CN105903501B - A kind of dimethyl silicone polymer-paper compound chip and its preparation method and purposes - Google Patents

A kind of dimethyl silicone polymer-paper compound chip and its preparation method and purposes Download PDF

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Publication number
CN105903501B
CN105903501B CN201610239287.2A CN201610239287A CN105903501B CN 105903501 B CN105903501 B CN 105903501B CN 201610239287 A CN201610239287 A CN 201610239287A CN 105903501 B CN105903501 B CN 105903501B
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paper
dimethyl silicone
silicone polymer
chip
pdms
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CN105903501A (en
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徐碧漪
上官金文
刘昱
徐静娟
陈洪渊
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Nanjing University
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Nanjing University
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01LCHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
    • B01L3/00Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
    • B01L3/50Containers for the purpose of retaining a material to be analysed, e.g. test tubes
    • B01L3/502Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures
    • B01L3/5027Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip
    • B01L3/502707Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip characterised by the manufacture of the container or its components
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01LCHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
    • B01L2200/00Solutions for specific problems relating to chemical or physical laboratory apparatus
    • B01L2200/10Integrating sample preparation and analysis in single entity, e.g. lab-on-a-chip concept
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01LCHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
    • B01L2200/00Solutions for specific problems relating to chemical or physical laboratory apparatus
    • B01L2200/12Specific details about manufacturing devices

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Hematology (AREA)
  • Clinical Laboratory Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

A kind of dimethyl silicone polymer-paper compound chip, it is that a kind of polydimethylsiloxanepatterns patterns are carried on paper forms the controllable dimethyl silicone polymer-paper compound chip of penetration depth.The chip had not only had the advantages that paper chip was easy to process, has been easy to supported reagent, but have the advantages that dimethyl silicone polymer (PDMS) chip can mutually fit, with excellent biocompatibility and be easy to its surface carry out Micro-flow pipe construction.

Description

A kind of dimethyl silicone polymer-paper compound chip and its preparation method and purposes
Technical field
The present invention relates to compound chips, especially are carried on to be formed on paper by dimethyl silicone polymer (PDMS) compartmentalization and seep The controllable dimethyl silicone polymer of saturating depth-paper compound chip and its preparation method.
Background technique
The concept of paper chip is mainly derived from the papery test paper of viable commercial product, and being allowed using the porous property of paper will be a variety of Detection reagent is carried on the different zones of paper, and usual papery test paper can be by direct-vision methodes such as metachromasias, directly to sample In many kinds of parameters characterized, have the characteristics that cheap, easy-to-use.Infiltration and capillarity of the paper fiber to liquid are utilized simultaneously Sample can be guided to carry out certain movement in paper chip, to reach the pre-separation and other effects to colored samples, eliminated Dependence to complex fluid driving device is suitable for amateur state, such as without professional equipment, layman, rapid broad spectrum sieve It is used when choosing.Nearly ten years, the Conceptual Extension of test paper is an important development, paper chip at paper chip by researcher Concept not only combine test paper test advantage, also concept sets such as pipeline, fluid control, process control in micro-fluidic At coming, application range further expansion, it is considered to be the most possible microfluidic system for obtaining commercialization.Various and paper chip Related technology of preparing, such as cerul patterning techniques, laser-engraving technique, printing technique, the development of paper folding technology etc. is even more abundant The possibility of paper chip design, has pushed the development in this field significantly.But stationery is since it innately has porous structure, it is whole A scraps of paper are the connection main bodys an of fluid permeable, it is therefore necessary to are just able to achieve pair by the flowing that certain method limits liquid The limitation of scraps of paper upper fluid flow range, to be conducive to the detection of quantification.Existing method is mainly by hydrophobic material The control of realizing fluid flow range and sequence is loaded on the scraps of paper by various patterning methods.Such as in black base paper Printing technique and cerul patterning techniques etc..The chip structure that such methods are produced is more coarse, even if passing through paper folding skill Art realizes three-dimensional tube structure, and since pipeline is made of the porous structure of paper base, sample flow speed is slow, sample absorption damage It loses seriously, limits this kind of chip broader practice.
In order to solve this problem, study group proposes by paper hollow out pipeline and the compound chip of paper, in this way by fluid The advantages of pipeline, combines with paper chip, has expanded the function and application range of paper chip.But such work is also limited to very much, Mainly wax and marking ink requires specially treated to be just able to achieve interlayer compound.In fact, using dimethyl silicone polymer (PDMS) there is multiple advantage as chip material, as the micro-fluidic being most widely used, PDMS has good Light transmission, gas permeability, excellent biocompatibility, cheap, simple processing, surface nature especially hydrophilic and hydrophobic can The change from hydrophobic to super hydrophilic is generated by processing such as simple plasma or ozone, is conducive to the control of fluid flow System, the building of three-dimensional structure chip is also able to achieve by such convenient disposal, makes chip functions more horn of plenty.But compare core Piece, PDMS thin slice have larger elasticity, are easy deformation, it is difficult to maintain rock-steady structure, while be difficult to load decorating molecule or its Its various reagents limits the application of PDMS.If the advantage of the advantage of paper chip and PDMS can be combined and take long benefit It is short, impressive progress will be brought for fields such as the quick analysis detections of micro-fluidic chip.The existing method master by PDMS in conjunction with paper If paper surface is carried out functionalization group grafting processing, paper and PDMS are then subjected to chemical friendship using these functionalization groups Connection, to fit together.The cross-linking procedure that such methods are related to is complicated, and the paper chip of acquisition is between each other and there is no mutual The relationship of infiltration, firm pasting are poor.And due to existing the chemical graft of paper is handled, seriously limiting can load on paper Substance classes are unfavorable for the functionalization of paper chip;Since relative liquid is one and can continuously permeate paper in such structure Object, therefore an interface can only be integrally served as in microchip, faciostenosis can be applied.It needs to develop in order to solve this problem A kind of completely new PDMS- paper combination method can overcome more than defect.
Summary of the invention
The invention solves main problem be how using dimethyl silicone polymer (PDMS) in conjunction with stationery discrete phase, It is allowed to not only retain the characteristics of paper chip is easily achieved the load of multiple types substance, stronger mechanical stability, but also has PDMS is easy to construct the advantage of microtube structure on surface, to expand the application range of paper chip.It is specifically exactly to be promoted Depth is combined longitudinally in the planar patterned precision and control PDMS and paper cohesive process that PDMS and paper combine.
In order to solve the above technical problems, the present invention forms the composite construction interpenetrated using PDMS and paper.Utilize temperature Depth in the range and its infiltration paper that PDMS extends on paper is controlled the regulating and controlling effect of PDMS solidification process speed, thus shape At PDMS- paper composite construction.Especially under conditions of temperature is relatively high PDMS can realize within a short period of time rapid curing at Type realizes the building of the PDMS pattern structure that degree of precision, penetration depth are controllable in substrate for the first time.
Technical scheme is as follows:
A kind of dimethyl silicone polymer-paper compound chip, it is that a kind of pattern dimethyl silicone polymer (PDMS) is born It is loaded on paper and forms the controllable dimethyl silicone polymer-paper compound chip of penetration depth.
Above-mentioned compound chip, the paper refers to all kinds of materials with porous structure, as made of wood pulp or straw pulp Stationery passes through weaving porous sheet, Non-woven fabrics lamella, polymer-based or fiberglass-based perforated membrane.
A method of above-mentioned compound chip being prepared, it includes the following steps:
The mixed solution of step 1. preparation dimethyl silicone polymer (PDMS) performed polymer and curing agent;
Step 2 passes through writing, seal, printing or method for printing screen, by above-mentioned dimethyl silicone polymer mixed solution It is transferred to the specific region of paper base;
Step 3. waits -30 minutes 0 second;
Entire material is made dimethyl silicone polymer solidify obtained polydimethylsiloxanes by step 4. in 100 DEG C of -200 DEG C of heating Alkane-paper compound chip.
The preparation method of above-mentioned compound chip, the printing process can be with plane or the method for roll-to-roll printing print Brush.
The preparation method of above-mentioned compound chip, the dimethyl silicone polymer narrated-paper recombination process can be primary poly- diformazan Radical siloxane-paper recombination process, or repeatedly dimethyl silicone polymer-paper recombination process.
Application of the above-mentioned compound chip in separating, analyzing, identifying or identifying.
Specific effect of the invention is as follows:
The present invention using dimethyl silicone polymer at relatively high temperatures controllable time polymerize the characteristics of, in conjunction with paper base pattern Method realize the PDMS- of patterned controllable penetration depth by controlling waiting time before curing and solidification temperature Paper complex method.Using this novel polydimethylsiloxaneoxygen-enrichment-paper compound chip preparation method, resulting chip can be made both to have Have that paper chip is easy to process, is easy to the advantages of supported reagent, and there is dimethyl silicone polymer (PDMS) chip can mutually be affixed It closes, have the advantages that excellent biocompatibility and be easy to carry out Micro-flow pipe construction on its surface.
Detailed description of the invention
Aggressiveness and curing agent mixture curing time vary with temperature relationship before Fig. 1 dimethyl silicone polymer (PDMS).This Locate the preceding aggressiveness selected and curing agent ratio is 10:1.When temperature is promoted to 100 degrees Celsius or more, curing time drops to lower It is horizontal;As solidification temperature increases, curing rate is accelerated.
Fig. 2 dimethyl silicone polymer (PDMS) paper chip patterns condition analysis.A.PDMS penetration depth and solidification temperature Relationship.Show that PDMS can be reduced to the penetration depth of paper base by increasing solidification temperature.B. filter paper PDMS planar diffusion range and solidification Temperature relation;C. printing paper PDMS planar diffusion range and solidification temperature relationship show that higher temperature is conducive to inhibit PDMS Planar diffusion, to obtain better patterning resolution.
Fig. 3 .A1-A2: dimethyl silicone polymer (PDMS) patterned paper chip;B. the novel of PDMS pipe layers is combined PDMS- paper chip sample.The PDMS paper chip for combining PDMS pipe layers directly utilizes composed between paper and PDMS reserve Pipeline flows fluid, rather than traditional paper chip transmits liquid using the capillarity of paper, so that the stream of liquid It is dynamic more quick, while decreasing the loss during liquid flowing.
Polymethyl methacrylate (PMMA) seal of pattern needed for Fig. 4 is used for chip.Wherein greyish white color part is PMMA Seal region.It can be made using this seal similar to the patterning chip in Fig. 3.
Fig. 5 .A: the PDMS paper chip printed by inkjet printing technology.The chip can use crooked pipeline for liquid The premixing of body and response analysis.B: it can be used for preparing the PMMA mold of chip upper pipeline.PMMA solution is toppled over when use It is heating and curing on mold.
Fig. 6 .A: the PDMS paper chip printed by screen printing technique.The chip can use crooked pipeline for liquid The premixing of body and response analysis.B: it can be used for preparing the PMMA mold of chip upper pipeline.PMMA solution is toppled over when use It is heating and curing on mold.
Polymethyl of Fig. 7 for dimethyl silicone polymer-paper compound chip preparation process of multistep recombination process Sour methyl esters (PMMA) seal.A. the seal deeper for positive penetration depth;B. the figure shallower for the penetration depth at the back side Chapter.The white space for needing to reserve the two when use is aligned.
Specific embodiment:
The invention will be further described with example with reference to the accompanying drawing.
Embodiment 1: dimethyl silicone polymer-paper compound chip preparation
Step 1. prepares the mixed solution of dimethyl silicone polymer (PDMS) performed polymer and curing agent, performed polymer and curing agent Mass ratio is 10:1;
The seal of pattern needed for step 2. carves chip, pattern are shown in Fig. 4, the seal for being carved with pattern needed for chip are stained with PDMS is taken, is then covered on printing paper (Zhenjiang Dadong Paper Co., Ltd., in emerging extra white electro-photographic paper) surface;
Step 3. waiting time 2 seconds;
Step 4. solidifies entire material at 200 DEG C, removes seal after solidification, and it is multiple that dimethyl silicone polymer-paper is made Close chip.
Step 5. topples over PDMS mixed solution on seal shown in Fig. 4, so that pattern is completely submerged;
Step 6.PDMS heats 30min solidification at 60 DEG C, removes seal with elbow tweezer;
After obtained PDMS reverse mould pipe surface is dipped a small amount of PDMS solution by step 7., with paper chip pipe alignment before Fitting;
In 200 DEG C of solidification 2s, NEW TYPE OF COMPOSITE chip is made in entire material by step 8. after solidification;
Methyl orange solution, colourless phenolphthalein solution, eriochrome black T is added dropwise in each border circular areas in periphery of chip in step 9. respectively Solution, starch solution, luminol reagent;
Step 10. entreat in the chips pipeline handover region successively inject dilute hydrochloric acid solution, diluted sodium hydroxide solution, hard water, Iodine water, blood sample simultaneously press the border circular areas where corresponding indicator and release respectively immediately after the implantation, make two kinds it is molten Liquid comes into full contact with reaction respectively.
Embodiment 2: dimethyl silicone polymer-paper compound chip preparation
Step 1. prepares the mixed solution of dimethyl silicone polymer (PDMS) performed polymer and curing agent, performed polymer and curing agent Mass ratio is 10:1;
The mixed solution is printed on printing paper by pattern needed for chip, is seen by printing of inkjet printer by step 2. Fig. 5 A;
Step 3. waits 30 minutes;
Step 4. solidifies entire material at 100 DEG C, and dimethyl silicone polymer-paper compound chip is made.
PDMS mixed solution is poured on seal shown in Fig. 5 B by step 5., so that pattern is completely submerged;
Step 6.PDMS heats 30min solidification at 60 DEG C, removes seal with elbow tweezer;
After obtained PDMS reverse mould pipe surface is dipped a small amount of PDMS solution by step 7., with paper chip pipe alignment before Fitting;
In 100 DEG C of solidification 2min, NEW TYPE OF COMPOSITE chip is made in entire material by step 8. after solidification;
Human blood sample product and erythrocyte cracked liquid (triumphant base biology, lot number KGP1150-KGP11100) are injected separately by step 9. Sample delivery point above y-branch;
Step 10. is pressed the PDMS film covered on the liquid storage tank of right side and is unclamped again, and allows blood sample and cell pyrolysis liquid in Y The sufficiently oscillation mixing in pipeline after type bifurcation crosses;
Standing 10min cracks red blood cell completely after the mixed sample of step 11. reaches liquid storage tank.
Carry out subsequent analysis can be sucked out in the obtained blood sample for having cracked red blood cell again.Due to the sample size that uses compared with It is few, so it is suitble to the mixing and subsequent processing of micro-example.
Embodiment 3: dimethyl silicone polymer-paper compound chip preparation
Step 1. prepares the mixed solution of dimethyl silicone polymer (PDMS) performed polymer and curing agent, performed polymer and curing agent Mass ratio is 10:1;
Step 2. is printed by quick silk screen, which is transferred on printing paper by pattern needed for chip, sees figure 6A;
Step 3. waits 0 second;
In 150 DEG C of solidifications rapidly, dimethyl silicone polymer-paper compound chip is made in paper by step 4..
PDMS mixed solution is poured on seal shown in Fig. 6 B by step 5., so that pattern is completely submerged;
Step 6.PDMS heats 30min solidification at 60 DEG C, removes seal with elbow tweezer;
After obtained PDMS reverse mould pipe surface is dipped a small amount of PDMS solution by step 7., with paper chip pipe alignment before Fitting;
In 100 DEG C of solidification 2min, NEW TYPE OF COMPOSITE chip is made in entire material by step 8. after solidification;
Human blood sample product and erythrocyte cracked liquid (triumphant base biology, lot number KGP1150-KGP11100) are injected separately by step 9. Sample delivery point above y-branch;
Step 10. is pressed the PDMS film covered on the liquid storage tank of right side and is unclamped again, and allows blood sample and cell pyrolysis liquid in Y The sufficiently oscillation mixing in pipeline after type bifurcation crosses;
Standing 10min cracks red blood cell completely after the mixed sample of step 11. reaches liquid storage tank.
Carry out subsequent analysis can be sucked out in the obtained blood sample for having cracked red blood cell again.Due to the amount of the sample used It is less, so it is suitble to the mixing and subsequent processing of micro-example.
Embodiment 4: the dimethyl silicone polymer of multistep recombination process-paper compound chip preparation
Step 1. prepares the mixed solution of dimethyl silicone polymer (PDMS) performed polymer and curing agent, performed polymer and curing agent Mass ratio is 10:1;
The seal for being carved with the pattern that dimethyl silicone polymer penetration depth is deeper needed for chip is picked PDMS by step 2., It covers and specifies region in filter paper (Hangzhou Wo Hua filter paper Co., Ltd enjoy a double blessing board 9mm qualitative filter paper), such as Fig. 7 A;
Step 3. waits 10 minutes, and PDMS is made thoroughly to infiltrate through paper base;
Step 4. solidifies entire material at 100 DEG C;
The seal for being carved with the pattern that dimethyl silicone polymer penetration depth is shallower needed for chip is picked PDMS by step 5., It covers and specifies region on filter paper, such as Fig. 7 B;
Step 6. waits 0 second;
Step 7. solidifies entire material at 180 DEG C, and dimethyl silicone polymer-paper compound chip is made.
The preparation of step 8. saccharomycete agar medium: sodium nitrate 3.0g, disodium hydrogen phosphate 1.0g, potassium chloride are weighed 0.5g, bitter salt 0.5g, ferrous sulfate 0.01g, sucrose 30.0g, agar 30g, distilled water 1000ml dissolution, 121 DEG C High-temperature sterilization.
The preparation of step 9. yeast bacteria culture fluid: repeating the operation of step 8, removes the step of agar is added;
Step 10. is mixed when culture medium solution is reduced to 40 DEG C or so, by saccharomycete suspension vol ratio 1:1 with culture medium It is even;
Step 11. will mix drop on polymethyl methacrylate (PMMA) film, suppress agar thin slice;
Thin slice is lain in chip shallower seal face side dot matrix area by step 12., and chip pipe line area is placed in culture solution, Every the Yeast Growth situation of observation in 2 hours.It can be found that saccharomycete may be implemented to continue division growth on chip.
The method achieve the infiltrations of the patterning of different depth PDMS structures a variety of on a paper base to control.

Claims (7)

1. a kind of dimethyl silicone polymer-paper compound chip, it is characterized in that: it is a kind of to bear polydimethylsiloxanepatterns patterns It is loaded in the dimethyl silicone polymer-paper compound chip formed on paper, the polydimethylsiloxanepatterns patterns penetration depth is controllable It is to regulate and control by standing -30 minutes 0 second after patterning and in 100 DEG C of -200 DEG C of heating.
2. compound chip according to claim 1, it is characterized in that: the paper refers to all kinds of materials with porous structure Material.
3. compound chip according to claim 2, it is characterized in that: the material with porous structure is wood pulp or grass Stationery made of starching passes through weaving porous sheet, Non-woven fabrics lamella, polymer-based or fiberglass-based perforated membrane.
4. a kind of method for preparing compound chip described in claim 1, it is characterized in that it includes the following steps:
The mixed solution of step 1. preparation dimethyl silicone polymer (PDMS) performed polymer and curing agent;
Above-mentioned dimethyl silicone polymer mixed solution is transferred to paper by seal, printing or method for printing screen by step 2. The specific region of base;
Step 3. waits -30 minutes 0 second;
Entire material is made dimethyl silicone polymer solidify obtained dimethyl silicone polymer-by step 4. in 100 DEG C of -200 DEG C of heating Paper compound chip.
5. according to the method described in claim 3, it is characterized in that: the printing process is the side with plane or roll-to-roll printing Method printing.
6. according to the method described in claim 3, it is characterized in that: the dimethyl silicone polymer-paper recombination process is primary Dimethyl silicone polymer-paper recombination process, or repeatedly dimethyl silicone polymer-paper recombination process.
7. dimethyl silicone polymer described in claim 1-application of the paper compound chip in separating, analyzing, identifying or identifying.
CN201610239287.2A 2016-04-18 2016-04-18 A kind of dimethyl silicone polymer-paper compound chip and its preparation method and purposes Expired - Fee Related CN105903501B (en)

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