CN1725007A - Preparation method of polymer microflow control chip having metal microelectrode - Google Patents
Preparation method of polymer microflow control chip having metal microelectrode Download PDFInfo
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- CN1725007A CN1725007A CN 200510050716 CN200510050716A CN1725007A CN 1725007 A CN1725007 A CN 1725007A CN 200510050716 CN200510050716 CN 200510050716 CN 200510050716 A CN200510050716 A CN 200510050716A CN 1725007 A CN1725007 A CN 1725007A
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- microelectrode
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- metal microelectrode
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Abstract
The invention provides a method for preparing high polymer micro-flow control chip with metallic microelectrode, characterized in integrating photochemical method and chemical plating to generate the microelectrode in the selective region of the high polymer surface; processing a cover plate plated with the microelectrode on the surface and a substrate with cross channel on the surface by oxygen plasma atmosphere and then sealing them by thermal pressing method to obtain the micro-flow control chip. The invention has the advantages of simple preparing technique, low cost and good analyzing effect.
Description
Technical field
The present invention relates to the method that a kind of preparation has the capillary electrophoresis electrochemical detection superpolymer chip of metal microelectrode.
Background technology
Micro-full analytical system (Miniaturized Total Analysis Systems, μ TAS) is one of new academic frontier of present analysis chemistry, and chip capillary cataphoresis then is one of main flow research field among the μ TAS.At present, chip capillary cataphoresis adopts high speed, efficient and highly sensitive the separation and analysis that laser-induced fluorescence (LIF) (LIF) detecting device is finished important complex biochemical sample such as DNA, protein more.But most compounds do not have natural fluoresence, could be after needing to derive, and the LIF detector volume is huge for LIF detect through fluorescence, influenced the microminiaturization of whole analytic system and integrated.The electrochemical detector cost is low, highly sensitive, it is integrated to be easy to, can directly detect chemical compound lot, is subject to people's attention more and more.The micro-fluidic chip that development has the Electrochemical Detection microelectrode becomes a current research and development focus.Preparation at present has the conventional method of the micro-fluidic chip of integrated microelectrode: the metal that 1. forms one deck electrode material on glass substrate by the method for sputter (perhaps thermal evaporation), after applying one deck optical cement, make the cover glass that has microelectrode by photoetching one wet etching technology again; 2. on another sheet glass substrate, prepare micro-channel; 3. will have that the microelectrode cover glass is aimed at the glass substrate that has micro-channel, involution together, form microfluidic analysis chip.This clean operating room of method needs and some expensive specific installations that prepare chip, the cost height.At present, also have the micro-channel preparation on dimethyl silicone polymer (PDMS is commonly called as silicon rubber) sheet, be combined into " hybridization " chip of forming by two kinds of materials with the cover glass that has microelectrode again.Though, overcome the difficult problem of involution, because two kinds of electroosmotic flow differences that material is supported have influenced electrophoretic separation efficient.
Reported in literature usefulness thermoplastic high polymer material such as polymethylmethacrylate (PMMA), polycarbonate (PC) preparation full-plastic microfluidic analysis chip are also arranged.This class chip adopts LIF to detect basically, is used for compartment analysises such as DNA.
(patent No.: it is a kind of by means of the photodegradation of ultraviolet light to superpolymer 20040191703) to have announced that Soper-McCarley research group of United States Louisiana state university invents for United States Patent (USP) recently, carry out the selective light chemical modification in Polymer Surface, thus the new technology that need not photoresist can carry out photoetching in Polymer Surface.Make ultraviolet light pass through the selection zone on quartz/chromium plate mask irradiation PMMA or PC surface, make this zone generation photochemical reaction and form carboxyl.On this basis,, can form the necessary active centre of electroless plating, realize the metallization in selection zone in the superpolymer immersion chemical plating fluid with the selectivity activation at PMMA or PC surface by amination, gold chloride processing, sodium borohydride reduction.
But, to use and be prone to the non-selective plating phenomenon of crossing when this technology prepares metal microelectrode on the PC sheet, the adhesion between coating and the PC sheet also owes strong.
Summary of the invention
The purpose of this invention is to provide the method that a kind of technology is simple, cost is low preparation has the micro-fluidic chip of metal microelectrode.
The invention provides the preparation method of the micro-fluidic chip that has metal microelectrode, it is characterized in that: the selective light chemical modification technology that adopts Polymer Surface, preparation has the thermoplastic high polymer material cover plate of metal microelectrode, prepared chip is made up of two high polymer materials: a slice is the high polymer material substrate that has the cruciform microchannel, another sheet is the high polymer material cover plate that has metal microelectrode, has the micro-fluidic chip of capillary electrophoresis electrochemical measuring ability by the method involution formation of hot pressing.
Concrete steps are:
(1) on the superpolymer cover plate, prepares metal microelectrode in conjunction with the electroless plating of selective area by the selective light chemical modification;
(2) use Ni-based formpiston or silicon formpiston, hot pressing forms cruciform passage substrate on the superpolymer substrate;
(3) adopt the pressure sintering involution to have metal microelectrode cover plate and cruciform passage substrate, obtain to have the microcurrent controlled capillary tube electrophoresis Electrochemical Detection superpolymer chip of metal microelectrode.
With the golden microelectrode of preparation on the PC sheet is example, and the method for preparing golden microelectrode on the PC cover plate of the present invention the steps include:
(1) is photomask with quartz/chromium plate, as light source irradiation carried out in the selection zone on PC cover plate surface with ultraviolet light;
(2) adopt ethylenediamine as amination liquid, 1-[3 '-(N, N-dimethyl amido) propyl group]-the 3-ethyl-carbodiimide hydrochloride is that coupling agent is to carrying out aminating reaction through the PC that selects area radiation;
(3) will be through reacting in the PC cover plate immersion chlorauric acid solution of selecting regional amination;
(4) after water cleans, it is immersed in the sodium borohydride solution reduce again;
(5) after water cleans, again it is immersed ultrasonic cleaning in the potassium bisulfide solution;
(6) will be immersed in the plating bath of forming by gold sodium sulfide, sodium sulphite and formaldehyde through the PC cover plate that cleans, reacted 30-60 minute down at 45-50 ℃.
(7) after the PC cover plate that will be coated with golden microelectrode is put into the baking oven annealing in process, promptly obtain the PC cover plate that has golden microelectrode of the present invention.
The present invention has the sealing method of golden microelectrode cover plate and cruciform passage substrate, the steps include:
(8) use Ni-based formpiston or the silicon formpiston that has the cross channel architecture, hot pressing on the PC substrate, the cooling back demoulding forms the PC substrate with cross passage;
(9) use drill bit, get out four liquid storage holes at four ends of the cross passage of PC substrate;
(10) PC gold microelectrode cover plate and surperficial PC substrate with cross passage are handled in low-temperature oxygen plasma atmosphere;
(11) rapidly cover plate is combined on the substrate with cross passage, pre-fixes with the relative position of solvent with two, the chip after fixing is placed between two sheet glass, use clamp, put into the baking oven heat-sealing, chip is taken out in the cooling back;
(12) be stained with the reservoir of suitable size with epoxy resin in four liquid storage hole positions of passage, obtain to have the microcurrent controlled capillary tube electrophoresis Electrochemical Detection chip of golden microelectrode.
The potassium bisulfide solution concentration that ultrasonic cleaning of the present invention is adopted is: 0.2-0.5mol/L, scavenging period is: 30-60 minute.
Cover plate annealing in process temperature of the present invention is: 138-142 ℃, and time 2-3 hour.
The solvent that chip of the present invention pre-fixes is a methylene chloride.
The heat-sealing of chip of the present invention is put into baking oven with the chip after fixing, is warming up to 146 ℃, is incubated after 20-30 minute, is cooled to room temperature, takes out chip.
The high polymer material of preparation chip of the present invention can be polycarbonate (PC), polyethylene terephthalate (PET), polymethylmethacrylate thermoplastic macromolecule materials such as (PMMA).
Metal microelectrode of the present invention can be noble metal or transition metal materials such as gold, copper, nickel, platinum, palladium, silver.
Metal microelectrode of the present invention can be single electrode, bipolar electrode, multi-electrode, array electrode etc.
Because the present invention carries out ultrasonic cleaning to the PC surface through overactivation in potassium bisulfide solution, the non-selective plating phenomenon of crossing that has occurred when having eliminated the chemical plating metal microelectrode; By the adhesion between annealing increase electrode and cover plate; The method of heat-sealing again after the substrate that will have the cover plate of microelectrode and have a cross microchannel with solvent pre-fixes has guaranteed the precision of chip involution.Characteristics of the present invention are: adopt the photochemistry metal microelectrode precision height that selective modification-the selective area electroless plating technology makes in Polymer Surface, analytical performance is good; The whole process of chip can be in the Experiment of General Chemistry chamber or comparatively be utilized general chemical ware and plant equipment to carry out in the workshop of cleaning, need not clean operating room and specific installation, and technology is easily grasped, and cost is low.
Description of drawings:
Fig. 1 has the micro-fluidic chip of golden microelectrode
Fig. 2 uses the electrophoresis spectrogram of chip separation detection dopamine shown in Figure 1 and catechol
Among the figure: (a) graphics chip behind the involution; (b) configuration of passage and microelectrode.1-sample solution pond, 2-sample waste liquid pool, the 3-buffer pool, 4-waste liquid pool (detection cell), 5-gold microelectrode, 6-has the substrate of cross passage, and 7-has the cover plate of microelectrode, 8-dopamine, 9-catechol.
Embodiment
Referring to Fig. 1, the step that preparation has the integrated capillary electrophoresis electrochemical detected in polycarbonate micro-fluidic chip of golden microelectrode is:
A, with low pressure mercury lamp as light source, quartz/chromium plate is made mask, irradiation was carried out 2.5 hours in the selection zone on PC cover plate 7 surfaces of, 4 * 6cm thick to 0.5-1mm.
B, the PC cover plate 7 that the width of cloth was shone are put into 0.36mol/L ethylenediamine-0.5mol/L 1-[3 '-(N, N-dimethyl amido) propyl group]-3-ethyl-carbodiimide hydrochloride solution in reaction 3 hours, clean up with distilled water.
C, will immerse in the 1mmol/L chlorauric acid solutions reaction through the PC cover plate 7 of (B) reaction 2.5 hours, after water cleans, again it be immersed in the 0.1mol/L sodium borohydride solution reaction 10 minutes.
D. will after the PC cover plate 7 waters flushing of (C) reaction, immerse in the 0.2-0.5mol/L potassium bisulfide solution ultrasonic cleaning 30-60 minute.
E, with after PC cover plate 7 waters after the ultrasonic cleaning flushings, be immersed in the chemical gold plating liquid (8mmol/L gold sodium sulfide, 0.125mol/L sodium sulphite and 0.6mol/L formaldehyde), reacted 30-60 minute down in 45-50 ℃, just can form even, fine and closely woven thin au microelectrode 5 in specific selection zone, clean, dry up.When noble metal such as preparation copper, nickel, platinum, palladium, silver or transition metal microelectrode, as long as change chemical plating fluid into the corresponding metal plating bath.
F, the PC cover plate 7 that will be coated with golden microelectrode 5 were put into baking oven, 138-142 ℃ of annealing 2-3 hour.
G, use Ni-based formpiston or the silicon formpiston have the cross channel architecture, at 142 ℃, under the condition of 1.0MPa, hot pressing is 2 minutes on the PC substrate of, 3 * 6cm thick at another sheet 2-4mm, and the cooling back demoulding forms the PC substrate 6 with cross passage.
H, use the drill bit of 1-2mm diameter, get out four liquid storage holes at four ends of cross passage.
I, the surface is coated with the PC cover plate (electrode surface upwards) of microelectrode and PC substrate (surface channel upwards) that the surface has the cross passage low-temperature oxygen plasma atmosphere processing 5 minutes.
J, the PC cover plate that will have an electrode rapidly are combined on the PC substrate with cross passage, the outlet that makes the microelectrode on the PC cover plate aim at split tunnel on the PC substrate at microscopically, make between electrode-channel outlet between from being controlled at 20-50 μ m, behind the aligning immediately at four jiaos of each methylene chloride of chip, in air, volatilize, so that the relative position of cover plate and substrate is fixed.
K, the chip after will fixing are placed between two sheet glass, use clamp, put into baking oven, are warming up to 146 ℃, are incubated after 20-30 minute, are cooled to room temperature, take out chip.
L, be stained with the sample solution pond 1 of suitable size with epoxy resin in four liquid storage hole positions of passage, sample waste liquid pool 2, buffer pool 3, waste liquid pool 4 is promptly made the micro-fluidic chip that has golden microelectrode of the present invention.
The above-mentioned microcurrent controlled capillary tube electrophoresis Electrochemical Detection chip that has golden microelectrode is used for separation detection dopamine and catechol, and analytical effect is good, sees the electrophoresis spectrogram of Fig. 2.8-dopamine among the figure, 9-catechol, concentration are 50 μ mol/L.Damping fluid, 25mmol/L MES; Separation voltage, 1200V; Detect current potential: 1.0V to saturated Ag/AgCl electrode.
Claims (10)
1, a kind of preparation method who has the micro-fluidic chip of metal microelectrode is characterized in that: adopt the photochemistry selective modification technology of Polymer Surface, preparation has the thermal plasticity high polymer material cover plate of metal microelectrode; Prepared chip is made up of two high polymer materials: a slice is the high polymer material substrate that has the cruciform microchannel, another sheet is the high polymer material cover plate that has metal microelectrode, method involution by hot pressing forms the micro-fluidic chip with capillary electrophoresis electrochemical measuring ability, and concrete steps are:
● on the superpolymer cover plate, prepare metal microelectrode in conjunction with the electroless plating of selective area by the photochemistry selective modification;
● use Ni-based formpiston or silicon formpiston, hot pressing forms cruciform passage substrate on the superpolymer substrate;
● adopt the pressure sintering involution to have metal microelectrode cover plate and cruciform passage substrate, obtain to have the microcurrent controlled capillary tube electrophoresis Electrochemical Detection chip of metal microelectrode.
2, the preparation method who has the micro-fluidic chip of metal microelectrode according to claim 1 is characterized in that: the method for metal microelectrode preparation on the superpolymer cover plate the steps include:
1) is photomask with quartz/chromium plate, as light source irradiation carried out in the selection zone on cover plate surface with ultraviolet light;
2) adopt ethylenediamine as amination liquid, 1-[3-(N, N-dimethyl amido) propyl group]-the 3-ethyl-carbodiimide hydrochloride is that coupling agent is to carrying out aminating reaction through the superpolymer of selecting area radiation;
3) will be through reacting in the superpolymer immersion chlorauric acid solution of selecting regional amination;
4) after water cleans, it is immersed in the sodium borohydride solution reduce again;
5) after water cleans, again it is immersed ultrasonic cleaning in the potassium bisulfide solution;
6) will be immersed in the plating bath that contains plating metal ion, complexing agent and reductive agent formaldehyde through the superpolymer cover plate that cleans, reacted 30-60 minute down in 45-50 ℃, after the cover plate that is coated with metal microelectrode put into the baking oven annealing in process, promptly obtain superpolymer metal microelectrode cover plate of the present invention.
3, the preparation method who has the micro-fluidic chip of metal microelectrode according to claim 2 is characterized in that plating before the microelectrode, and the potassium bisulfide solution that adopts 0.5mol/L was to the Polymer Surface ultrasonic cleaning after activating 30 minutes.
4, the preparation method who has the micro-fluidic chip of metal microelectrode according to claim 2 is characterized in that the cover plate that is coated with microelectrode was annealed 3 hours down at 142 ℃.
5, the preparation method who has the micro-fluidic chip of metal microelectrode according to claim 1 is characterized in that the pressure sintering involution has the sealing method of metal microelectrode cover plate and cruciform passage substrate, the steps include:
7) use Ni-based formpiston or the silicon formpiston that has the cross channel architecture, in 142 ℃, the back demoulding is cooled off in hot pressing under the condition of 1.0MPa, forms the superpolymer substrate with cross passage on substrate;
8) use drill bit, get out four liquid storage holes at four ends of superpolymer substrate cross passage;
9) superpolymer metal microelectrode cover plate and surperficial superpolymer substrate with cross passage are handled in low-temperature oxygen plasma atmosphere;
10) rapidly cover plate is combined on the substrate with cross passage, pre-fixes, the chip after fixing is placed between two sheet glass, use clamp, put into baking oven and seal with the relative position of two of solvents;
11) be stained with the reservoir of suitable size with epoxy resin in four liquid storage hole positions of passage, obtain to have the micro-fluidic chip of metal microelectrode.
6, the preparation method who has the micro-fluidic chip of metal microelectrode according to claim 5 is characterized in that the described cover plate that is coated with microelectrode was handled 5 minutes in low-temperature oxygen plasma atmosphere with the substrate with cross passage.
7, the preparation method who has the micro-fluidic chip of metal microelectrode according to claim 5, it is characterized in that describedly pre-fixing with the relative position of solvent with two superpolymer sheets, make the outlet of split tunnel on the microelectrode alignment substrate on the cover plate at microscopically, make between electrode-channel outlet between from being controlled at 20-50 μ m, behind the aligning immediately four jiaos of chip each-drip methylene chloride, in air, volatilize, so that the relative position of cover plate and substrate is fixed.
8, the preparation method who has the micro-fluidic chip of metal microelectrode according to claim 5, the chip after the heat sealing that it is characterized in that described chip will be fixed is put into baking oven, is warming up to 146 ℃, is incubated after 20 minutes, is cooled to room temperature, takes out chip.
9, according to claim 1,2, the 5 described preparation methods that have the micro-fluidic chip of metal microelectrode, the high polymer material that it is characterized in that described preparation chip can be a kind of of polycarbonate, polyethylene terephthalate, polymethylmethacrylate thermoplastic macromolecule material.
10, according to claim 1,2, the 5 described preparation methods that have the micro-fluidic chip of metal microelectrode, it is characterized in that described metal microelectrode is: single electrode, bipolar electrode, multi-electrode or array electrode, the metal microelectrode material is: gold, copper, nickel, platinum, palladium, silver etc.
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