EP1222031B1 - Procede et dispositif de deplacement controle et de depot de gouttelettes de liquide - Google Patents

Procede et dispositif de deplacement controle et de depot de gouttelettes de liquide Download PDF

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Publication number
EP1222031B1
EP1222031B1 EP00966067A EP00966067A EP1222031B1 EP 1222031 B1 EP1222031 B1 EP 1222031B1 EP 00966067 A EP00966067 A EP 00966067A EP 00966067 A EP00966067 A EP 00966067A EP 1222031 B1 EP1222031 B1 EP 1222031B1
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EP
European Patent Office
Prior art keywords
substrate
ultraphobic
electrodes
substrate according
hydrophobic
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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.)
Expired - Lifetime
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EP00966067A
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German (de)
English (en)
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EP1222031A1 (fr
Inventor
Karsten Reihs
Burkhard KÖHLER
Dieter RÜHLE
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Sunyx Surface Nanotechnologies GmbH
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Sunyx Surface Nanotechnologies GmbH
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
    • B01L3/00—Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
    • B01L3/02—Burettes; Pipettes
    • B01L3/0241—Drop counters; Drop formers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
    • B01L3/00—Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
    • B01L3/50—Containers for the purpose of retaining a material to be analysed, e.g. test tubes
    • B01L3/502—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures
    • B01L3/5027—Containers 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
    • B01L3/502769—Containers 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 multiphase flow arrangements
    • B01L3/502784—Containers 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 multiphase flow arrangements specially adapted for droplet or plug flow, e.g. digital microfluidics
    • B01L3/502792—Containers 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 multiphase flow arrangements specially adapted for droplet or plug flow, e.g. digital microfluidics for moving individual droplets on a plate, e.g. by locally altering surface tension
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
    • B01L2300/00—Additional constructional details
    • B01L2300/08—Geometry, shape and general structure
    • B01L2300/089—Virtual walls for guiding liquids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
    • B01L2400/00—Moving or stopping fluids
    • B01L2400/04—Moving fluids with specific forces or mechanical means
    • B01L2400/0403—Moving fluids with specific forces or mechanical means specific forces
    • B01L2400/0415—Moving fluids with specific forces or mechanical means specific forces electrical forces, e.g. electrokinetic

Definitions

  • the present invention relates to a method and apparatus for moving and metering liquid quantities on a microscopic scale with a volume of in particular 10 -12 to 10 -6 liters with an electric field using a carrier with an ultraphobic surface optionally in combination with an ultraphobic dosing tip ,
  • the object is achieved by providing a method for Microdosing liquid droplets solved in which the liquid droplets with an inhomogeneous electric field on a support with an ultraphobic surface be moved lossless.
  • the invention relates to a substrate according to claim 1 and a method according to claim 10 and a method according to Claim 16 and uses of the substrate according to claims 14 and 15.
  • the manipulator is an electrically charged tip or a wire, in particular a tip or a wire with an ultraphobic surface used.
  • the tension can vary greatly depending on Geometry of the arrangement.
  • a liquid drop according to the invention consists of any liquid and preferably has a volume of 10 -12 to 10 -6 liters, more preferably from 10 -9 to 10 -6 liters. According to the invention, such a drop is moved without loss with a displaceable electric field on an ultraphobic surface.
  • liquid drop by means of the electric field divided off a liquid reservoir.
  • Several drops of liquid can by means of of the electric field united on an ultraphobic surface and to be mixed. All of these process steps can also be in any Combined with each other.
  • the electric field is between a Tip, which preferably has a diameter of 0.01 to 1 mm, any Length has an ultraphobic surface, and one preferably metallic carrier. With this tip drops of liquid on the ultraphoben Surface moved. This makes the tip an ultraphobic surface have no liquid components adhere to the tip.
  • liquid reservoir of the Device on an arrangement for electrostatic charging.
  • Ultraphobic surfaces according to the invention are characterized in that the Contact angle of a water drop lying on the surface, more than 150 ° is and the roll angle does not exceed 10 °.
  • a rolling angle here is the inclination angle of a basically planar but textured surface against the horizontal understood, where a standing Drops of water of volume 10 ⁇ l due to gravity is moved when the Surface is tilted.
  • Such an ultraphobic surface is described in international patent application WO 99/10322.
  • a hydrophobic material in the context of the invention is a material that is on a even, non-textured surface a contact angle, relative to water, of greater than 90 °.
  • An oleophobic material in the context of the invention is a material which is based on a even, non-textured surface a contact angle, based on long-chain n-alkanes, such as n-decane, of greater than 90 °.
  • the ultraphobic surface is an aluminum surface that has microstructures provided, anodized, optionally gesealt, calcined, optionally with coated with a primer layer and then with a hydrophobic and / or oleophobic coating is provided, as it is in the international Patent application WO 99/10323 is described.
  • the manipulator and / or the carrier can be made entirely of aluminum or preferably has an aluminum coating, wherein the aluminum, such as treated above.
  • the ultraphobic surface is an aluminum surface that optionally anodically oxidized, with hot water or steam gesealt, optionally coated with a primer layer and then with a hydrophobic and / or oleophobic coating is provided, as in the international patent application WO 99/10324.
  • the dosing tip can be made entirely of aluminum or preferably has one Aluminum coating, wherein the aluminum treated as stated above becomes.
  • the ultraphobic surface is preferably a surface which is coated with Ni (OH) 2 particles, optionally coated with an adhesion promoter and subsequently provided with a hydrophobic and / or oleophobic coating, as described in international patent application WO 99/10111 is.
  • the Ni (OH) 2 particles have a diameter d 50 of 0.5 to 20 microns.
  • the ultraphobic surface is made Tungsten carbide structured with a laser, optionally with a coupling agent coated and then with a hydrophobic and / or oleophobic Cover is provided, as in the international patent application WO 99/10113 is described.
  • the metering tip is only with Tungsten carbide, which is then treated as indicated above.
  • the tungsten carbide has a layer thickness of 10 to 500 microns.
  • the surface is sandblasted with a blasting agent, optionally coated with a primer layer and then with a provided hydrophobic and / or oleophobic coating, as in the international Patent application WO 99/10112 is described.
  • Suitable as a hydrophobic and / or oleophobic coating of said surfaces all interface-active repellents with any molecular weights. at these compounds are cationic, anionic, amphoteric and / or non-ionic surface-active compounds, such as e.g. in the register "Surfactants Europe, A Dictionary of Surface Active Agents available in Europe, Edited by Gordon L. Hollis, Royal Socity of Chemistry, Cambridge, 1995 become.
  • anionic repellents which may be mentioned are: alkyl sulfates, Ether sulfates, ether carboxylates, phosphate esters, sulfosuccinates, sulfosuccinamides, Paraffin sulfonates, olefin sulfonates, sarcosinates, isothionates, taurates and lingnins Links.
  • cationic repellent auxiliary agents are, for example, quaternary alkylammonium compounds and to call imidazoles.
  • Amphoteric repellents are, for example, betaines, glycinates, propionates and imidazoles.
  • Nonionic repellents are, for example: alkoxylates, alkylamides, Esters, amine oxides and alkyl polyglycosides. Also suitable: reaction products of alkylene oxides with alkylatable compounds, such as. B. fatty alcohols, Fatty amines, fatty acids, phenols, alkylphenols, arylalkylphenols, such as Styrene-phenol condensates, carboxylic acid amides and resin acids.
  • repellents in which 1 to 100%, especially preferably 60 to 95% of the hydrogen atoms are substituted by fluorine atoms.
  • exemplary be perfluorinated alkyl sulfate, perfluorinated alkyl sulfonates, perfluorinated Alkyl phosphonates, perfluorinated alkyl phosphinates and perfluorinated carboxylic acids called.
  • These polymeric repellents may be nonionic, anionic, cationic or amphoteric compounds.
  • these polymeric repellents may be homo- and copolymers, graft and graft copolymers and random block polymers.
  • Particularly preferred polymeric repellents are those of the type AB-, BAB and ABC block polymers.
  • the AB or BAB block polymers is the A segment a hydrophilic homopolymer or copolymer, and the B block is a hydrophobic one Homopolymer or copolymer or a salt thereof.
  • anionic, polymeric repellents in particular Condensation products of aromatic sulfonic acids with formaldehyde and alkylnaphthalenesulfonic acids or from formaldehyde, naphthalenesulfonic acids and / or benzenesulfonic acids, condensation products of optionally substituted Phenol with formaldehyde and sodium bisulfite.
  • condensation products obtained by reaction of Naphthols with alkanols, additions of alkylene oxide and at least partial Conversion of the terminal hydroxy groups in sulfo groups or half esters of Maleic acid and phthalic acid or succinic acid are available.
  • the repellent auxiliary is selected from the group of sulfosuccinic acid esters and alkylbenzenesulfonates.
  • sulfated, alkoxylated fatty acids or salts thereof are in particular those having from 5 to 120, with 6 to 60, most preferably provided with 7 to 30 ethylene oxide C 6 -C 22 -Fettklarealkohole, which are saturated or unsaturated, in particular stearyl, understood.
  • the sulfated alkoxylated fatty acid alcohols are preferably present as salt, in particular as alkali or amine salts, preferably as diethylamine salt.
  • the inventive method is easier to perform than the conventional Microdosing with the help of pressing. Due to the minimal adhesion of the liquid drops on the ultraphobic surfaces, the manupulation is of the smallest Liquid quantities without losses possible. As a result, dosing errors can be avoided become.
  • Another object of the invention is the use of the device according to the invention for metering liquids on a microscopic scale, in particular in the range of 10 -6 to 10 -12 liters.
  • FIG. 1 shows a device 1 according to the invention for residue-free movement of liquid drops (here aqueous solutions) on solid surfaces.
  • the device consists of a substrate 2 (here Plexiglas), on its surface round electrically conductive electrodes 3 (diameter 1 mm, spacing 5 mm) introduced are flush with the surface of the substrate. To the individual Electrodes 3 different voltages can be applied against each other.
  • the surface of the substrate 2 is coated with an approximately 5 microns thick electrically insulating provided with ultraphobic coating. This is on the substrate about 5 microns thick Layer of aluminum evaporated.
  • the Al layer is anodized, with treated with hot steam and provided with a hydrophobic coating. to Preparation of the hydrophobic coating, the substrate is 5 hours at pH 7 in a 1 wt .-% solution of Fluowet PL80 Clariant immersed, with water rinsed and dried at 60 ° C.
  • the Al layer is completely in an aluminum oxide layer by this treatment been converted.
  • One Drop 5 may be on the surface in the direction of a directly adjacent electrode be moved by facing this electrode to a potential of 800V the other electrodes is switched. Then the drop is above the relevant one Electrode.
  • the movement can be of the droplet 5 on the surface arbitrarily control within the electrode grid. In this way, also different drops 4, 5 moved to the same place and united with each other.
  • a drop 4 (diameter about 1 mm) of a solution of 4- (6-diethylamino-3-diethylimino-3H-xanthe-9-yl) -1,3-benzodisulfonic acid (Kiton Red, concentration 1 x 10 -2 mol / l in water) is located on the ultraphobic surface.
  • the drop 4 is displaced along a closed path over 8 electrodes (length of the path 40 mm). This process is repeated 10 times, so that the total distance is 400 mm. Subsequently, the drop is removed and a drop of pure water along the previously used closed path also moved 10 times.
  • This water droplet is examined spectrophotometrically. Up to the detection limit of 10 -10 mol / l (based on the drop volume) no dye can be detected. The losses due to the displacement of the droplet are thus less than 10 ppb.
  • liquid drops used which are surrounded by solid walls from all sides, e.g. in Columns or tubes. These designs thus allow lossless promotion of liquids solely by the change of electric fields, i. without mechanically moving parts.
  • FIG. 2 shows a device 6 for complete transmission of liquid drops (here aqueous solutions) by means of a mobile Tip 10.
  • the device has a support plate 7 made of aluminum with an ultraphoben Plating and a top 10 on.
  • the tip also has an ultraphobic surface on.
  • the preparation of the ultraphobic coating is carried out according to Example 1.
  • a drop 8 of a solution of 4- (6-diethylamino-3-diethylimino-2H-xanthe-9-yl) -1,3-benzodisulfonic acid (Kiton Red, concentration 1 ⁇ 10 -2 mol / l in water) is on the ultraphobic surface.
  • the drop 8 can be recorded. This is approached the tip to a distance of about 5 mm, with between 10 and the top Substrate plate 7, a voltage of 800 V is applied. The radius of the tip is approx. 0.5 mm.
  • the drop hanging on top is placed in a jar containing 65 ⁇ l of water by switching off the voltage.
  • Another example shows the metering and complete transfer of liquid drops with the aid of the device in FIG. 2.
  • a drop 8 of a solution of 4- (6-diethylamino-3-diethylimino-3H-xanthe-9-yl) -1,3-benzodisulfonic acid (Kiton Red, concentration 1 x 10 -2 mol / l in water) is on the ultraphobic surface.
  • Example 2 With the help of the tip 10 of the drop 8 is recorded as in Example 2.
  • the on the tip hanging drops is in a recess 11 of the device by switching off the voltage is stored.
  • the other drop 9 is taken up with the tip and united with the drop 8 in the well. Then be pick up both drops with the tip and place in a container with 65 ⁇ l of water according to Example 2 transferred.
  • the dye concentrations in the water were then determined spectrophotometrically.
  • the transfer was carried out 5 times in the same way, resulting in no loss of the transferred volumes V 3 and V 4 within the relative dosing error of 1.5%.
  • Fig. 3 shows an arrangement for the controlled removal of small known liquid volumes from a supply (cross-sectional drawing).
  • the arrangement consists of an electrode 12 with a round tip (diameter 1 mm) and an annular electrode 13 (inner diameter 0.5 mm). Both electrodes are provided with an ultrahydrophobic coating, the preparation of which is described in Example 1.
  • the assembly is immersed in an aqueous solution of 4- (6-diethylamino-3-diethylimino-3Hxanthe-9-yl) -1,3-benzodisulfonic acid (Kiton Red, concentration 10 -2 mol / L in water) (as shown in FIG. 3).
  • FIG. 4 instead of the annular electrode 13 of the device in FIG. 3, an arrangement as in FIG. 4 may also be used.
  • three round electrodes 16 (diameter 1 mm) are provided with an ultrahydrophobic coating, whose preparation is described in Example 1.
  • the electrodes 16 are arranged as described in Fig. 4 for forming a nearly triangular-shaped spade M, which has the same function of the ring electrode 13 in FIG.
  • a drop of liquid is removed from a supply. Reproducing the dose 30 times gives a volume of (50.0 ⁇ 0.3) ⁇ 10 -12 liters.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Clinical Laboratory Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Hematology (AREA)
  • Apparatus Associated With Microorganisms And Enzymes (AREA)
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  • Application Of Or Painting With Fluid Materials (AREA)
  • Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)
  • Extraction Or Liquid Replacement (AREA)
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  • Physical Or Chemical Processes And Apparatus (AREA)

Claims (18)

  1. Substrat (2), dans lequel sont incorporées plusieurs électrodes (3), auxquelles peuvent être appliquées des tensions individuelles différentes les unes des autres et qui est muni d'un revêtement ultraphobe.
  2. Substrat selon la revendication 1, caractérisé en ce que les électrodes (3) affleurent à la surface du substrat (2).
  3. Substrat selon la revendication 2, caractérisé en ce que les électrodes sont agencées selon un réseau régulier.
  4. Substrat selon l'une quelconque des revendications qui précèdent, caractérisé en ce que la surface ultraphobe présente une topographie de surface telle que la fréquence locale f des composants de Fourier individuelles et leur amplitude a(f) exprimée par l'intégrale S(log(f)) = a(f).f calculée entre les limites d'intégration log(f1/µm-1) = -3 et log(f1/µm-1) = 3 a une valeur d'au moins 0,3 et qu'elle est constituée de polymères ultraphobes ou de matériaux durablement ultraphobes.
  5. Substrat selon l'une quelconque des revendications qui précèdent, caractérisé en ce que la surface ultraphobe est une surface d'aluminium structurée et revêtue d'un matériau hydrophobe et/ou oléophobe.
  6. Substrat selon l'une des revendications 1 à 4, caractérisé en ce que la surface ultraphobe est une surface d'aluminium traitée par de la vapeur d'eau et revêtue d'un matériau hydrophobe et/ou oléophobe.
  7. Substrat selon l'une des revendications 1 à 4, caractérisé en ce que la surface ultraphobe est une surface recouverte de particules de Ni(OH)2 et revêtue d'un matériau hydrophobe et/ou oléophobe.
  8. Substrat selon l'une des revendications 1 à 4, caractérisé en ce que la surface ultraphobe est une surface sablée et revêtue d'un matériau hydrophobe et/ou oléophobe.
  9. Substrat ou dispositif selon l'une des revendications 1 à 4, caractérisé en ce que la surface ultraphobe est une surface de carbure de tungstène structurée au laser et revêtue d'un matériau hydrophobe et/ou oléophobe.
  10. Procédé pour le déplacement ou le dosage d'une goutte de liquide à l'échelle microscopique avec un substrat selon l'une des revendications 1 à 9, caractérisé en ce que la goutte de liquide (8,9) est déplacée au moyen des électrodes (3).
  11. Procédé selon la revendication 10, caractérisé en ce que des tensions individuelles différentes les unes des autres sont appliquées aux électrodes.
  12. Procédé selon la revendication 10 ou 11, caractérisé en ce qu'une goutte de liquide est déplacée à volonté au sein d'un réseau d'électrodes.
  13. Procédé selon la revendication 12, caractérisé en ce que plusieurs gouttes sont déplacées dans le réseau d'électrodes et ainsi réunies ensemble.
  14. Utilisation du substrat selon l'une quelconque des revendications 1 à 9 et du procédé selon l'une quelconque des revendications 10 à 13 pour le dosage de liquides à l'échelle microscopique, de préférence de l'ordre de 10-6 à 10-12 litre, plus préférentiellement de l'ordre de 10-6 à 10-9 litre.
  15. Utilisation du substrat selon l'une quelconque des revendications 1 à 9 et du procédé selon l'une quelconque des revendications 10 à 13 pour l'exécution de processus chimiques ou biochimiques, de préférence des PCR, ELISA, et/ou pour la détermination des activités enzymatiques.
  16. Procédé de préparation d'un substrat selon l'une des revendications 1 à 9, caractérisé en ce que les électrodes sont intégrées au substrat et que la surface du substrat est munie d'un revêtement ultraphobe.
  17. Procédé selon la revendication 16, caractérisé en ce que les électrodes sont agencées de manière à affleurer à la surface du substrat.
  18. Procédé selon l'une des revendications 16 ou 17, caractérisé en ce que les électrodes sont intégrées au substrat selon un réseau régulier.
EP00966067A 1999-10-05 2000-09-22 Procede et dispositif de deplacement controle et de depot de gouttelettes de liquide Expired - Lifetime EP1222031B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19947788 1999-10-05
DE19947788A DE19947788A1 (de) 1999-10-05 1999-10-05 Verfahren und Vorrichtung zum Bewegen von Flüssigkeiten
PCT/EP2000/009272 WO2001024934A1 (fr) 1999-10-05 2000-09-22 Procede et dispositif de deplacement controle et de depot de gouttelettes de liquide

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EP1222031A1 EP1222031A1 (fr) 2002-07-17
EP1222031B1 true EP1222031B1 (fr) 2003-09-17

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US (1) US7214302B1 (fr)
EP (1) EP1222031B1 (fr)
JP (1) JP2003511247A (fr)
AT (1) ATE249886T1 (fr)
AU (1) AU779566B2 (fr)
CA (1) CA2387581C (fr)
DE (2) DE19947788A1 (fr)
WO (1) WO2001024934A1 (fr)

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CN107649223B (zh) * 2017-09-27 2019-10-15 京东方科技集团股份有限公司 液滴控制检测器件及其工作方法
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WO2020210292A1 (fr) 2019-04-08 2020-10-15 Miroculus Inc. Appareils microfluidiques numériques à cartouches multiples et procédés d'utilisation
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US7214302B1 (en) 2007-05-08
EP1222031A1 (fr) 2002-07-17
CA2387581A1 (fr) 2001-04-12
ATE249886T1 (de) 2003-10-15
DE50003758D1 (de) 2003-10-23
AU779566B2 (en) 2005-01-27
DE19947788A1 (de) 2001-04-12
CA2387581C (fr) 2009-06-16
WO2001024934A1 (fr) 2001-04-12
JP2003511247A (ja) 2003-03-25
AU7658900A (en) 2001-05-10

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