CN103008038B - Bipolar electrode-paper-based microfluidics type chip and preparation method thereof - Google Patents
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Abstract
The invention discloses a bipolar electrode-paper-based microfluidics type chip and a preparation method of the bipolar electrode-paper-based microfluidics type chip. The chip comprises a paper substrate, a paper cover plate, a nanometer electrode and a bipolar electrode, wherein the nanometer electrode and the bipolar electrode are deposited on the surface of the paper substrate; the nanometer electrode is used as a driving unit used for electroosmotic flow in a microfluidic channel and electrochemistry of the bipolar electrode; the bipolar electrode is used a non-uniform field which enables the components to be highly concentrated in the microfluidic channel, and the detected components are subjected to oxidation-reduction reaction at two ends of the bipolar electrode. The invention discloses a method for producing the chip through three different photoresists and diluents. The bipolar electrode-paper-based microfluidics type chip is light in weight, convenient to carry, low in cost and disposable; the required sample is small in size and fast to be analyzed; and the bipolar electrode-paper-based microfluidics type chip is applicable to detection on complex samples of foundations or on-board spaceship life science instruments.
Description
Technical field:
The present invention relates to micro-fluidic chip of a kind of bipolar electrode-paper substrate and preparation method thereof, belong to microfluidic analysis technical field.
Background technology:
Since 20th century, the nineties proposed the concept of micro-total analysis system, micro-fluidic chip is own through becoming Overseas Development one of field the most rapidly as core technology wherein.Paper substrate is micro-fluidic be in recent years micro-fluidic chip research a new direction.It is using filter paper as chip material, use photoetching technique, plotter technology, ink-jet printing technology, wax printing technology, paper-cut, serigraphy, flexographic printing, printing PDMS and plasma oxidation, laser treatment, paper folding art etc. can be used for separately making paper substrate micro-fluidic chip, they by oneself through being successfully used in the fields such as colorimetric analysis, electrochemical analysis, biological sample analysis.Due to it have lightweight, easy to carry, can single use, with low cost, required sample little, the analysis speed of volume fast, can the advantages such as many kinds of substance detects simultaneously be carried out, oneself is through being applied to the fields such as chemistry, biology, medical science more and more.
Many chemical analyses and chemical reaction are all using paper as carrier, and filter paper is widely used at droplet test, pH test paper and paper chromatography etc.Paper substrate is micro-fluidic is proposed first in 2007 years by the people such as Martinez [Martinez et al., Angew.Chem.Int.Ed.2007,46,1318-1320].Ordinary filter paper is made up of cellulose, and in hydrophily, its fibrolaminar capillarity can make the aqueous solution automatically permeate, for creating good condition with papery facture of microchip and application.Compared with the micro-fluidic chip base materials such as silicon chip, glass, PDMS, papery micro-fluidic chip has that cost is low, preparation is simple, without the need to features such as complex peripheral equipment, be highly suitable under the extreme condition such as scarcity of resources or space carrying, further develop a series of biochemistry detection new method.
For bipolar electrode (the Bipolar electrode in In Microfluidic Analytical Systems, BPE), refer to a conductor be placed in microchannel, when being applied to the ion buffer solution in microchannel when sufficiently high electric field, there is oxidation reaction in this conductor one end, there is reduction reaction in one end, this conductor is just called BPE.Bipolar electrode chip apparatus reported in the world mainly based on glass and PDMS, and the paper substrate that this patent is announced micro-fluidic-bipolar electrode electrophoretic separation chip and preparation method thereof also do not appear in the newspapers.
Summary of the invention:
The object of this invention is to provide micro-fluidic chip of a kind of bipolar electrode-paper substrate and preparation method thereof, bipolar electrode-paper substrate micro-fluidic chip have lightweight, easy to carry, with low cost, can single use, required sample the feature that volume is little, analysis speed is fast, be applicable to the detection etc. of the complex sample of ground or space carrying Life Science Instruments.
For achieving the above object, the present invention is by the following technical solutions:
The chip that bipolar electrode-paper substrate is micro-fluidic, comprises paper substrate, papery cover plate, nano-electrode, bipolar electrode; Papery cover plate lithographically has hydrophobic barrier to form microfluidic channel, and nano-electrode and bipolar electrode (7) amass in paper substrate surface, between paper substrate and papery cover plate; Nano-electrode has two, lays respectively at the both sides of bipolar electrode; Papery cover plate is provided with sample introduction inlet region and outlet area, pre-separation enrichment region is microchannel first half, microchannel forms paper electrophoresis-paper chromatography, described nano-electrode is as EOF in microchannel and the electrochemical driver element of bipolar electrode, bipolar electrode makes component high power concentrate as the formation inhomogeneous field of microchannel, and make detected component occur in bipolar electrode two ends generation redox reaction, focusing is carried out to abundance material low in complex sample and concentrates and detect analysis.
Described nano-electrode thickness is 100nm;
Described bipolar electrode thickness is 100nm, vertical with the microchannel of cover plate;
Described nano-electrode is oxide semiconductor electrode or metal electrode;
Described bipolar electrode material is gold or platinum or indium tin oxide target;
Described paper substrate and papery patch material are paper;
Described nano-electrode and bipolar electrode are the nano thin-film structure that magnetron sputtering is formed;
Prepare a method for bipolar electrode-paper substrate micro-fluidic chip, comprise the steps:
1) making of papery cover plate
By photoresist and diluent according to volume ratio 1:(4 ~ 8) dilute, photoresist after the dilution of 0.5ml is evenly coated on the chromatographic paper that diameter is 5cm, after drying at room temperature, directly on litho machine, mask film is alignd with chromatographic paper and expose 30s, acetone development 5min, obtains the papery cover plate with microchannel;
2) making of paper substrate
The scraps of paper being cut into a certain size with common A4 paper work as mask, and according to the size and shape of the electrode of chromatographic paper design, scraps of paper electrode district is cut, ready-made paper mask is placed on above chromatographic paper, adopt magnetron sputtering indium tin oxide target film or metallic film, obtain the thick nano-electrode of 100nm and bipolar electrode; Bipolar electrode is placed in the middle of two nano-electrodes, obtains paper substrate;
3) papery chip involution
Suitable figure is cut out in advance on double faced adhesive tape, the part of cutting is consistent with the shape of electrode, by double faced adhesive tape and the glutinous jail of underlying basal Accurate align, again papery cover plate is alignd with double faced adhesive tape, use layer of transparent adhesive tape plastic film covering at the upper surface of papery cover plate more in addition, obtain paper substrate of the present invention micro-fluidic-bipolar electrode chip.
Compared with prior art, paper substrate of the present invention micro-fluidic bipolar electrode chip and preparation method thereof at least has the following advantages: simplify the even glue in traditional paper substrate chip photoetching technique, front baking, rear baking process, paper substrate of the present invention micro-fluidic-bipolar electrode chip in, microchannel previous section will carry out pre-separation and pre-concentration to complex sample, after nano-electrode adds certain voltage, BPE two ends in microchannel produce and drive electromotive force, realize microchannel bipolar electrode high power and concentrate and detect.Paper substrate of the present invention is micro-fluidic-bipolar electrode chip is lightweight, easy to carry, can single use, with low cost, required sample volume little, analysis speed fast, is applicable to the detection etc. of the complex sample of ground or space carrying Life Science Instruments.
Accompanying drawing illustrates:
Fig. 1 is bipolar electrode of the present invention-paper substrate micro-fluidic chip machining sketch chart, wherein: the whole bipolar electrode of Fig. 1 (a)-paper substrate microfluidic chip structure figure; The flow process chart of Fig. 1 (b) microchannel; Fig. 1 (c) nano-electrode and bipolar electrode processing structure figure; Fig. 1 (d) paper substrate microchannel and paper substrate nano-electrode and bipolar electrode assembling side elevation.
Fig. 2 is the structure chart of the present invention's a kind of bipolar electrode-paper substrate micro-fluidic chip.
Fig. 3 is the Electric Field Distribution schematic diagram of the present invention's a kind of bipolar electrode-paper substrate micro-fluidic chip.
Detailed description of the invention:
Below in conjunction with accompanying drawing, the present invention is described in detail.
Chip structure of the present invention for: as shown in Fig. 1 (a), comprise paper substrate 1, papery cover plate 5, first and second nano-electrode 6,8, bipolar electrode 7; Papery cover plate 5 lithographically has hydrophobic barrier 2 to form microfluidic channel 3, and first, second nano-electrode 6,8 and bipolar electrode 7 are deposited on paper substrate 5 surface, between paper substrate and papery cover plate; First and second nano-electrodes 6,8 lay respectively at the both sides of bipolar electrode 7; Papery cover plate is provided with sample introduction inlet region 10 and outlet area 11, pre-separation enrichment region 4 is microchannel 3 first half, microchannel 3 forms paper electrophoresis-paper chromatography, described nano-electrode 6,8 is as EOF in microchannel and the electrochemical driver element of bipolar electrode 7, bipolar electrode 7 makes component high power concentrate as the formation inhomogeneous field of microchannel, make detected component occur in bipolar electrode two ends and redox reaction occurs, focusing is carried out to abundance material low in complex sample and concentrates and detect analysis.
As shown in Fig. 1 (b) He Fig. 1 (c), as follows to the preparation method of chip of the present invention:
1) making of cover plate
With CorelDraw or other mapping softwares design microchannel network, with more than 2400dpi resolution ratio, laser photocomposing machine exports and be used as photomask (general advertisement company all can provide this to serve) on transparent film, in darkroom (or through subtracting dark common laboratory), photomask being covered on filter paper, being placed in and litho machine exposes 30s(need adjusting according to light intensity); Laser photocomposing machine according to 5080dpi exports the lateral resolution that can obtain 25 μm, it is 8 μm that photograph plotter according to 20000dpi exports lateral resolution, and (according to chromium plate mask, resolution ratio can lower than 8 μm, but the mask fabrication time is long, costly).Therefore, film makes the not too high photomask of microchannel linewidth requirements as at uv-exposure.According to Fig. 1 (b), photoresist SU-8100 and cyclopentanone are necessarily diluted according to volume ratio, photoresist after the dilution of 0.5ml is evenly coated on the chromatographic paper that diameter is 5cm, after 2min drying at room temperature, directly on litho machine (OL-2MaskAligner, AB-M, Inc), mask film is alignd with chromatographic paper and expose 30s, acetone development 5min, obtains the papery cover plate with microchannel;
2) making of paper substrate
Shown in Fig. 1 (c), the scraps of paper being cut into a certain size with common A4 paper work as mask, and according to the size and shape of the electrode of chromatographic paper design, scraps of paper electrode district is cut, ready-made paper mask is placed on above chromatographic paper, adopt magnetron sputtering indium tin oxide target film or metallic film, obtain the thick nano-electrode of 100nm and bipolar electrode; Bipolar electrode is placed in the middle of two nano-electrodes, obtains paper substrate;
3) papery chip involution
Suitable figure is cut out in advance on double faced adhesive tape, the part of cutting is consistent with the shape of electrode, by double faced adhesive tape and the glutinous jail of underlying basal Accurate align, again papery cover plate is alignd with double faced adhesive tape, use layer of transparent adhesive tape plastic film covering at the upper surface of papery cover plate more in addition, obtain paper substrate of the present invention micro-fluidic-bipolar electrode chip.
Below, shown in Fig. 2 and Fig. 3, to paper substrate micro-fluidic-bipolar electrode elaborates along the electric field space distribution schematic diagram of microchannel axis.
Bipolar electrode is sheet type, vertical with microchannel in upper strata cover plate 5, and its width is greater than whole microfluidic channel width; Described nano-electrode is conductor oxidate/metal electrode; Described nano-electrode is indium tin oxide target or Pt electrode or gold; Described thin slice bipolar electrode material is gold (Au) or platinum (Pt) or indium tin oxide target; Described substrate 1 and cover plate 5 material are paper; Described nano-electrode and bipolar electrode deposit formation by magnetron sputtering on paper substrate substrate 1; Described nano-electrode and bipolar electrode thickness are about 100nm.
Nano-electrode 6,8 applies certain electric field, and the two ends of the bipolar electrode (7) of BPE gold film produce potential drop, and cation is to movable cathode; Anion anode moves, axially the redox potential that potential drop forms BPE two ends is formed with along microchannel at the two ends of the accurate equipotentiality body of rectangle BPE gold film, there is redox reaction, inhomogeneous field is formed around BPE gold film 7 simultaneously in split tunnel, the effect of concentrating efficiently is taken up to molecule, and papery microchannel itself also has certain pre-separation inspissation, both are combined, will extremely be conducive to the analysis of complex sample and low abundance material.
Embodiment 1:
A. the making of paper substrate cover plate
According to Fig. 1 (b), photoresist SU-82025 and SU-82000 diluent are diluted according to volume ratio 1:6, photoresist after the dilution of 0.5ml is evenly coated on the chromatographic paper that diameter is 5cm, after 2min drying at room temperature, directly on litho machine (OL-2Mask Aligner, AB-M, Inc), mask film is alignd with chromatographic paper and expose 30s, acetone development 5min, obtains the papery cover plate with microchannel;
B. the making of paper substrate substrate
Shown in Fig. 1 (c), the scraps of paper being cut into a certain size with common A4 paper work as mask, and according to the size and shape of the electrode of chromatographic paper design, scraps of paper electrode district is cut, ready-made paper mask is placed on above chromatographic paper, adopt magnetron sputtering indium tin oxide target film, obtain the thick nano-electrode of 100nm and bipolar electrode; Bipolar electrode is placed in the middle of two nano-electrodes, obtains paper substrate;
C. papery chip involution
Suitable figure is cut out in advance on double faced adhesive tape, the part of cutting is consistent with the shape of electrode, by double faced adhesive tape and the glutinous jail of underlying basal Accurate align, again papery cover plate is alignd with double faced adhesive tape, use layer of transparent adhesive tape plastic film covering at the upper surface of papery cover plate more in addition, obtain paper substrate of the present invention micro-fluidic-bipolar electrode chip.
Embodiment 2:
A. the making of paper substrate cover plate
According to Fig. 1 (b), photoresist SU-82150 and chloroform are diluted according to volume ratio 1:4, photoresist after the dilution of 0.5ml is evenly coated on the chromatographic paper that diameter is 5cm, after 2min drying at room temperature, directly on litho machine (OL-2MaskAligner, AB-M, Inc), mask film is alignd with chromatographic paper and expose 30s, acetone development 5min, obtains the papery cover plate with microchannel;
B. the making of paper substrate substrate
Shown in Fig. 1 (c), the scraps of paper being cut into a certain size with common A4 paper work as mask, and according to the size and shape of the electrode of chromatographic paper design, scraps of paper electrode district is cut, ready-made paper mask is placed on above chromatographic paper, adopt magnetron sputtering Au film, obtain the thick nano-electrode of 100nm and bipolar electrode; Bipolar electrode is placed in the middle of two nano-electrodes, obtains paper substrate;
C. papery chip involution
Suitable figure is cut out in advance on double faced adhesive tape, the part of cutting is consistent with the shape of electrode, by double faced adhesive tape and lower floor's paper chip (substrate) Accurate align, affix, cover plate and double faced adhesive tape to affixing thereafter, finally transparent adhesive tape is covered the upper surface of cover plate, obtain paper substrate of the present invention micro-fluidic-bipolar electrode chip.
Embodiment 2 is from embodiment 1 main difference part: the photoresist of different model and diluent and dilution ratio different, nano-electrode and bipolar electrode material are Au.
Embodiment 3:
A. the making of paper substrate cover plate
According to Fig. 1 (b), photoresist SU-8100 and cyclopentanone are diluted according to volume ratio 1:8, photoresist after the dilution of 0.5ml is evenly coated on the chromatographic paper that diameter is 5cm, after 2min drying at room temperature, directly on litho machine (OL-2Mask Aligner, AB-M, Inc), mask film is alignd with chromatographic paper and expose 30s, acetone development 5min, obtains the papery cover plate with microchannel;
B. the making of paper substrate substrate
Shown in Fig. 1 (c), the scraps of paper being cut into a certain size with common A4 paper work as mask, and according to the size and shape of the electrode of chromatographic paper design, scraps of paper electrode district is cut, ready-made paper mask is placed on above chromatographic paper, adopt magnetron sputtering platinum film, obtain the thick nano-electrode of 100nm and bipolar electrode; Bipolar electrode is placed in the middle of two nano-electrodes, obtains paper substrate;
C. papery chip involution
Suitable figure is cut out in advance on double faced adhesive tape, the part of cutting is consistent with the shape of electrode, by double faced adhesive tape and the glutinous jail of underlying basal Accurate align, again papery cover plate is alignd with double faced adhesive tape, use layer of transparent adhesive tape plastic film covering at the upper surface of papery cover plate more in addition, obtain paper substrate of the present invention micro-fluidic-bipolar electrode chip.
Embodiment 3 is from embodiment 1,2 main difference part: the photoresist of different model and diluent and dilution ratio different; Nano-electrode and bipolar electrode are platinum.
The invention has the beneficial effects as follows:
1) achieve with paper substrate micro-fluidic-bipolar electrode chip;
2) paper substrate of the present invention micro-fluidic-bipolar electrode chip have lightweight, easy to carry, can single use, with low cost, required sample the feature that volume is little, analysis speed is fast, be applicable to the detection etc. of the complex sample of ground or space carrying Life Science Instruments.
Claims (5)
1. the chip that bipolar electrode-paper substrate is micro-fluidic, is characterized in that: comprise paper substrate (1), papery cover plate (5), nano-electrode (6,8), bipolar electrode (7), papery cover plate lithographically has hydrophobic barrier (2) to form microfluidic channel (3), nano-electrode (6,8) and bipolar electrode (7) are deposited on paper substrate (1) surface, between paper substrate and papery cover plate, nano-electrode (6,8) has two, lays respectively at the both sides of bipolar electrode (7), papery cover plate is provided with sample introduction inlet region (10) and outlet area (11), pre-separation enrichment region (4) is microfluidic channel (3) first half, microfluidic channel (3) forms paper electrophoresis-paper chromatography, described nano-electrode (6, 8) as EOF in microfluidic channel and bipolar electrode (7) electrochemical driver element, bipolar electrode (7) makes component high power concentrate as the formation inhomogeneous field of microfluidic channel, and make detected component occur in bipolar electrode two ends generation redox reaction, carry out focusing to abundance material low in complex sample concentrate and detect analysis, bipolar electrode is sheet type, vertical with microfluidic channel in the cover plate of upper strata, and its width is greater than whole microfluidic channel width, described nano-electrode is conductor oxidate/metal electrode, described bipolar electrode material is gold or platinum or indium tin oxide target, described substrate and patch material are paper, described nano-electrode and bipolar electrode are formed at paper substrate deposition on substrate by magnetron sputtering, described nano-electrode and bipolar electrode thickness are 100nm.
2. the chip that bipolar electrode-paper substrate according to claim 1 is micro-fluidic, is characterized in that: described nano-electrode is indium tin oxide target or Pt electrode or gold.
3. prepare a method for micro-fluidic chip, it is characterized in that, comprise the steps:
1) making of papery cover plate
By photoresist and diluent according to volume ratio 1:(4 ~ 8) dilute, photoresist after the dilution of 0.5ml is evenly coated on the chromatographic paper that diameter is 5cm, after drying at room temperature, directly on litho machine, mask film is alignd with chromatographic paper and expose 30s, acetone development 5min, obtains the papery cover plate with microchannel;
2) making of paper substrate
The scraps of paper being cut into a certain size with common A4 paper work as mask, according to the size and shape of the electrode of chromatographic paper design, scraps of paper electrode district is cut, ready-made paper mask is placed on above chromatographic paper, adopt magnetron sputtering indium tin oxide target film or metallic film, obtain the thick nano-electrode of 100nm and bipolar electrode; Bipolar electrode is placed in the middle of two nano-electrodes, obtains paper substrate;
3) papery chip involution
Suitable figure is cut out in advance on double faced adhesive tape, the part of cutting is consistent with the shape of electrode, by double faced adhesive tape and the glutinous jail of underlying basal Accurate align, again papery cover plate is alignd with double faced adhesive tape, with the upper surface of layer of transparent adhesive tape plastic film covering at papery cover plate, obtain the chip that bipolar electrode-paper substrate is micro-fluidic.
4. a kind of method preparing micro-fluidic chip as claimed in claim 3, is characterized in that: described photoresist is selected from photoresist SU-8 100 or photoresist SU-8 2025 or photoresist SU-8 2150.
5. a kind of method preparing micro-fluidic chip as claimed in claim 3, is characterized in that: described diluent selects cyclopentanone or chloroform.
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