following structure:
38. the composition of claim 4, wherein this low surface energy polymeric material has the surface energy less than about 20 dynes per centimeter.
39. the composition of claim 4, wherein this low surface energy polymeric material has the surface energy less than about 18 dynes per centimeter.
40. the composition of claim 4, wherein this low surface energy polymeric material has the surface energy less than about 15 dynes per centimeter.
41. the composition of claim 1, wherein this second curable functional group keeps available after described first curable functional group is activated, thus this second curable functional group can with the group, hydroxyl, another kind of functional group and its built up section that constitute another kind of polymkeric substance.
42. the composition of claim 3, wherein this PFPE is by cycloaliphatic epoxide structure division end-blocking.
43. the composition of claim 3, wherein this PFPE has about 16000 molecular weight and the about modulus of 800kPa.
44. the composition of claim 3, wherein this PFPE has the molecular weight less than about 16000.
45. the composition of claim 3, wherein this PFPE has the modulus greater than about 500kPa.
46. the composition of claim 3, wherein this PFPE has about 16000 molecular weight and about 200% elongation at break.
47. the composition of claim 3, wherein this PFPE has the elongation at break less than about 200%.
48. the composition of claim 1, a kind of elongation at break that comprises in wherein said first component or second component is about 300% fluoropolymer.
49. the composition of claim 1, a kind of elongation at break that comprises in wherein said first component or second component is about 200% fluoropolymer.
50. the composition of claim 1, a kind of elongation at break that comprises in wherein said first component or second component is the fluoropolymer of about 100%-about 300%.
51. the composition of claim 1, a kind of elongation at break that comprises in wherein said first component or second component is the PFPE of about 200%-about 300%.
52. polymer composition comprises:
The fluoropolymer that comprises at least two kinds of functional groups, wherein after making this fluoropolymer polymerization, second functional group keeps can activating so that this fluoropolymer is adhered on another chemical group in that first functional group is activated.
53. the polymer composition of claim 52, wherein this another chemical group is selected from group, hydroxyl, another kind of functional group and their combination that constitutes another kind of polymkeric substance.
54. micro element comprises:
The microfluidic device that comprises first fluoropolymer component.
55. the micro element of claim 54, wherein this first fluoropolymer component comprises PFPE.
56. the micro element of claim 54, wherein this first fluoropolymer component comprises first curable functional group.
57. the micro element of claim 56 also comprises second fluoropolymer component.
58. the micro element of claim 57, wherein this second fluoropolymer component comprises second curable functional group.
59. the micro element of claim 57, the wherein at least a PFPE that comprises in this first fluoropolymer component or second fluoropolymer component.
60. the micro element of claim 56, wherein this first curable functional group comprises the first photocurable functional group.
61. the micro element of claim 58, wherein this second curable functional group comprises the first thermal curable functional group.
62. the micro element of claim 58, wherein this second curable functional group comprises the second photocurable functional group.
63. the micro element of claim 60, wherein this first photocurable functional group comprises photo curable diurethanes methacrylic ester.
64. the micro element of claim 61, wherein this first thermal curable functional group comprises vulcabond.
65. the micro element of claim 61, wherein this first thermal curable functional group comprises the diepoxy group.
66. the micro element of claim 61, wherein this first thermal curable functional group comprises diamines.
67. the micro element of claim 62, wherein this second photocurable functional group comprises photo curable diepoxy group.
68. the micro element of claim 58 also comprises the 3rd fluoropolymer component, wherein the 3rd fluoropolymer component comprises the 3rd curable functional group.
69. the micro element of claim 68, wherein the 3rd curable functional group comprises the second thermal curable functional group.
70. the micro element of claim 69, wherein this second thermal curable functional group comprises triol.
71. the micro element of claim 69, wherein this second thermal curable functional group comprises tetrol.
72. the micro element of claim 68, wherein this first curable functional group comprises photo curable diurethanes methacrylic ester, and second curable functional group comprises vulcabond, and the 3rd curable functional group comprises triol.
73. the micro element of claim 68, wherein this first curable functional group comprises photo curable diurethanes methacrylic ester, and second curable functional group comprises vulcabond, and the 3rd curable functional group comprises tetrol.
74. the micro element of claim 68, wherein this first curable functional group comprises photo curable diurethanes methacrylic ester, and second curable functional group comprises the diepoxy group, and the 3rd curable functional group comprises diamines.
75. the micro element of claim 58, wherein this first curable functional group comprises photo curable diurethanes methacrylic ester, and second curable functional group comprises photo curable diepoxy group.
76. the micro element of claim 58, wherein this first curable functional group comprises photo curable diurethanes methacrylic ester, and second curable functional group comprises vulcabond.
77. the micro element of claim 62, wherein this first curable functional group comprises the first photocurable functional group, and wherein this first photocurable functional group reacts to different wavelength with the second photocurable functional group.
78. the micro element of claim 68, at least a PFPE that comprises in wherein said first fluoropolymer component, second fluoropolymer component and the 3rd fluoropolymer component.
79. the micro element of claim 68, wherein said first fluoropolymer component, second fluoropolymer component and the 3rd fluoropolymer component comprise PFPE.
80. the micro element of claim 55, wherein this PFPE component has structure: C
3F
7O[CF (CF
3) CF
2O]
xC
2F
5
81. the micro element of claim 55, wherein this PFPE has structure: C
3F
7O[CF (CF
3) CF
2O]
x(CF
2O)
yC
2F
5
82. the micro element of claim 55, wherein this PFPE has structure: CF
3O (CF
2CF
2O)
x(CF
2O)
yCF
3
83. the micro element of claim 54 also comprises and the described first fluoropolymer component bonded silicone components.
84. the micro element of claim 83, wherein this microfluidic device that has with described silicone components bonded first fluoropolymer component has the adhesive power that can tolerate up to about 120 pounds/square inch (psi).
85. the micro element of claim 54, wherein this first fluoropolymer component has about 300% elongation at break.
86. the micro element of claim 54, wherein this first fluoropolymer component has about 200% elongation at break.
87. the micro element of claim 54, wherein this first fluoropolymer component has the elongation at break of about 100%-about 300%.
88. the micro element of claim 54, wherein this first fluoropolymer component has the elongation at break of about 200%-about 300%.
89. the micro element of claim 54, wherein this fluoropolymer comprises the low surface energy fluoropolymer.
90. the micro element of claim 89, wherein this low surface energy fluoropolymer has the surface energy less than about 20 dynes per centimeter.
91. the micro element of claim 89, wherein this low surface energy fluoropolymer has the surface energy less than about 18 dynes per centimeter.
92. the micro element of claim 89, wherein this low surface energy fluoropolymer has the surface energy less than about 15 dynes per centimeter.
93. the micro element of claim 54 also comprises the component that is selected from following material: the diurethanes methacrylic ester; The diurethanes methacrylic ester of chain extension; Vulcabond; The vulcabond of chain extension; End capped vulcabond; The triol of PFPE three arms; The PFPE toluylene; Diepoxy resin; Diamines; The PU-tetrol of thermofixation; The PU-triol of thermofixation; The Resins, epoxy of thermofixation; The Resins, epoxy of photocuring and their combination.
94. the micro element of claim 54, wherein this first fluoropolymer component is substantially free of trace-metal.
95. the micro element of claim 54, wherein this first fluoropolymer component is solvent-proof basically.
96. the micro element of claim 54, wherein when being communicated with organic solvent, this first fluoropolymer component swelling is less than about 10wt%.
97. the micro element of claim 54, wherein when being communicated with organic solvent, this fluoropolymer component swelling is less than about 5wt%.
98. the micro element of claim 54, wherein this fluoropolymer component has about 1: 2 carbon and fluorine ratio.
99. the micro element of claim 54, wherein this fluoropolymer component has about 1: 1 carbon and fluorine ratio.
100. the micro element of claim 54, wherein this fluoropolymer component has about 2: 1 carbon and fluorine ratio.
101. the micro element of claim 54, wherein this fluoropolymer component has about 1: carbon and fluorine ratio that 1-is about 2: 1.
102. the micro element of claim 54, wherein this fluoropolymer component has about 1: carbon and fluorine ratio that 1-is about 1: 2.
103. the micro element of claim 54, wherein this microfluidic device also comprises laminated between first parts and second parts;
This laminated chemical bond that comprises between these first parts and this second parts wherein; With
Wherein under about 120 pounds/square inch pressure these first parts not with this second component layer from.
104. the micro element of claim 54 also comprises:
Limit first parts of raceway groove wherein; With
Be positioned at the valve of this raceway groove;
Wherein this valve can drive under the pressure of about about 60psi of 40psi-and can not damage this microfluidic device.
105. the micro element of claim 54 also comprises:
Limit first parts of raceway groove wherein; With
Be positioned at the valve of this raceway groove;
Wherein this valve can drive under the pressure of about about 60psi of 50psi-and can not damage this microfluidic device.
106. the micro element of claim 54, wherein this fluoropolymer is made by fluoro-alkyl iodine precursor.
107. the micro element of claim 54, wherein this first fluoropolymer component is included in the coating on the raceway groove of this microfluidic device.
108. the micro element of claim 54, wherein this first fluoropolymer component has about 16000 molecular weight and the about modulus of 800kPa.
109. the micro element of claim 54, wherein this first fluoropolymer component has the molecular weight less than about 16000.
110. the micro element of claim 54, wherein this first fluoropolymer component has the modulus greater than about 500kPa.
111. the micro element of claim 54, wherein this first fluoropolymer component has about 16000 molecular weight and about 200% elongation at break.
112. the micro element of claim 54, wherein this first fluoropolymer component has the elongation at break less than about 200%.
113. microfluidic device comprises:
Microfluidic device, this microfluidic device comprise the PFPE Resins, epoxy that contains PAG; Wherein this binding substances is selected from 2, the free radical photo-initiation blend of 2-dimethoxy-acetophenone, 1-hydroxycyclohexylphenylketone or diethoxy acetophenone with about about 5 moles of % of 1-.
114. the microfluidic device of claim 113, the wherein said PFPE Resins, epoxy that contains PAG can be under two or more wavelength photocuring.
115. microfluidic device comprises:
Comprise by first parts of PFPE structure with by the microfluidic device of second parts of silicone structure.
116. micro element comprises:
Microfluidic device by the method preparation that may further comprise the steps:
The hydrogen atom of handling in nitrogen in this device so that this fluorine and this device with the solution that comprises 0.5% fluorine gas carries out the surface passivation that therefore free radical reaction also makes this device.
117. have the infiltrative device of increase, comprising:
The microfluidic device of the method preparation by may further comprise the steps:
Fluorinated fluids is added in the polymer precursor of this microfluidic device, wherein this polymer precursor comprises photo curable precursor or heat-setting precursor;
By handling this polymkeric substance with optical radiation or heat energy respectively with this polymer cure; With
From this cured polymer, remove this fluorinated fluids.
118. the device of claim 117, wherein this remove be the evaporation.
119. the device of claim 117, wherein this remove be the dissolving.
120. the device of claim 117, the concentration of wherein said fluorinated fluids is less than about 15%.
121. the device of claim 117, the concentration of wherein said fluorinated fluids is less than about 10%.
122. the device of claim 117, the concentration of wherein said fluorinated fluids is less than about 5%.
123. the device of claim 117 wherein after the evaporation of described fluorinated fluids, stays the polymkeric substance with nano level hole.
124. micro element comprises:
Microfluidic device with surface;
Wherein should the surface by end capped precursor passivation.
125. the device of claim 124, wherein this end capped precursor comprises the end capped Liquid precursor of vinylbenzene.
126. the device of claim 124, wherein this surface comprises the surface of valve.
127. the device of claim 124, wherein this surface comprises the surface of raceway groove.
128. the device of claim 124, wherein this surface comprises the surface of reservoir.
129. the device of claim 124, wherein this surface comprises the surface of film.
130. the device of claim 124, wherein this surface comprises the surface of wall.
131. the component parts of microfluidic device comprises:
By the valve of first polymeric constituent and the manufacturing of second polymeric constituent,
Wherein this first polymeric constituent comprises the fluoropolymer that contains first curable functional group;
Wherein this second polymeric constituent comprises the fluoropolymer that contains second curable functional group.
132. the component parts of claim 131 also comprises the terpolymer component, wherein this terpolymer component comprises the fluoropolymer that contains the 3rd curable functional group.
133. the component parts of claim 132, contains the fluoropolymer of second curable functional group or contains at least a PFPE that comprises in the fluoropolymer of the 3rd curable functional group the wherein said fluoropolymer that contains first curable functional group.
134. the component parts of claim 132, contains the fluoropolymer of second curable functional group or contains at least a low surface energy polymeric material that comprises in the fluoropolymer of the 3rd curable functional group the wherein said fluoropolymer that contains first curable functional group.
135. the component parts of claim 131, the wherein said fluoropolymer that contains first curable functional group comprises photocurable functional group.
136. the component parts of claim 131, the wherein said fluoropolymer that contains second curable functional group comprises thermal curable functional group.
137. the component parts of claim 135, wherein this photocurable functional group is selected from photo curable diurethanes methacrylic ester, photo curable diepoxy group and their combination.
138. the component parts of claim 136, wherein this thermal curable functional group can be triol, vulcabond, tetrol, diepoxy group, diamines or their combination.
139. the component parts of claim 131, wherein this first curable functional group and second curable functional group are selected from the diurethanes methacrylic ester; The diurethanes methacrylic ester of chain extension; Vulcabond; The vulcabond of chain extension; End capped vulcabond; The triol of PFPE three arms; The PFPE toluylene; The diepoxy group; Diamines; The PU-tetrol of thermofixation; The PU-triol of thermofixation; The epoxide group of thermofixation; The epoxide group of photocuring and their combination.
140. the component parts of microfluidic device comprises:
The valve that comprises fluoropolymer component.
141. the component parts of microfluidic device comprises:
The part of the raceway groove of microfluidic device, wherein this part of this raceway groove comprises fluoropolymer.
142. the component parts of claim 141, wherein this fluoropolymer comprises: first polymeric constituent, and wherein this first polymeric constituent comprises the fluoropolymer that contains first curable functional group; With
Second polymeric constituent, wherein this second polymeric constituent comprises the fluoropolymer that contains second curable functional group.
143. the component parts of claim 142, wherein this fluoropolymer also comprises:
The terpolymer component, wherein this terpolymer component comprises the fluoropolymer that contains the 3rd curable functional group.
144. the component parts of microfluidic device comprises:
The film of microfluidic device, wherein this film comprises fluoropolymer.
145. the component parts of claim 144, wherein this film comprises two-layer PFPE laminate, and this laminate has the toluylene material that is laminated on the PFPE diurethanes methacrylic acid ester material.
146. the component parts of claim 144, wherein this fluoropolymer also comprises the hole that is limited to wherein.
147. the component parts of claim 146, wherein this hole is less than about 15%.
148. the component parts of claim 146, wherein this hole is less than about 10%.
149. the component parts of claim 146, wherein this hole is less than about 5%.
150. the component parts of claim 146, wherein this fluoropolymer comprises: first polymeric constituent, and wherein this first polymeric constituent comprises the fluoropolymer that contains first curable functional group; With
Second polymeric constituent, wherein this second polymeric constituent comprises the fluoropolymer that contains second curable functional group.
151. the component parts of claim 150, wherein this fluoropolymer also comprises:
The terpolymer component, wherein this terpolymer component comprises the fluoropolymer that contains the 3rd curable functional group.
152. the component parts of microfluidic device comprises:
The valve of microfluidic device, wherein this valve comprises fluoropolymer.
153. the component parts of claim 152, wherein this valve comprises two-layer PFPE laminate, and this laminate has the toluylene material that is laminated on the PFPE diurethanes methacrylic acid ester material.
154. the component parts of claim 152, wherein this fluoropolymer also comprises the hole that is limited to wherein.
155. the component parts of claim 154, wherein this hole is less than about 15%.
156. the component parts of claim 154, wherein this hole is less than about 10%.
157. the component parts of claim 154, wherein this hole is less than about 5%.
158. the component parts of claim 152, wherein this fluoropolymer comprises: first polymeric constituent, and wherein this first polymeric constituent comprises the fluoropolymer that contains first curable functional group; With
Second polymeric constituent, wherein this second polymeric constituent comprises the fluoropolymer that contains second curable functional group.
159. the component parts of claim 153, wherein this fluoropolymer also comprises:
The terpolymer component, wherein this terpolymer component comprises the fluoropolymer that contains the 3rd curable functional group.
160. the component parts of microfluidic device comprises:
The reservoir of microfluidic device, wherein this reservoir comprises fluoropolymer.
161. the component parts of claim 160, wherein this fluoropolymer comprises: first polymeric constituent, and wherein this first polymeric constituent comprises the fluoropolymer that contains first curable functional group; With
Second polymeric constituent, wherein this second polymeric constituent comprises the fluoropolymer that contains second curable functional group.
162. the component parts of claim 161, wherein this fluoropolymer also comprises:
The terpolymer component, wherein this terpolymer component comprises the fluoropolymer that contains the 3rd curable functional group.
163. the component parts of microfluidic device comprises:
The wall of microfluidic device, wherein this wall comprises fluoropolymer.
164. the component parts of claim 163, wherein this fluoropolymer comprises: first polymeric constituent, and wherein this first polymeric constituent comprises the fluoropolymer that contains first curable functional group; With
Second polymeric constituent, wherein this second polymeric constituent comprises the fluoropolymer that contains second curable functional group.
165. the component parts of claim 164, wherein this fluoropolymer also comprises:
The terpolymer component, wherein this terpolymer component comprises the fluoropolymer that contains the 3rd curable functional group.
166. the component parts of microfluidic device comprises:
The surface of microfluidic device, wherein this surface comprises fluoropolymer.
167. the component parts of claim 166, wherein this fluoropolymer comprises: first polymeric constituent, and wherein this first polymeric constituent comprises the fluoropolymer that contains first curable functional group; With
Second polymeric constituent, wherein this second polymeric constituent comprises the fluoropolymer that contains second curable functional group.
168. the component parts of claim 167, wherein this fluoropolymer also comprises:
The terpolymer component, wherein this terpolymer component comprises the fluoropolymer that contains the 3rd curable functional group.
169. the manufacture method of micro element comprises:
Make microfluidic device by fluoropolymer.
170. the method for claim 169, wherein this fluoropolymer comprises PFPE.
171. the method for claim 169, wherein this fluoropolymer comprises:
First fluoropolymer component that contains first curable functional group; With
Second fluoropolymer component that contains second curable functional group.
172. the method for claim 171, at least a PFPE that comprises in wherein said first fluoropolymer component or second fluoropolymer component.
173. the method for claim 171, wherein this first curable functional group comprises photocurable functional group.
174. the method for claim 171, wherein this second curable functional group comprises thermal curable functional group.
175. the manufacture method of microfluidic device comprises:
From polymkeric substance, remove trace-metal;
Use this polymkeric substance to make microfluidic device, wherein this microfluidic device is substantially free of trace-metal.
176. the method for claim 175, wherein this polymkeric substance comprises fluoropolymer.
177. the method for claim 176, wherein this fluoropolymer comprises PFPE.
178. the method for reacting comprises:
Microfluidic device is provided, and this microfluidic device comprises the polymkeric substance that is substantially free of trace-metal;
In this microfluidic device, relate to the reaction of F-so that this F-basically not by the trace-metal quencher in the polymkeric substance of this microfluidic device.
179. the treatment process of polymer device comprises:
Surface with sodium naphthalene etchant process fluoropolymer microfluidic device.
180. the method for claim 179, wherein this fluoropolymer comprises PFPE.
181. the manufacture method of microfluidic device comprises:
Fluoropolymer is cast on the caster, and wherein this caster comprises space pattern;
This fluoropolymer solidified so that this fluoropolymer keeps the basic mirror image of this space pattern;
To gather (dimethyl siloxane) is cast on this cured fluoropolymer;
(dimethyl siloxane) curing will be gathered so that the basic mirror image that (dimethyl siloxane) keeps the pattern of this curing fluoropolymer should be gathered; With
Use this solidified poly-(dimethyl siloxane) to be used for other fluoropolymer component of molding as mould.
182. the method for claim 181, wherein this fluoropolymer is a PFPE.
183. the manufacture method of microfluidic device comprises:
The thin layer of uncured polymer is spun in the first part of microfluidic device;
This first part is arranged on the second section of this microfluidic device so that the thin layer of this spin coating is communicated with the second section of this microfluidic device; With
The thin layer that this binding substances is solidified consequently this spin coating solidifies.
184. the manufacture method of polymer device comprises:
Photo curable PFPE polymkeric substance is provided;
Between this polymkeric substance and light source, wherein this mask defines the space of predetermined size and dimension with mask-placement;
Activate this light source, wherein this light source passes the space in this mask and the photocurable reagent activation of the polymkeric substance in the first cure polymer district that will be corresponding with the space in this mask;
Remove this mask; With
Remove uncured liquid polymers.
185. the method for claim 184 also comprises, after removing uncured polymkeric substance,
Fill by removing the space that uncured polymkeric substance stays with sacrifice layer;
The photocurable PFPE polymkeric substance of second quantity is incorporated on this first cure polymer and the sacrifice layer;
Arrange second mask, this second mask defines second space with respect to the PFPE polymkeric substance of this second quantity;
This second mask is exposed under the light source, and wherein this light source passes unreacted photocurable PFPE polymer activation in this second space and the zone that will be corresponding with this second space to form the second cure polymer district;
Wherein this first cure polymer district of part is connected with this second cure polymer district of part;
Remove this second mask; With
Remove this sacrifice layer.
186. increase the method for the chemical compatibility of polymer device, comprising:
The polymer device that comprises potential methacrylic ester, acrylate and/or styrene group with the solution-treated that comprises the end capped precursor solution of vinylbenzene;
The film of this solution evaporation so that the end capped precursor of this vinylbenzene is retained on the surface of this polymer device; With
The end capped precursor film of this vinylbenzene solidified thus this film via adhering on the surface of this polymer device with the reaction of potential methacrylic ester, acrylate and/or the styrene group of this polymer device.
187. the method for claim 186, wherein this polymer device comprises PFPE.
188. the method for claim 186, wherein the end capped precursor of this vinylbenzene comprises photo curable component and by this precursor being exposed under the optical radiation and with its curing.
189. the treatment process of microfluidic device comprises:
The surface that comprises the microfluidic device of potential methacrylic ester, acrylate or styrene group with the solution-treated that comprises the end capped precursor of vinylbenzene;
The film of this solution evaporation so that the end capped precursor of this vinylbenzene is retained on the surface treated of this microfluidic device; With
Potential methacrylic ester, acrylate or styrene group reaction with the end capped precursor cures of this vinylbenzene so that this film and this microfluidic device.
190. the method for claim 189, wherein this microfluidic device comprises PFPE.
191. the method for claim 189, wherein the end capped precursor of this vinylbenzene comprises photo curable component and by this precursor being exposed under the optical radiation and with its curing.
192. increase the method for the chemical compatibility of polymkeric substance, comprising:
The hydrogen atom of handling in nitrogen in this polymkeric substance so that this fluorine and this polymkeric substance with the solution that comprises 0.5% fluorine gas carries out the surface passivation that therefore free radical reaction also makes this polymkeric substance.
193. the treatment process of microfluidic device comprises:
The hydrogen atom of handling in nitrogen in this microfluidic device so that this fluorine and this microfluidic device with the solution that comprises 0.5% fluorine gas carries out the surface passivation that therefore free radical reaction also makes this microfluidic device.
194. the method for claim 193, wherein raceway groove so that this raceway groove with mixture process this microfluidic device of 0.5% fluorine gas in nitrogen experiences surface passivation.
195. increase the infiltrative method of microfluidic device, comprising:
Fluorated solvent is added in the fluoropolymer precursors of microfluidic device, wherein this fluoropolymer precursors comprises photocurable or heat-setting precursor;
By handling this fluoropolymer with optical radiation or heat energy respectively this fluoropolymer is solidified; With
This fluorated solvent of evaporation from this cured fluoropolymer.
196. the method for claim 195, wherein the concentration of this fluorated solvent is less than about 15%.
197. the method for claim 195, wherein the concentration of this fluorated solvent is less than about 10%.
198. the method for claim 195, wherein the concentration of this fluorated solvent is less than about 5%.
199. the method for claim 195, wherein this polymkeric substance comprises PFPE.
200. the manufacture method of solvent-proof micro element comprises:
Part with the fluoropolymer-coated microfluidic device.
201. the method for claim 200, wherein this fluoropolymer comprises PFPE.
202. the using method of micro element comprises:
Make microfluidic device by fluoropolymer, wherein this microfluidic device comprises raceway groove; With
Allow liquid flow through this raceway groove at least in part.
203. the method for claim 202, wherein this liquid comprises organic solvent.
204. the method for claim 203, wherein this organic solvent comprises hydrocarbon solvent.
205. the method for claim 204, wherein this hydrocarbon solvent is selected from tetrahydrofuran (THF), toluene, methylene dichloride, hexane, chloroform, Virahol, hexanaphthene, methyl ethyl ketone, acetone and their combination.
206. the method for claim 202, wherein this fluoropolymer be substantially free of trace-metal and wherein this liquid comprise F-.
207. the using method of microfluidic device comprises:
Microfluidic device with raceway groove is provided, wherein scribbles to this channel part fluoropolymer; With
Material is introduced in the raceway groove of this microfluidic device.
208. the method for claim 207, wherein this material comprises organic solvent.
209. polymer composition comprises:
First component that comprises the fluoropolymer that contains first curable functional group; With
Second component that comprises the polymkeric substance that contains second curable functional group.
210. the composition of claim 209 also comprises the 3rd component, the 3rd component comprises the polymkeric substance that contains the 3rd curable functional group.
211. the composition of claim 209, the wherein said fluoropolymer that contains first curable functional group comprises PFPE.
212. the composition of claim 210, the wherein said fluoropolymer that contains first curable functional group comprises low surface energy polymeric material.
213. the composition of claim 209, wherein this first curable functional group comprises the first photocurable functional group, and second curable functional group comprises the second photocurable functional group.
214. the composition of claim 209, wherein this first curable functional group comprises the first photocurable functional group, and second curable functional group comprises the first thermal curable functional group.
215. the composition of claim 210, wherein this first curable functional group comprises the first photocurable functional group, and second curable functional group comprises the first thermal curable functional group, and the 3rd curable functional group comprises the second thermal curable functional group.
216. the composition of claim 214, wherein this first photocurable functional group comprises photo curable diurethanes methacrylic ester, and the first thermal curable functional group comprises vulcabond.
217. the composition of claim 214, wherein this first photocurable functional group comprises photo curable diurethanes methacrylic ester, and the first thermal curable functional group comprises the diepoxy group.
218. the composition of claim 214, wherein this first photocurable functional group comprises photo curable diurethanes methacrylic ester, and the first thermal curable functional group comprises diamines.
219. the composition of claim 213, wherein this first photocurable functional group comprises photo curable diurethanes methacrylic ester, and the second photocurable functional group comprises photo curable diepoxy group.
220. the composition of claim 210, wherein this first curable functional group comprises photo curable diurethanes methacrylic ester, and second curable functional group comprises the thermal curable vulcabond, and the 3rd curable functional group comprises the thermal curable triol.
221. the composition of claim 210, wherein this first curable functional group comprises photo curable diurethanes methacrylic ester, and second curable functional group comprises the thermal curable vulcabond, and the 3rd curable functional group comprises the thermal curable tetrol.
222. the composition of claim 210, wherein this first curable functional group comprises photo curable diurethanes methacrylic ester, and second curable functional group comprises thermal curable diepoxy group, and the 3rd curable functional group comprises the thermal curable diamines.
223. the composition of claim 209, wherein this first curable functional group comprises photo curable diurethanes methacrylic ester, and second curable functional group comprises photo curable diepoxy group.
224. the composition of claim 209, wherein this first curable functional group comprises photo curable diurethanes methacrylic ester, and second curable functional group comprises the thermal curable vulcabond.
225. the composition of claim 213, wherein this first photocurable functional group reacts under first wavelength, and the second photocurable functional group reacts under second wavelength.
226. the composition of claim 1, wherein this fluoropolymer can with this polymkeric substance mixing.
227. the composition of claim 1, wherein this fluoropolymer not with this polymkeric substance mixing.
228. microfluidic device comprises:
First component that comprises the polymkeric substance that contains first curable functional group; With
Second component that comprises the polymkeric substance that contains second curable functional group.
229. the microfluidic device of claim 228, wherein this first curable functional group comprises photocurable functional group, and second curable functional group comprises thermal curable functional group.
230. the microfluidic device of claim 228, wherein this first curable functional group comprises the first photocurable functional group, and second curable functional group comprises the second photocurable functional group; With
Wherein this first photocurable functional group can solidify under first wavelength, and the second photocurable functional group can solidify under second wavelength.
231. the microfluidic device of claim 228, wherein this first curable functional group comprises the first thermal curable functional group, and second curable functional group comprises the second thermal curable functional group;
Wherein this first thermal curable functional group can solidify under first temperature, and the second thermal curable functional group can solidify under second temperature.
232. the microfluidic device of claim 228, wherein this first curable functional group comprises the first thermal curable functional group, and second curable functional group comprises the second thermal curable functional group; With
Wherein this first thermal curable functional group can solidify under first elapsed time, and the second thermal curable functional group can solidify under second elapsed time.
233. the microfluidic device of claim 228 also comprises the polymkeric substance that contains the 3rd curable functional group.
234. the microfluidic device of claim 229, wherein this photocurable functional group comprises that photo curable diurethanes methacrylic ester and this thermal curable functional group comprise vulcabond.
235. the microfluidic device of claim 229, wherein this photocurable functional group comprises that photo curable diurethanes methacrylic ester and this thermal curable functional group comprise the diepoxy group.
236. the microfluidic device of claim 229, wherein this photocurable functional group comprises that photo curable diurethanes methacrylic ester and this thermal curable functional group comprise diamines.
237. the microfluidic device of claim 230, wherein this first photocurable functional group comprises that photo curable diurethanes methacrylic ester and this second photocurable functional group comprise photo curable diepoxy group.
238. the microfluidic device of claim 233, wherein this first curable functional group comprises photo curable diurethanes methacrylic ester, this second curable functional group comprises that heat-setting vulcabond and the 3rd curable functional group comprise heat-setting triol.
239. the microfluidic device of claim 233, wherein this first curable functional group comprises photo curable diurethanes methacrylic ester, this second curable functional group comprises that heat-setting vulcabond and the 3rd curable functional group comprise heat-setting tetrol.
240. the microfluidic device of claim 233, wherein this first curable functional group comprises photo curable diurethanes methacrylic ester, this second curable functional group comprises that heat-setting diepoxy group and the 3rd curable functional group comprise heat-setting diamines.
241. microfluidic device comprises:
The film of microfluidic device, wherein this film comprises:
First component that comprises the polymkeric substance that contains first curable functional group; With
Second component that comprises the polymkeric substance that contains second curable functional group.
242. the microfluidic device of claim 241, wherein this first curable functional group comprises photocurable functional group, and second curable functional group comprises thermal curable functional group.
243. the microfluidic device of claim 241, wherein this first curable functional group comprises the first photocurable functional group, and second curable functional group comprises the second photocurable functional group; With
Wherein this first photocurable functional group can solidify under first wavelength, and the second photocurable functional group can solidify under second wavelength.
244. the microfluidic device of claim 241, wherein this first curable functional group comprises the first thermal curable functional group, and second curable functional group comprises the second thermal curable functional group; With
Wherein this first thermal curable functional group can solidify under first temperature, and the second thermal curable functional group can solidify under second temperature.
245. the microfluidic device of claim 241, wherein this first curable functional group comprises the first thermal curable functional group, and second curable functional group comprises the second thermal curable functional group; With
Wherein this first thermal curable functional group can solidify under first elapsed time, and the second thermal curable functional group can solidify under second elapsed time.
246. microfluidic device comprises:
The valve of microfluidic device, wherein this valve comprises:
First component that comprises the polymkeric substance that contains first curable functional group; With
Second component that comprises the polymkeric substance that contains second curable functional group.
247. the microfluidic device of claim 246, wherein this first curable functional group comprises photocurable functional group, and second curable functional group comprises thermal curable functional group.
248. the microfluidic device of claim 246, wherein this first curable functional group comprises the first photocurable functional group, and second curable functional group comprises the second photocurable functional group; With
Wherein this first photocurable functional group can solidify under first wavelength, and the second photocurable functional group can solidify under second wavelength.
249. the microfluidic device of claim 246, wherein this first curable functional group comprises the first thermal curable functional group, and second curable functional group comprises the second thermal curable functional group; With
Wherein this first thermal curable functional group can solidify under first temperature, and the second thermal curable functional group can solidify under second temperature.
250. the microfluidic device of claim 246, wherein this first curable functional group comprises the first thermal curable functional group, and second curable functional group comprises the second thermal curable functional group; With
Wherein this first thermal curable functional group can solidify under first elapsed time, and the second thermal curable functional group can solidify under second elapsed time.
251. microfluidic device comprises:
Expanded ptfe, this expanded ptfe have solidified PFPE in its hole.
252. the microfluidic device of claim 251, wherein this PFPE comprises curable functional group.
253. the microfluidic device of claim 252, wherein this curable functional group comprises photocurable functional group.
254. the microfluidic device of claim 253, wherein this photocurable functional group comprises photo curable diurethanes methacrylic ester or photo curable diepoxy group.
255. the microfluidic device of claim 252, wherein this curable functional group comprises thermal curable functional group.
256. the microfluidic device of claim 255, wherein this thermal curable functional group comprises heat-setting vulcabond, diepoxy group, diamines, triol, tetrol or their combination.
257. the microfluidic device of claim 251, wherein this PFPE comprises the PFPE toluylene.
258. the manufacture method of microfluidic device comprises:
The surface that is made of expanded ptfe at least in part is provided;
Enter the hole of this expanded ptfe with wetting this expanded ptfe of curable PFPE so that this PFPE; With
Solidify this PFPE.
259. the method for claim 258, wherein this curable PFPE comprises the curable functional group and second curable functional group.
260. the method for claim 259, wherein this curable functional group comprises photocurable functional group or thermal curable functional group.
261. the method for claim 258, wherein this curable PFPE comprises photocurable functional group and thermal curable functional group.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US70678605P | 2005-08-09 | 2005-08-09 | |
| US60/706,786 | 2005-08-09 | ||
| US60/732,727 | 2005-11-02 | ||
| US60/799,317 | 2006-05-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101283042A true CN101283042A (en) | 2008-10-08 |
Family
ID=40014893
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006800375059A Pending CN101283042A (en) | 2005-08-09 | 2006-08-09 | Methods and materials for fabricating microfluidic devices |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101283042A (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102527451A (en) * | 2010-12-01 | 2012-07-04 | 爱科来株式会社 | Device and method for manufacturing the same |
| CN102899244A (en) * | 2012-09-27 | 2013-01-30 | 中国科学院半导体研究所 | Solid phase-digital PCR (Polymerase Chain Reaction) chip and method for fabricating solid phase-digital PCR chip |
| CN103477218A (en) * | 2011-02-09 | 2013-12-25 | 于利奇研究中心有限公司 | Method for producing a device for detecting an analyte and device and use thereof |
| CN103718030A (en) * | 2011-05-05 | 2014-04-09 | 达克雷诊断器材有限公司 | Conductive patterns and methods for making conductive patterns |
| CN104093662A (en) * | 2011-12-07 | 2014-10-08 | 佐治亚技术研究公司 | Packaging compatible wafer level capping of mems devices |
| CN104583256A (en) * | 2012-08-28 | 2015-04-29 | 株式会社普利司通 | Member having cured layer formed by curing curable resin composition on at least surface thereof |
| CN107661619A (en) * | 2017-10-25 | 2018-02-06 | 上海长海医院 | A kind of naval officers and men for adapting to unstable ship environment moves integrated system apparatus |
| CN110082442A (en) * | 2019-04-22 | 2019-08-02 | 中昊晨光化工研究院有限公司 | A kind of fluorine-containing small molecule compound gas-chromatography packed column and the preparation method and application thereof |
| CN110088158A (en) * | 2016-08-05 | 2019-08-02 | 迈克罗欧普提克斯股份有限公司 | Polymeric device and manufacturing method |
| CN111295125A (en) * | 2017-12-29 | 2020-06-16 | 金昌潽 | Surgical instrument for endoscope |
| CN111346575A (en) * | 2020-03-31 | 2020-06-30 | 齐鲁工业大学 | Capillary microfluidic reactor with controllable catalytic material fixed area and preparation method thereof |
| CN112969325A (en) * | 2021-02-24 | 2021-06-15 | Oppo广东移动通信有限公司 | Shell assembly, preparation method thereof and electronic equipment |
| CN113985505A (en) * | 2021-10-21 | 2022-01-28 | 浙江大学 | Method for preparing micro-lens array based on hydrogel microstructure template |
| CN114251531A (en) * | 2021-12-21 | 2022-03-29 | 华中科技大学 | Fluid connecting pipe and application thereof |
| CN115646563A (en) * | 2022-10-14 | 2023-01-31 | 广州迪澳医疗科技有限公司 | Micro-fluidic chip and preparation method thereof |
-
2006
- 2006-08-09 CN CNA2006800375059A patent/CN101283042A/en active Pending
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9039880B2 (en) | 2010-12-01 | 2015-05-26 | Arkray, Inc. | Device and method for manufacturing the same |
| CN102527451B (en) * | 2010-12-01 | 2016-01-20 | 爱科来株式会社 | Device and manufacture method thereof |
| CN102527451A (en) * | 2010-12-01 | 2012-07-04 | 爱科来株式会社 | Device and method for manufacturing the same |
| CN103477218A (en) * | 2011-02-09 | 2013-12-25 | 于利奇研究中心有限公司 | Method for producing a device for detecting an analyte and device and use thereof |
| CN103477218B (en) * | 2011-02-09 | 2016-01-20 | 于利奇研究中心有限公司 | For the manufacture of the method for the device for validating analysis thing and device and application thereof |
| CN103718030A (en) * | 2011-05-05 | 2014-04-09 | 达克雷诊断器材有限公司 | Conductive patterns and methods for making conductive patterns |
| CN104093662A (en) * | 2011-12-07 | 2014-10-08 | 佐治亚技术研究公司 | Packaging compatible wafer level capping of mems devices |
| CN104093662B (en) * | 2011-12-07 | 2015-11-25 | 佐治亚技术研究公司 | The compatible wafer scale capping of encapsulation of MEMS |
| CN104583256A (en) * | 2012-08-28 | 2015-04-29 | 株式会社普利司通 | Member having cured layer formed by curing curable resin composition on at least surface thereof |
| CN102899244A (en) * | 2012-09-27 | 2013-01-30 | 中国科学院半导体研究所 | Solid phase-digital PCR (Polymerase Chain Reaction) chip and method for fabricating solid phase-digital PCR chip |
| CN110088158A (en) * | 2016-08-05 | 2019-08-02 | 迈克罗欧普提克斯股份有限公司 | Polymeric device and manufacturing method |
| CN107661619A (en) * | 2017-10-25 | 2018-02-06 | 上海长海医院 | A kind of naval officers and men for adapting to unstable ship environment moves integrated system apparatus |
| CN111295125A (en) * | 2017-12-29 | 2020-06-16 | 金昌潽 | Surgical instrument for endoscope |
| CN110082442A (en) * | 2019-04-22 | 2019-08-02 | 中昊晨光化工研究院有限公司 | A kind of fluorine-containing small molecule compound gas-chromatography packed column and the preparation method and application thereof |
| CN111346575A (en) * | 2020-03-31 | 2020-06-30 | 齐鲁工业大学 | Capillary microfluidic reactor with controllable catalytic material fixed area and preparation method thereof |
| CN111346575B (en) * | 2020-03-31 | 2021-10-01 | 齐鲁工业大学 | Capillary microfluidic reactor with controllable catalytic material fixed area and preparation method thereof |
| CN112969325A (en) * | 2021-02-24 | 2021-06-15 | Oppo广东移动通信有限公司 | Shell assembly, preparation method thereof and electronic equipment |
| CN113985505A (en) * | 2021-10-21 | 2022-01-28 | 浙江大学 | Method for preparing micro-lens array based on hydrogel microstructure template |
| CN114251531A (en) * | 2021-12-21 | 2022-03-29 | 华中科技大学 | Fluid connecting pipe and application thereof |
| CN115646563A (en) * | 2022-10-14 | 2023-01-31 | 广州迪澳医疗科技有限公司 | Micro-fluidic chip and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101283042A (en) | Methods and materials for fabricating microfluidic devices | |
| US8158728B2 (en) | Methods and materials for fabricating microfluidic devices | |
| CN101189271A (en) | Functional materials and novel methods for the fabrication of microfluidic devices | |
| CN1997691B (en) | Photocurable perfluoropolyethers for use as novel materials in microfluidic devices | |
| Sticker et al. | Thiol–ene based polymers as versatile materials for microfluidic devices for life sciences applications | |
| US20070178133A1 (en) | Medical device, materials, and methods | |
| CN101156107B (en) | Low surface energy polymeric material for use in liquid crystal displays | |
| US7368163B2 (en) | Polymer surface modification | |
| Jon et al. | Construction of nonbiofouling surfaces by polymeric self-assembled monolayers | |
| Khademhosseini et al. | A soft lithographic approach to fabricate patterned microfluidic channels | |
| Hu et al. | Surface modification of poly (dimethylsiloxane) microfluidic devices by ultraviolet polymer grafting | |
| Kitsara et al. | Integration of functional materials and surface modification for polymeric microfluidic systems | |
| Chen et al. | Fabrication of discontinuous surface patterns within microfluidic channels using photodefinable vapor-based polymer coatings | |
| CN103831914A (en) | Methods and materials for fabricating laminate nanomolds and nanoparticles therefrom | |
| Hu et al. | Surface grafting on polymer surface using physisorbed free radical initiators | |
| Hong et al. | Click chemistry at the microscale | |
| Dogbevi et al. | Pumpless,“self-driven” microfluidic channels with controlled blood flow using an amphiphilic silicone | |
| Suhard et al. | When energetic materials, PDMS-based elastomers, and microelectronic processes work together: fabrication of a disposable microactuator | |
| Mays | Tuning Bulk and Surface Properties of Polymers for Micro-and Nanofabrication. |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20081008 |