CN108855259A - A kind of surface modifying method of micro-array chip - Google Patents
A kind of surface modifying method of micro-array chip Download PDFInfo
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- CN108855259A CN108855259A CN201810568211.3A CN201810568211A CN108855259A CN 108855259 A CN108855259 A CN 108855259A CN 201810568211 A CN201810568211 A CN 201810568211A CN 108855259 A CN108855259 A CN 108855259A
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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
- B01L3/50—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
- B01L3/502707—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 the manufacture of the container or its components
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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
- B01L2300/00—Additional constructional details
- B01L2300/16—Surface properties and coatings
- B01L2300/161—Control and use of surface tension forces, e.g. hydrophobic, hydrophilic
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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
- B01L2300/00—Additional constructional details
- B01L2300/16—Surface properties and coatings
- B01L2300/161—Control and use of surface tension forces, e.g. hydrophobic, hydrophilic
- B01L2300/165—Specific details about hydrophobic, oleophobic surfaces
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Abstract
The invention belongs to process for modifying surface fields, more particularly to a kind of surface modifying method of micro-array chip, for the method to generate the chip surface and micropore with hydrophilic Si-OH group using oxidizing substance and silicon base chip oxidation, reacting to obtain with chip surface using fluorosilane-type materials after covering micropore has hydrophobic chip surface.The present invention is modified chip surface using the modified method of substep, reduce the liquid residual of chip surface, it avoids sample and detects the cross contamination between signal, reduce the difficulty of later period signal and image processing, substantially increase the precision and sensitivity of biology sample detection.Compared with the hydrophilic and hydrophobicity in the prior art by way of coating hydrophilic/hydrophobic film to chip surface to change chip surface, its hydrophilic and hydrophobic property of the chip that method of modifying of the invention obtains is more evenly stable, and the oxidation that is corroded is not easy in air, weak acid or mild alkaline conditions.
Description
Technical field
The invention belongs to process for modifying surface fields, and in particular to a kind of surface modifying method of micro-array chip.
Background technique
Biochip (biochip or bioarray) be according to the principle specifically to interact between biomolecule, will be biochemical
Analytic process is integrated in chip surface, to realize the high throughput to DNA, RNA, polypeptide, protein and other biological ingredient
Quickly detection.The biochip concept of narrow sense refers to biomolecule (oligonucleotides, cDNA, genomic through distinct methods
DNA, polypeptide, antibody, antigen etc.) it is bonded in the solid phase mediators such as silicon wafer, sheet glass (pearl), plastic sheet (pearl), gel, nylon membrane
The biomolecule dot matrix of formation, therefore biochip is also known as micro-array chip.The main feature of micro-array chip is embodied in：It is micro-
Type, thousands of a biochemical reactions carry out on chip simultaneously；High pass quantization, by one-time detection, that you can get it is thousands of
Information；Height intersection, be related to the intersections of the technologies such as life science, medicine, material science, information science with merge.Cause
Micro-array chip has the advantages that various, is widely used in the scientific research of genomics and proteomics, clinical disease
The fields such as sick diagnosis, new drug development, judicial expertise and food safety.
The existing micro-array chip micropore with 2~1,000,000 geometries every square centimeter has between each micropore
Certain spacing, preparation process are generally：Film first is formed in the main surface of substrate and coats resist in film surface, is then passed through
By the exposure mask with micropore pattern to the non-cured section for removing resist after anti-aging drug, then etch mask and substrate is sudden and violent
Reveal part, finally removes etching agent.It is completely physically isolated although being able to achieve between each micropore by the above method, due to chip
The hydrophobicity on surface and hydrophilicrty in micropore are inadequate, and liquid is not easily accessible micropore when sample introduction, and big quantity of fluid remains in core
Piece surface increases the difficulty and shadow of later period signal and image processing so as to cause the cross contamination between sample and detection signal
Ring the precision and sensitivity of biology sample detection.Therefore, it is necessary to micro-array chip carry out surface it is modified with change that its is hydrophobic/
Hydrophily.
In the prior art, the modification of chip surface is mainly realized by modes such as Microcontact printing or plasmas
The patterning of close and distant water area is modified, and is modified as Chinese patent literature CN101080670A discloses one kind by surface with pattern
The method for changing processing, including the aperture mask of changeable position is positioned at substrate proximity and selectively exposes the substrate
A part to carry out surface modification treatment, however, inhomogenous by the film hydrophilic and hydrophobic that above-mentioned coating method obtains, and one
As under high temperature, illumination under conditions of fixed, film is easy to fall off, meanwhile, this method is cumbersome, is not easy to industrialized mass production.
Summary of the invention
Therefore, the technical problem to be solved in the present invention is that the chip for overcoming existing surface modification technology to obtain has parent
The unstable defect of water hydrophobic property, to provide, a kind of hydrophilic and hydrophobic property is uniform and stable and the microarray core of simple process
The surface modifying method of piece.
In order to solve the above-mentioned technical problems, the present invention provides a kind of surface modifying methods of micro-array chip, including such as
Lower step：
Hydrophilicity-imparting treatment is carried out to the surface of the micro-array chip；
At least fill the port of micropore on the micro-array chip；
Silicic acid anhydride is carried out to the surface of the micro-array chip；
Remove the filler in the micropore.
Further, the surface progress hydrophilizing treatment step to the micro-array chip includes：By micro- battle array
Column chip is immersed in hydrophilizing agent, heating reaction at least 1min at 35~45 DEG C.
Further, the hydrophilizing agent includes hydrogen peroxide, further includes ammonium hydroxide, acetic acid, the concentrated sulfuric acid, hydrochloric acid or hydroxide
At least one of sodium；The volume content of hydrogen peroxide is 15~50% in the hydrophilizing agent.
Further, the filler is water, trichloro ethylene, n-hexane, silicone oil, atoleine, solid paraffin, fluorination
Oil, blue at least one of film or PDMS.
Further, the surface progress silicic acid anhydride step to the micro-array chip is：
Hydrophobic reagent is hydrolyzed, hydrating solution is obtained；
The micro-array chip is immersed in the hydrating solution and reacts at least 30s；
The hydrophobic reagent is perfluoro decyl trimethoxy silane, octadecyl trichlorosilane alkane, octadecyl trimethoxy
At least one of base silane, hexadecyl, hexyl triethoxysilane or octyltrichlorosilane.
Further, described step is hydrolyzed to the hydrophobic reagent to be：
The hydrophobic reagent is added in the first polar organic solvent, heating reaction at least 30min at 25~35 DEG C；Institute
Stating the first polar organic solvent is trichloro ethylene, ethyl alcohol, isopropanol, n-hexane, acetone, N,N-Dimethylformamide, tetrahydro furan
It one or more of mutters with the mixing of arbitrary proportion.
It is further, described that step is hydrolyzed to the hydrophobic reagent further includes in first polar organic solvent
The step of middle addition catalyst, the catalyst are acetic acid.
Further, the filler step in the removal micropore is：
At least it is cleaned by ultrasonic with the second polar organic solvent primary；Second polar organic solvent is trichloro ethylene, third
One or more of ketone, ethyl alcohol, isopropanol are with the mixing of arbitrary proportion.
It further, further include to described before the surface to the micro-array chip carries out hydrophilizing treatment step
The step of micro-array chip carries out cleaning for the first time and dries for the first time.
It further, further include to described after the surface to the micro-array chip carries out hydrophilizing treatment step
The step of micro-array chip carries out second of cleaning and dries for second.
The above PDMS is dimethyl silicone polymer, full name in English Polydimethylsiloxane.
Technical solution of the present invention has the following advantages that：
1. the surface modifying method of micro-array chip provided by the invention is given birth to using oxidizing substance and silicon base chip oxidation
At chip surface and micropore with hydrophilic Si-OH group, reacted using fluorosilane-type materials with chip surface after covering micropore
To with hydrophobic chip surface.The present invention is modified chip surface using the modified method of substep, reduces chip
The liquid on surface remains, and avoids sample and detects the cross contamination between signal, reduces the difficulty of later period signal and image processing
Degree, substantially increases the precision and sensitivity of biology sample detection.With in the prior art by chip surface coat it is hydrophilic/dredge
The mode of moisture film is compared to change the hydrophilic and hydrophobicity of chip surface, the chip that method of modifying of the invention obtains its it is hydrophilic and
Hydrophobic property is more evenly stable, and the oxidation that is corroded is not easy in air, weak acid or mild alkaline conditions.
2. the surface modifying method of micro-array chip provided by the invention, first pretreating surface is dredged before surface-hydrophobicized processing
Hydration process reagent improves the reaction rate of subsequent process reagent and chip surface, increases chip surface hydrophobic grouping
Grafting rate, be conducive to obtain the higher hydrophobic surface of hydrophobicity.
Detailed description of the invention
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, is also possible to obtain other drawings based on these drawings.
Fig. 1 is the contact angle test result schematic diagram of the micro-array chip of the embodiment of the present invention 1；
Fig. 2 is the contact angle test result schematic diagram for not carrying out the modified micro-array chip in surface.
Specific embodiment
Technical solution of the present invention will be clearly and completely described below, it is clear that described embodiment is this hair
Bright a part of the embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not having
Every other embodiment obtained under the premise of creative work is made, shall fall within the protection scope of the present invention.In addition, below
Technical characteristic involved in described different embodiments of the present invention as long as they do not conflict with each other can be mutual
In conjunction with.
Embodiment 1
The present embodiment 1 provides a kind of surface modifying method of micro-array chip, and concrete operations are as follows：
(1) it cleans：Microwell array chip is sequentially placed into 30mL trichloro ethylene, 30mL acetone and 30mL ethyl alcohol respectively and is surpassed
Sound cleans three times, each 30min.After cleaning, chip is taken out, is dried up with nitrogen gun, and in 40 DEG C of heating 2min.This implementation
Chip material length, width and height are 1cm × 1cm × 300 μm in example, and chip surface about 20,000 micropores, the diameter of each micropore is about
It is 60 μm, but chip of the invention is not limited in this way, can adjust according to actual needs.
(2) surface hydrophilic is handled：25mL 28v% concentrated ammonia liquor is taken to mix with 25mL 60v% hydrogen peroxide, by step (1)
Chip be placed in mixed solution, take out chip after 40 DEG C of heating 1min, it is each to be successively respectively placed in 30mL ionized water, 30mL ethyl alcohol
It is cleaned by ultrasonic three times, each 30min.After cleaning, chip is taken out, in 40 DEG C of heating 2min.
(3) prehydrolysis：1g perfluoro decyl trimethoxy silane, 99g isopropanol and 1g acetic acid are weighed respectively, are uniformly mixed,
30min is reacted at 30 DEG C, for use.
(4) surface-hydrophobicized processing：The chip micropore of step (2) is filled up with silicone oil, and places it in the system of step (3)
In, standing adsorption 30s.Chip is taken out, with isopropanol repeated flushing chip to clean, is dried up with nitrogen gun, and is heated at 40 DEG C
30s, then gained chip is sequentially placed into 30mL trichloro ethylene, 30mL acetone and 30mL isopropanol and is cleaned by ultrasonic three times, every time
30min.After cleaning, chip is taken out, and chip is placed in ethyl alcohol for use.
Embodiment 2
The present embodiment 2 provides a kind of surface modifying method of micro-array chip, and concrete operations are as follows：
(1) it cleans：Microwell array chip is sequentially placed into respectively in 30mL trichloro ethylene, 30mL acetone and 30mL isopropanol
It is cleaned by ultrasonic three times, each 30min.After cleaning, chip is taken out, is dried up with nitrogen gun, and in 40 DEG C of heating 2min.This reality
Applying chip material length, width and height in example is 1cm × 1cm × 300 μm, chip surface about 20,000 micropores, the diameter of each micropore
About 60 μm, but chip of the invention is not limited in this way, can adjust according to actual needs.
(2) surface hydrophilic is handled：The 35mL 98v% concentrated sulfuric acid is taken to mix with 15mL 60v% hydrogen peroxide, by step (1)
Chip be placed in mixed solution, take out chip after 35 DEG C of heating 2min, it is each to be successively respectively placed in 30mL ionized water, 30mL ethyl alcohol
It is cleaned by ultrasonic three times, each 30min.After cleaning, chip is taken out, in 40 DEG C of heating 2min.
(3) prehydrolysis：1g octadecyl trichlorosilane alkane, 99g acetone and 1g acetic acid are weighed respectively, are uniformly mixed, at 25 DEG C
35min is reacted, for use.
(4) surface-hydrophobicized processing：The chip micropore of step (2) is filled up with water, and places it in the system of step (3)
In, standing adsorption 5min.Chip is taken out, with isopropanol repeated flushing chip to clean, is dried up with nitrogen gun, and is heated at 40 DEG C
1min, then gained chip is sequentially placed into 30mL trichloro ethylene, 30mL acetone and 30mL ethyl alcohol and is cleaned by ultrasonic three times, every time
30min.After cleaning, chip is taken out, and chip is placed in ethyl alcohol for use.
Embodiment 3
The present embodiment 3 provides a kind of surface modifying method of micro-array chip, and concrete operations are as follows：
(1) it cleans：Microwell array chip is sequentially placed into respectively in 30mL trichloro ethylene, 30mL acetone and 30mL isopropanol
It is cleaned by ultrasonic three times, each 30min.After cleaning, chip is taken out, is dried up with nitrogen gun, and in 40 DEG C of heating 2min.This reality
Applying chip material length, width and height in example is 1cm × 1cm × 300 μm, chip surface about 20,000 micropores, the diameter of each micropore
About 60 μm, but chip of the invention is not limited in this way, can adjust according to actual needs.
(2) surface hydrophilic is handled：68mL 40v% sodium hydroxide is taken to mix with 12mL 60v% hydrogen peroxide, by step
(1) chip is placed in mixed solution, is taken out chip after 45 DEG C of heating 1min, is successively respectively placed in 30mL ionized water, 30mL second
Alcohol is respectively cleaned by ultrasonic three times, each 30min.After cleaning, chip is taken out, in 40 DEG C of heating 2min.
(3) prehydrolysis：1g hexadecyl, 99g N,N-dimethylformamide and 1g second are weighed respectively
Acid is uniformly mixed, 30min is reacted at 35 DEG C, for use.
(4) surface-hydrophobicized processing：The chip micropore of step (2) is filled up with solid paraffin, and places it in step (3)
In system, standing adsorption 45s.Chip is taken out, with isopropanol repeated flushing chip to clean, is dried up with nitrogen gun, and at 40 DEG C
45s is heated, then gained chip is sequentially placed into 30mL trichloro ethylene, 30mL acetone and 30mL ethyl alcohol and is cleaned by ultrasonic three times, often
Secondary 30min.After cleaning, chip is taken out, and chip is placed in ethyl alcohol for use.
Embodiment 4
The present embodiment 4 provides a kind of surface modifying method of micro-array chip, and concrete operations are as follows：
(1) it cleans：Microwell array chip is sequentially placed into 30mL trichloro ethylene, 30mL acetone and 30mL ethyl alcohol respectively and is surpassed
Sound cleans three times, each 30min.After cleaning, chip is taken out, is dried up with nitrogen gun, and in 40 DEG C of heating 2min.This implementation
Chip material length, width and height are 1cm × 1cm × 300 μm in example, and chip surface about 20,000 micropores, the diameter of each micropore is about
It is 60 μm, but chip of the invention is not limited in this way, can adjust according to actual needs.
(2) surface hydrophilic is handled：50mL 37v% hydrochloric acid is taken to mix with 10mL 60v% hydrogen peroxide, by step (1)
Chip is placed in mixed solution, takes out chip after 40 DEG C of heating 1min, and it is each super to be successively respectively placed in 30mL ionized water, 30mL ethyl alcohol
Sound cleans three times, each 30min.After cleaning, chip is taken out, in 40 DEG C of heating 2min.
(3) prehydrolysis：1g octyltrichlorosilane, 45g tetrahydrofuran, 44g n-hexane and 1g acetic acid are weighed respectively, and mixing is equal
It is even, 30min is reacted at 30 DEG C, for use.
(4) surface-hydrophobicized processing：The chip micropore of step (2) is filled up with PDMS, and places it in the system of step (3)
In, standing adsorption 3h.Chip is taken out, with isopropanol repeated flushing chip to clean, is dried up with nitrogen gun, and is heated at 40 DEG C
30s, then gained chip is sequentially placed into 30mL trichloro ethylene, 30mL acetone and 30mL isopropanol and is cleaned by ultrasonic three times, every time
30min.After cleaning, chip is taken out, and chip is placed in ethyl alcohol for use.
Comparative example 1
This comparative example 1 provides a kind of surface modifying method of micro-array chip, and concrete operations are：
(1) it cleans：Microwell array chip is sequentially placed into 30mL trichloro ethylene, 30mL acetone and 30mL ethyl alcohol respectively and is surpassed
Sound cleans three times, each 30min.After cleaning, chip is taken out, is dried up with nitrogen gun, and in 40 DEG C of heating 2min.This implementation
Chip material length, width and height are 1cm × 1cm × 300 μm in example, and chip surface about 20,000 micropores, the diameter of each micropore is about
It is 60 μm, but chip of the invention is not limited in this way, can adjust according to actual needs.
(2) hydrophilic film is coated：Using infusion process, the chip of step (1) is put into and mainly contains TiO2Hydrophilic coating in,
10~15min is stood, is dried at room temperature, the chip that entire surface is hydrophilic film is obtained.
(3) micropore is covered：The chip micropore of step (2) is filled up with silicone oil.
(4) hydrophobic coating is coated：The hydrophobic coating main component of this comparative example is aided with a variety of based on organic siliconresin
The compound resin of low surface resin mixes inorganic nano and micron filler and various auxiliary agents and the super-hydrophobic painting of manufactured environment-friendly type
Material, is coated, specially using spray coating method：The spray gun for selecting 0.3~0.8mm bore, in the case where 1~4 atmospheric pressure acts on, gun slot
Chip 10~30cm of the diameter apart from step (3) sprays hydrophobic coating.Spraying finishes, with isopropanol repeated flushing chip to clean,
It is dried up with nitrogen gun, and is sequentially placed into 30mL trichloro ethylene, 30mL acetone and 30mL in 40 DEG C of heating 30s, then by gained chip
It is cleaned by ultrasonic in isopropanol three times, each 30min.After cleaning, chip is taken out, and chip is placed in ethyl alcohol for use.
Experimental example 1
After 3 months, the micro-array chip of 1-4 of the embodiment of the present invention and the modification of 1 surface of comparative example are observed respectively with microscope
The situation on chip surface layer in different environments.It is as shown in table 1 below to observe result：
The situation on the modified micro-array chip in 1 surface of table chip surface layer in different environments
| Micro-array chip | Air (H > 50%) | Diluted acid (pH=6.5) | Diluted alkaline (pH=7.5) |
| Embodiment 1 | Uniform, nothing falls off | Uniform, nothing falls off | Uniform, nothing falls off |
| Embodiment 2 | Uniform, nothing falls off | Uniform, nothing falls off | Uniform, nothing falls off |
| Embodiment 3 | Uniform, nothing falls off | Uniform, nothing falls off | Uniform, nothing falls off |
| Embodiment 4 | Uniform, nothing falls off | Uniform, nothing falls off | Uniform, nothing falls off |
| Comparative example 1 | Uniform, nothing falls off | Bumps have and fall off | Bumps have and fall off |
Experimental example 2
It does not carry out the micro-array chip of embodiment 1 and the modified micro-array chip in surface to impregnate respectively in water, 1min
After take out, measure the contact angle of chip surface, measurement result is shown in Fig. 1 and Fig. 2.It can be found by the comparison of Fig. 1 and Fig. 2, the present invention
Surface modifying method significantly improve the hydrophobicity of chip surface.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments, and it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (10)
1. a kind of surface modifying method of micro-array chip, which is characterized in that include the following steps：
Hydrophilicity-imparting treatment is carried out to the surface of the micro-array chip；
At least fill the port of micropore on the micro-array chip；
Silicic acid anhydride is carried out to the surface of the micro-array chip；
Remove the filler in the micropore.
2. the method according to claim 1, wherein the surface to the micro-array chip carries out hydrophiling
Processing step includes：
The micro-array chip is immersed in hydrophilizing agent, heating reaction at least 1min at 35~45 DEG C.
3. according to the method described in claim 2, it is characterized in that, the hydrophilizing agent includes hydrogen peroxide, further include ammonium hydroxide,
At least one of acetic acid, the concentrated sulfuric acid, hydrochloric acid or sodium hydroxide；In the hydrophilizing agent volume content of hydrogen peroxide be 15~
50%.
4. method according to claim 1-3, which is characterized in that the filler be water, trichloro ethylene, just oneself
Alkane, silicone oil, atoleine, solid paraffin, fluorinated oil, blue at least one of film or PDMS.
5. method according to claim 1-4, which is characterized in that the surface to the micro-array chip into
Row silicic acid anhydride step is：
Hydrophobic reagent is hydrolyzed, hydrating solution is obtained；
The micro-array chip is immersed in the hydrating solution and reacts at least 30s；
The hydrophobic reagent is perfluoro decyl trimethoxy silane, octadecyl trichlorosilane alkane, octadecyl silicon
At least one of alkane, hexadecyl, hexyl triethoxysilane or octyltrichlorosilane.
6. according to the method described in claim 5, it is characterized in that, described be hydrolyzed step to the hydrophobic reagent and be：
The hydrophobic reagent is added in the first polar organic solvent, heating reaction at least 30min at 25~35 DEG C；Described
One polar organic solvent is trichloro ethylene, in ethyl alcohol, isopropanol, n-hexane, acetone, N,N-Dimethylformamide, tetrahydrofuran
One or more of mixing with arbitrary proportion.
7. method according to claim 5 or 6, which is characterized in that described that step is hydrolyzed to the hydrophobic reagent
Further include the steps that catalyst is added in first polar organic solvent, the catalyst is acetic acid.
8. method according to claim 1-7, which is characterized in that the filler step in the removal micropore
Suddenly it is：
At least it is cleaned by ultrasonic with the second polar organic solvent primary；Second polar organic solvent is trichloro ethylene, acetone, second
One or more of alcohol, isopropanol are with the mixing of arbitrary proportion.
9. method according to claim 1-8, which is characterized in that the surface to the micro-array chip into
Further include the steps that carrying out the micro-array chip cleaning for the first time before row hydrophilizing treatment step and dry for the first time.
10. -9 described in any item methods according to claim 1, which is characterized in that the surface to the micro-array chip
It carries out further including the steps that carrying out the micro-array chip second of cleaning and second dries after hydrophilizing treatment step.
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| CN109701672A (en) * | 2019-01-18 | 2019-05-03 | 中国科学院苏州生物医学工程技术研究所 | Ultra-high throughput microarray unimolecule chip and preparation method thereof and imaging system |
| CN110628567A (en) * | 2019-09-25 | 2019-12-31 | 中国科学院苏州生物医学工程技术研究所 | Ultrahigh-flux single-cell nucleic acid molecule real-time fluorescence quantitative analysis chip |
| CN111701629A (en) * | 2020-07-03 | 2020-09-25 | 清华大学 | Super-hydrophobic micro-pit array chip and preparation method and device thereof |
| CN113138249A (en) * | 2021-04-12 | 2021-07-20 | 北京蛋白质组研究中心 | Micro-sample metabolome, proteome and phosphoproteome multi-group chemical analysis method based on micropore array chip |
| CN113638017A (en) * | 2021-08-12 | 2021-11-12 | 深圳先进技术研究院 | Method for electroplating Pt on metal conductive pattern |
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