CN105903501A - Polydimethylsiloxane-paper composite chip and preparation method and application thereof - Google Patents

Polydimethylsiloxane-paper composite chip and preparation method and application thereof Download PDF

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Publication number
CN105903501A
CN105903501A CN201610239287.2A CN201610239287A CN105903501A CN 105903501 A CN105903501 A CN 105903501A CN 201610239287 A CN201610239287 A CN 201610239287A CN 105903501 A CN105903501 A CN 105903501A
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paper
polydimethylsiloxane
chip
pdms
compound chip
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CN105903501B (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)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)

Abstract

A polydimethylsiloxane-paper composite chip is the polydimethylsiloxane-paper composite chip with controllable depth of penetration that is formed by patterned loading polydimethylsiloxane on paper. A paper chip is easy to process and easy to load a reagent; and a polydimethylsiloxane (PDMS) chip has advantages of mutual fitting, excellent biocompatibility and easy microfluidic pipeline construction on surface. The chip provided by the invention has all advantages of the paper chip and the polydimethylsiloxane chip.

Description

A kind of polydimethylsiloxane-paper compound chip and preparation method thereof and purposes
Technical field
The present invention relates to compound chip, particularly polydimethylsiloxane (PDMS) compartmentalization is carried on paper Polydimethylsiloxane-paper compound chip that upper formation length of penetration is controlled and preparation method thereof.
Background technology
The concept of paper chip is mainly derived from the papery reagent paper of viable commercial product, utilize the porous character of paper allow by Multiple detectable is carried on the zones of different of paper, and usual papery reagent paper can pass through the direct-vision methodes such as metachromasia, Directly the many kinds of parameters in sample is characterized, there is cheap, easy-to-use feature.Utilize paper fiber pair simultaneously The infiltration of liquid and capillarity can guide sample to carry out certain motion in paper chip, thus reach having The effects such as the pre-separation of tinctorial pattern product, eliminate the dependence to complex fluid driving means, be suitable for amateur state, As used when professional equipment, layman, rapid broad spectrum screening.Nearly ten years, researcher will The Conceptual Extension of reagent paper becomes paper chip to be an important development, and the concept of paper chip not only combines the survey of reagent paper The advantage of examination, also the pipeline in micro-fluidic, fluid controls, process control etc., concept is integrated comes, application model Enclose and expand further it is considered to be most possibly obtain the microfluidic system of commercialization.Various relevant with paper chip Technology of preparing, such as cerul patterning techniques, laser-engraving technique, printing technique, the development of paper folding technology etc. is more It is the possibility enriching paper chip design, has significantly promoted the development in this field.But stationery is born due to it Having loose structure, the whole scraps of paper are the connection main bodys of a fluid permeable, it is therefore necessary to by certain method The flowing limiting liquid could realize the restriction to scraps of paper upper fluid flow range, thus the inspection of beneficially quantification Survey.Hydrophobic material is mainly loaded on the scraps of paper by various patterning methods thus realizes by existing method Fluid flow scope and the control of order.Such as in ink base paper printing technique and cerul patterning techniques etc..This The chip structure that class method is produced is the most coarse, even if realizing three-dimensional tube structure by paper folding technology, by Being all to be made up of the loose structure of paper substrate in pipeline, sample flow speed is slow, and sample adsorption loss is serious, limits This kind of chip broader practice.
In order to solve this problem, there is seminar to propose chip compound with paper for paper hollow out pipeline, so will The advantage of fluid line combines with paper chip, has expanded the function and application scope of paper chip.But it is such Work limit to the most very much, mainly wax and marking ink be required for special handling could realize interlayer be combined.It is true that Polydimethylsiloxane (PDMS) is used to have multiple advantage as chip material, as being most widely used Micro-fluidic, PDMS has good printing opacity, breathability, excellent biocompatibility, price Cheap, processing simplicity, its surface nature particularly hydrophilic and hydrophobic can pass through simple plasma or ozone Producing the change from hydrophobic to super hydrophilic Deng process, the beneficially control of fluid flow, at this kind of simplicity Reason can also realize the structure of three dimensional structure chip, makes chip functions more horn of plenty.But compare paper chip, PDMS thin slice has bigger elasticity, easy deformation, it is difficult to maintain rock-steady structure, is difficult to load modification point simultaneously Son or other various reagent, limit the application of PDMS.If able to by the advantage of paper chip and PDMS Advantage combine and learn from other's strong points to offset one's weaknesses, will quickly analyze the fields such as detection for micro-fluidic chip and bring impressive progress. The existing method being combined with paper by PDMS is mainly and paper surface carries out functionalization group grafting process, so After utilize these functionalization groups to be chemically crosslinked with PDMS by paper, thus fit together.This kind of side The cross-linking procedure that method relates to is complicated, it is thus achieved that paper chip the most there is not the relation interpenetrated, paste Fastness is poor.And process owing to there is the chemical graft to paper, seriously limit the material kind that can load on paper Class, is unfavorable for the functionalization of paper chip;Can permeate continuously owing to paper relative liquid in this kind of structure is one Object, therefore in microchip, entirety can only serve as an interface, can application surface narrow.In order to solve this Problem needs a kind of brand-new PDMS-paper associated methods of exploitation badly can overcome above defect.
Summary of the invention
The subject matter that the invention solves the problems that is how to utilize polydimethylsiloxane (PDMS) and stationery substrate Combine, be allowed to both retain paper chip and be easily achieved the load of polytype material, the spy of stronger mechanical stability Point, having again PDMS is prone to the advantage at surface construction microtube structure simultaneously, thus expands paper chip Range of application.The most just it is an up PDMS and planar patterned precision that paper combines and control PDMS longitudinal direction in paper cohesive process is combined the degree of depth.
For solving above-mentioned technical problem, the present invention uses PDMS and paper to form interpenetrative composite construction. Utilize temperature that the regulating and controlling effect of PDMS solidification process speed is controlled scope that PDMS extends on paper and Penetrate into the degree of depth in paper, be consequently formed PDMS-paper composite construction.Particularly under conditions of temperature is higher PDMS can realize fast curing-formed within a short period of time, achieves PDMS first more high-precision in substrate The pattern structure structure that degree, length of penetration are controlled.
Technical scheme is as follows:
A kind of polydimethylsiloxane-paper compound chip, it is a kind of by polydimethylsiloxane (PDMS) figure Case is carried on paper and forms polydimethylsiloxane-paper compound chip that length of penetration is controlled.
Above-mentioned compound chip, described paper refers to all kinds of material with loose structure, such as wood pulp or straw pulp system Become stationery, by weaving porous sheet, Non-woven fabrics lamella, polymer-based or fiberglass-based perforated membrane.
A kind of method preparing above-mentioned compound chip, it comprises the steps:
Step 1. prepares polydimethylsiloxane (PDMS) performed polymer and the mixed solution of firming agent;
Step 2, by writing, seal, printing or method for printing screen, by above-mentioned polydimethylsiloxane Mixed solution transfers to the specific region of paper substrate;
Step 3. waits 0 second 30 minutes;
Whole material is made polydimethylsiloxane solidification prepare poly-diformazan 100 DEG C of-200 DEG C of heating by step 4. Radical siloxane-paper compound chip.
The preparation method of above-mentioned compound chip, described printing process can be the method printed with plane or volume to volume Printing.
The preparation method of above-mentioned compound chip, the polydimethylsiloxane paper recombination process narrated can be once to gather Dimethyl siloxane paper recombination process, or repeatedly polydimethylsiloxane paper recombination process.
The application in separating, analyze, differentiate or identifying of the above-mentioned compound chip.
The concrete effect of the present invention is as follows:
The present invention utilizes the feature that polydimethylsiloxane controllable time at relatively high temperatures is polymerized, in conjunction with paper substrate figure The method of case, the waiting time before being solidified by control and solidification temperature, it is achieved that patterning, controlled ooze The PDMS-paper complex method of the degree of depth thoroughly.Utilize this novel polydimethylsiloxaneoxygen-enrichment-paper compound chip preparation side Method, it is possible to make the chip of gained both have paper chip and be prone to processing, be prone to the advantage of supported reagent, have again poly- Dimethyl siloxane (PDMS) chip can fit mutually, has the biocompatibility of excellence and be prone at it The advantage that surface carries out Micro-flow pipe structure.
Accompanying drawing explanation
Fig. 1. polydimethylsiloxane (PDMS) front aggressiveness and curing agent mixture vary with temperature hardening time Relation.The front aggressiveness herein selected and firming agent ratio are 10:1.When temperature rises to more than 100 degrees Celsius, Hardening time drops to reduced levels;Along with solidification temperature raises, curing rate is accelerated.
Fig. 2. polydimethylsiloxane (PDMS) paper chip patterning condition analysis.A.PDMS infiltration is deep Degree and solidification temperature relation.Show that raising solidification temperature can reduce the PDMS length of penetration to paper substrate.B. filter Paper PDMS planar diffusion scope and solidification temperature relation;C. printing paper PDMS planar diffusion scope and solidification Temperature relation, shows that higher temperature is conducive to suppressing the planar diffusion of PDMS, thus obtains preferably figure Case resolution.
The paper chip that Fig. 3 .A1-A2: polydimethylsiloxane (PDMS) patterns;B. PDMS is combined The novel PDMS-paper chip sample of pipe layers.The PDMS paper chip combining PDMS pipe layers is the most sharp The preserved pipeline formed between paper using and PDMS makes fluid flowing rather than traditional paper chip utilize paper Capillarity transmit liquid, so make the flowing of liquid more quick, decrease liquid flowing simultaneously During loss.
Fig. 4. for polymethyl methacrylate (PMMA) seal of chip desirable pattern.Wherein canescence Part is PMMA seal region.Utilize this seal can make the patterning chip being similar in Fig. 3.
Fig. 5 .A: the PDMS paper chip printed by inkjet technology.This chip can utilize swan-neck Road is used for premixing and the response analysis of liquid.B: can be used for preparing the PMMA mould of chip upper strata pipeline. During use, PMMA solution is poured on mould and is heating and curing.
Fig. 6 .A: the PDMS paper chip printed by screen printing technique.This chip can utilize swan-neck Road is used for premixing and the response analysis of liquid.B: can be used for preparing the PMMA mould of chip upper strata pipeline. During use, PMMA solution is poured on mould and is heating and curing.
Fig. 7. for the poly-methyl of preparation process of the polydimethylsiloxane-paper compound chip of multistep recombination process Acrylic acid methyl ester. (PMMA) seal.A. the seal that the length of penetration in front is deeper it is used for;B. for the back side The seal that length of penetration is shallower.The white space alignment both reserved is needed during use.
Detailed description of the invention:
The invention will be further described with example below in conjunction with the accompanying drawings.
Embodiment 1: the preparation of polydimethylsiloxane-paper compound chip
Step 1. prepares polydimethylsiloxane (PDMS) performed polymer and the mixed solution of firming agent, performed polymer It is 10:1 with firming agent mass ratio;
Step 2. carves the seal of chip desirable pattern, and Fig. 4 is shown in by its pattern, will be carved with chip desirable pattern Seal picks PDMS, then cover printing paper (Zhenjiang Dadong Paper Co., Ltd., in emerging extra white xerography Paper) surface;
2 seconds step 3. waiting time;
Seal 200 DEG C of solidifications, is taken off after solidification by step 4. by whole material, prepares polydimethylsiloxanes Alkane-paper compound chip.
PDMS mixed solution is poured on the seal shown in Fig. 4 by step 5. so that pattern is completely submerged;
Step 6.PDMS heats 30min solidification at 60 DEG C, peels off seal with elbow tweezer;
After the PDMS reverse mould pipe surface obtained is dipped a small amount of PDMS solution by step 7., with refill before Sheet pipe alignment is fitted;
Whole material is solidified 2s at 200 DEG C by step 8., prepares NEW TYPE OF COMPOSITE chip after solidification;
Step 9. drip respectively in each border circular areas of the periphery of chip methyl orange solution, colourless phenolphthalein solution, C.I. 14645. 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 also press the border circular areas at corresponding indicator place also the most respectively Unclamp, make two kinds of solution be fully contacted reaction respectively.
Embodiment 2: the preparation of polydimethylsiloxane-paper compound chip
Step 1. prepares polydimethylsiloxane (PDMS) performed polymer and the mixed solution of firming agent, pre-polymerization Body and firming agent mass ratio are 10:1;
Step 2. passes through printing of inkjet printer, and by chip desirable pattern, this mixed solution is printed to printing paper On, see Fig. 5 A;
Step 3. waits 30 minutes;
Whole material 100 DEG C of solidifications, is prepared polydimethylsiloxane-paper compound chip by step 4..
PDMS mixed solution is poured on the seal shown in Fig. 5 B by step 5. so that pattern is soaked completely Not yet;
Step 6.PDMS heats 30min solidification at 60 DEG C, peels off seal with elbow tweezer;
After the PDMS reverse mould pipe surface obtained is dipped a small amount of PDMS solution by step 7., with refill before Sheet pipe alignment is fitted;
Whole material is solidified 2min at 100 DEG C by step 8., prepares NEW TYPE OF COMPOSITE chip after solidification;
Step 9. is by human blood sample and erythrocyte cracked liquid (triumphant base is biological, lot number KGP1150-KGP11100) It is injected separately into the 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, allows blood sample and cell Lysate fully vibrates after crossing at y-branch mixing in pipeline;
The mixed sample of step 11. stands 10min after arriving liquid storage tank makes erythrocyte crack completely.
Obtain has cracked erythrocytic blood sample and sucking-off can carry out subsequent analysis again.Due to the sample used Measure less, so being suitable for mixing and the subsequent treatment of micro-example.
Embodiment 3: the preparation of polydimethylsiloxane-paper compound chip
Step 1. prepares polydimethylsiloxane (PDMS) performed polymer and the mixed solution of firming agent, pre-polymerization Body and firming agent mass ratio are 10:1;
Step 2. is printed by quick silk screen, transfers on printing paper by this mixed solution by chip desirable pattern, See Fig. 6 A;
Step 3. waits 0 second;
Paper 150 DEG C of rapid solidifications, is prepared polydimethylsiloxane-paper compound chip by step 4..
PDMS mixed solution is poured on the seal shown in Fig. 6 B by step 5. so that pattern is soaked completely Not yet;
Step 6.PDMS heats 30min solidification at 60 DEG C, peels off seal with elbow tweezer;
After the PDMS reverse mould pipe surface obtained is dipped a small amount of PDMS solution by step 7., with refill before Sheet pipe alignment is fitted;
Whole material is solidified 2min at 100 DEG C by step 8., prepares NEW TYPE OF COMPOSITE chip after solidification;
Step 9. is by human blood sample and erythrocyte cracked liquid (triumphant base is biological, lot number KGP1150-KGP11100) It is injected separately into the 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, allows blood sample and cell Lysate fully vibrates after crossing at y-branch mixing in pipeline;
The mixed sample of step 11. stands 10min after arriving liquid storage tank makes erythrocyte crack completely.
Obtain has cracked erythrocytic blood sample and sucking-off can carry out subsequent analysis again.Due to the sample used Amount less, so being suitable for the mixing of micro-example and subsequent treatment.
Embodiment 4: the preparation of the polydimethylsiloxane of multistep recombination process-paper compound chip
Step 1. prepares polydimethylsiloxane (PDMS) performed polymer and the mixed solution of firming agent, pre-polymerization Body and firming agent mass ratio are 10:1;
Needed for step 2. will be carved with chip, the seal of the deeper pattern of polydimethylsiloxane length of penetration picks PDMS, covers and specifies region on filter paper (Hangzhou Wo Hua filter paper company limited enjoy a double blessing board 9mm qualitative filter paper), Such as Fig. 7 A;
Step 3. waits 10 minutes, makes PDMS thoroughly infiltrate through paper substrate;
Step 4. by whole material 100 DEG C of solidifications;
Needed for step 5. will be carved with chip, the seal of the shallower pattern of polydimethylsiloxane length of penetration picks PDMS, covers appointment region on filter paper, such as Fig. 7 B;
Step 6. waits 0 second;
Whole material 180 DEG C of solidifications, is prepared polydimethylsiloxane-paper compound chip by step 7..
The preparation of step 8. yeast agar culture medium: weigh sodium nitrate 3.0g, disodium hydrogen phosphate 1.0g, chlorine Change potassium 0.5g, bitter salt 0.5g, ferrous sulfate 0.01g, sucrose 30.0g, agar 30g, distilled water 1000ml dissolves, 121 DEG C of high temperature sterilizes.
The preparation of step 9. yeast culture fluid: repeat the operation of step 8, removes the step adding agar;
Step 10. is when culture medium solution is reduced to about 40 DEG C, by yeast suspension vol than 1:1 and training Support base mixing;
Mixed liquor is dropped on polymethyl methacrylate (PMMA) thin film by step 11., suppresses agar thin slice;
Thin slice is lain in dot matrix area, side, chip shallower seal face by step 12., and chip pipe line area is placed in cultivation In liquid, observed a Yeast Growth situation every 2 hours.It appeared that yeast can realize on chip Persistently divide growth.
The patterning infiltration the method achieving multiple different depth PDMS structure on a paper substrate controls.

Claims (6)

1. polydimethylsiloxane-paper compound chip, is characterized in that: it is a kind of by polydimethylsiloxanes Alkane patterning is carried on paper and forms polydimethylsiloxane-paper compound chip that length of penetration is controlled.
Compound chip the most according to claim 1, is characterized in that: described paper refer to all kinds of have many The material of pore structure, the stationery made such as wood pulp or straw pulp, by weaving porous sheet, Non-woven fabrics lamella, Polymer-based or fiberglass-based perforated membrane.
3. the method preparing compound chip described in claim 1, is characterized in that it comprises the steps:
Step 1. prepares polydimethylsiloxane (PDMS) performed polymer and the mixed solution of firming agent;
Step 2, by writing, seal, printing or method for printing screen, by above-mentioned poly dimethyl silicon Oxygen alkane mixed solution transfers to the specific region of paper substrate;
Step 3. waits 0 second 30 minutes;
Whole material is made polydimethylsiloxane solidification prepare poly-two 100 DEG C of-200 DEG C of heating by step 4. Methylsiloxane-paper compound chip.
4., according to the preparation method of the above-mentioned compound chip of claim 3, it is characterized in that: described printing process It it is the method printing printed with plane or volume to volume.
The preparation method of compound chip the most according to claim 3, is characterized in that: described poly dimethyl silicon Oxygen alkane paper recombination process is a polydimethylsiloxane paper recombination process, or repeatedly polydimethylsiloxane Paper recombination process.
6. the application in separating, analyze, differentiate or identifying of the compound chip described in claim 1.
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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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109482247A (en) * 2018-10-18 2019-03-19 哈尔滨工业大学(深圳) A kind of micro-fluidic chip manufacturing process and micro-fluidic chip

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CN103203257A (en) * 2013-03-12 2013-07-17 西安交通大学 Method for manufacturing paper micro-fluidic chip
CN103394384A (en) * 2013-08-12 2013-11-20 广东顺德西安交通大学研究院 Paper-based microfluidic chip and preparation method thereof
CN104209153A (en) * 2014-09-10 2014-12-17 南京邮电大学 Preparation method of paper micro-fluidic chips
CN105013545A (en) * 2015-06-30 2015-11-04 苏州东辰林达检测技术有限公司 Preparation method of paper-based micro fluidic chip

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Publication number Priority date Publication date Assignee Title
WO2010118637A1 (en) * 2009-04-14 2010-10-21 Huang Yanyi Microfluidic distribution device, production method and application thereof
CN103203257A (en) * 2013-03-12 2013-07-17 西安交通大学 Method for manufacturing paper micro-fluidic chip
CN103394384A (en) * 2013-08-12 2013-11-20 广东顺德西安交通大学研究院 Paper-based microfluidic chip and preparation method thereof
CN104209153A (en) * 2014-09-10 2014-12-17 南京邮电大学 Preparation method of paper micro-fluidic chips
CN105013545A (en) * 2015-06-30 2015-11-04 苏州东辰林达检测技术有限公司 Preparation method of paper-based micro fluidic chip

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109482247A (en) * 2018-10-18 2019-03-19 哈尔滨工业大学(深圳) A kind of micro-fluidic chip manufacturing process and micro-fluidic chip
CN109482247B (en) * 2018-10-18 2021-04-13 哈尔滨工业大学(深圳) Micro-fluidic chip manufacturing process and micro-fluidic chip

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