CN102507671A - Porous silicon biochip and preparation method thereof - Google Patents
Porous silicon biochip and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of biotechnology, and discloses a porous silicon biochip and a preparation method thereof. The porous silicon preparation method provided by the invention comprises the steps of adopting electrochemical anodic oxidation technology to corrode a single face polished silicon wafer to obtain the porous silicon, wherein the oxidation mode is constant current electrolysis, the current density is 3mA/cm2 and the electrolysis time is 500-700 seconds; then performing modified decoration for the surface of the porous silicon by a functional silane coupling agent to obtain a modified layer containing active groups; and then preparing the porous silicon biochip by the functional porous silicon as a carrier. The preparation method provided by the invention is simple and convenient, requires fewer devices and is suitable for volume-production. The porous silicon biochip obtained by the method of the invention has the advantages of high sensitivity, good selectivity, good repeatability and the like, and can be used to study the interaction among biological macromolecules.
Description
Technical field
The present invention relates to biological technical field, relate to a kind of porous silicon biochip and preparation method thereof specifically.
Background technology
Porous silica material is a kind of novel silicon nano material that forms, has spongy structure through electrochemical oxidation monocrystalline silicon; Because its unique institutional framework and quantum effect; Make it have high efficiency photoluminescence and electroluminescence characters; Therefore, porous silicon is considered to one of material that has the huge applications prospect.Simultaneously, as silica-base material, porous silicon not only has good physics photoelectron performance; Also have huge specific surface area, good chemical activity and biocompatibility, this all is applied to the transducer sensor of biomolecule, cell and tissue for porous silicon; Aspects such as inorganic non-metallic biomaterial and biomedicine provide possibility (silicon materials and device, Silicon-Based Material and Devices, Edited by Hari Singh Nalwa; 2001, Academic Press).
At present, in the bio-sensing field, use the most extensive according to the porous silicon optical sensor of Fabry-Perot interference effect preparation; It utilizes the variation of porous silicon reflection interference spectrum figure; Can realize detection (science, Science, 1997 to biomolecule, bacterium, virus etc.; 278,840-842; U.S. chemical institute magazine, J.Am.Chem.Soc., 1998,120,12108-12116; U.S. chemical institute magazine, J.Am.Chem.Soc., 2005,127,11636-11645; Analytical chemistry, Anal.Chem., 2007,79,1502-1506; Practical new material, Adv.Funct.Mater., 2010,20,2269-2277; Analytical chemistry, Anal.Chem., 2011,83,3282-3289).
Biochip is the important tool of present genomics, protein science research, has advantages such as high flux, robotization, sample consumption be little.But at present, biochip mainly is carrier with glass, thus the diversity of detection means and and other highly sensitive detection technique integrated aspect still have certain disadvantages.Therefore, the application of expansion semiconductor material aspect the biochip carrier is significant to its development.The porous silicon semiconductor material is combined with biochip technology, help to promote the application of microelectric technique and photoelectron technology in the biochip field.
Summary of the invention
In view of this, it is good that the object of the invention provides a kind of selection type, highly sensitive porous silicon biochip and preparation method thereof.
For realizing the object of the invention, the present invention adopts following technical scheme:
A kind of preparation method of porous silicon biochip comprises:
Step 1: the polished surface of single-sided polishing silicon chip is contacted with electrolytic solution and connects cathode voltage through electrolytic solution; The back side contacts with conductor and connects anode voltage through conductor; Carry out electrochemical anodic oxidation then and obtain porous silicon, wherein, said oxidation model is constant-current electrolysis, current density 3mA/cm
2, electrolysis time is 500～700 seconds;
Step 2: the porous silicon that step 1 is made carries out functional modification, utilizes the biochip point sample system evenly to drip the biomacromolecule titer then and promptly gets.
The present invention adopts the electrochemical anodic oxidation technology that the single-sided polishing silicon chip is corroded and obtains porous silicon.Wherein, it is 1-10 Ω/cm that said single-sided polishing silicon chip is preferably resistivity, and the crystal orientation is the p type boron-doping monocrystalline silicon of < 100>single-sided polishing.
The oxidation model of electrochemical anodic oxidation according to the invention is constant-current electrolysis, current density 3mA/cm
2, electrolysis time is 500～700 seconds.Being preferably electrolysis time is 600 seconds.
Preferably, electrolytic solution described in the electrochemical anodic oxidation process according to the invention is that volume fraction is 25% hydrofluorite ethanolic solution.
According to the present invention, before carrying out galvanic corrosion, need clean completely silicon chip, to remove the original oxide layer of silicon chip surface, therefore before step 1, also comprise the step of said single-sided polishing silicon chip being carried out surface clean.
Wherein, as preferably, silicon chip surface according to the invention cleans and specifically comprises:
Step a: silicon chip is put into acetone, cyclohexane, acetone, absolute ethyl alcohol successively carry out ultrasonic cleaning, each scavenging period is 3 minutes, dries naturally;
Step b: the silicon chip that will dry is put into the solution that volume ratio is 3: 1 concentrated sulphuric acids and oxydol, no longer includes bubble to silicon chip surface and produces and take out, and earlier with a large amount of cold deionized water rinsings, the reusable heat deionized water rinsing is clean;
Step c: clean silicon chip immersion volume fraction is 5% hydrofluoric acid aqueous solution, soaks 1 minute, rinses well with deionized water then, and it is subsequent use to put into absolute ethyl alcohol.
The preparation method of porous silicon biochip according to the invention need carry out functional modification to porous silicon after making porous silicon, combine required functionalization group so that porous silicon surface has with different biomacromolecules.In certain embodiments, the said functional modification of preparation method's step 3 according to the invention is that epoxidation is modified, to combine glucide, preparation porous silicon carbohydrate chip.
As preferably, epoxidation according to the invention is modified to be specially and is utilized silane coupling agent under the protection of nitrogen stream, and 120 ℃, stirring and refluxing 24 hours promptly gets.Wherein, as preferably, said silane coupling agent is that massfraction is the anhydrous N of γ-glycidyl ether oxygen propyl trimethoxy silicane of 1%, dinethylformamide solution.
Preparation method's step 2 according to the invention is utilized the biochip point sample system evenly to drip the biomacromolecule titer and is prepared the porous silicon biochip after the porous silicon that step 1 is made carries out functional modification.Wherein, said biomacromolecule comprises the product that albumen, nucleic acid, carbohydrate, lipid and they mutually combine, like glycoprotein, lipoprotein, nucleoprotein etc.In certain embodiments, biomacromolecule according to the invention is a carbohydrate, and the porous silicon biochip that promptly makes is the carbohydrate biochip.In certain embodiments; Said carbohydrate is 4-aminophenyl-β-D-gala pyranose or 4-aminophenyl-α-D-mannopyranose, and said sampling liquid also comprises: the 0.3mol/L PBS that contains 0.15mol/L sodium chloride of the glycerine of volume fraction 20% and pH7.5.Behind the point sample, said porous silicon chip reacted 12 hours under 25 ℃, vacuum environment, and after the reaction, selecting massfraction for use is promptly to get after 0.5% bovine serum albumin(BSA) seals unreacted epoxy groups group.
The present invention also provides the porous silicon biochip that utilizes preparation method's preparation according to the invention.
Porous silicon preparation method provided by the invention is that the employing oxidation model is constant-current electrolysis, current density 3mA/cm
2, electrolysis time is that 500～700 seconds electrochemical anodic oxidation technology is corroded the single-sided polishing silicon chip and obtained porous silicon; Utilize the silane coupling agent of functionalization that porous silicon surface is carried out functional modification afterwards; Obtain containing the decorative layer of reactive group; Porous silicon with functionalization is a carrier then, preparation porous silicon biochip.Preparation method according to the invention is easy, and device requirement is few, the suitable production in enormous quantities in enormous quantities.The porous silicon biochip that utilizes the method for the invention to prepare has highly sensitive, and advantage such as the good and reappearance of selectivity is good can be used for the Study of Interaction of biomacromolecule.Experiment shows; Compare with existing brilliant core
optical grade epoxy substrate, porous silicon biochip according to the invention can improve detectability two one magnitude to monose and agglutinin.
Description of drawings
Fig. 1 shows that 4-aminophenyl-β-D-gala pyranose concentration of using the different etching times of the method for the invention to make is the porous silicon carbohydrate chip of 50mM and the typical curve of brilliant core
epoxy chip detection castor bean agglutinin (RCA120); Wherein, a: the porous silicon carbohydrate chip of etching time 500s, b: the porous silicon carbohydrate chip of etching time 600s, c: the porous silicon carbohydrate chip of etching time 700s, d: brilliant core
epoxy chip;
Fig. 2 shows that castor bean agglutinin (RCA 120) concentration that makes with the different etching times of the method for the invention is the porous silicon carbohydrate chip of 100 μ g/mL and the typical curve of brilliant core
epoxy chip detection 4-aminophenyl-β-D-gala pyranose; Wherein, a: the porous silicon carbohydrate chip of etching time 500s, b: the porous silicon carbohydrate chip of etching time 600s, c: the porous silicon carbohydrate chip of etching time 700s, d: brilliant core
epoxy chip;
Fig. 3 shows that 4-aminophenyl-α-D-mannopyranose concentration of using the different etching times of the method for the invention to make is the porous silicon carbohydrate chip of 50mM and the typical curve of brilliant core
epoxy chip detection concanavalin agglutinin (Con A); Wherein, a: the porous silicon carbohydrate chip of etching time 500s, b: the porous silicon carbohydrate chip of etching time 600s, c: the porous silicon carbohydrate chip of etching time 700s, d: brilliant core
epoxy chip;
Fig. 4 shows that concanavalin agglutinin (Con A) concentration that makes with the different etching times of the method for the invention is the porous silicon carbohydrate chip of 100 μ g/mL and the typical curve of brilliant core
epoxy chip detection 4-aminophenyl-α-D-mannopyranose; Wherein, a: the porous silicon carbohydrate chip of etching time 500s, b: the porous silicon carbohydrate chip of etching time 600s, c: the porous silicon carbohydrate chip of etching time 700s, d: brilliant core
epoxy chip.
Embodiment
The embodiment of the invention discloses a kind of porous silicon biochip and preparation method thereof.Those skilled in the art can use for reference this paper content, suitably improve technological parameter and realize.Special needs to be pointed out is that all similarly replace and change apparent to those skilled in the art, they all are regarded as and are included in the present invention.Product of the present invention and method are described through preferred embodiment, and the related personnel obviously can change or suitably change and combination method as herein described in not breaking away from content of the present invention, spirit and scope, realizes and use technology of the present invention.
In order further to understand the present invention, the present invention is elaborated below in conjunction with embodiment.
The detection of embodiment 1:4-aminophenyl-β-D-gala pyranose
Before carrying out galvanic corrosion, clean completely silicon chip.The concrete steps of cleaning are following: with resistivity is that acetone, cyclohexane are put into successively for the p type boron-doping monocrystalline silicon silicon chip of < 100>single-sided polishing in 1-10 Ω cm, crystal orientation; Acetone; Carry out ultrasonic cleaning in the absolute ethyl alcohol, each scavenging period is 3 minutes, and the back that finishes is taken out nature and dried; Again silicon chip being put into concentrated sulphuric acid oxydol volume ratio is 3: 1 solution to silicon chip surface when no longer including bubble and producing, and takes out, and earlier with a large amount of cold deionized water rinsings, the reusable heat deionized water rinsing is clean; Silicon chip through above processing immerses 5% hydrofluoric acid aqueous solution, soaks and removes oxide layer in 1 minute, rinses well with deionized water, and it is for use to put into absolute ethyl alcohol.
With the polished surface of cleaned silicon chip and percent by volume is that 25% hydrofluorite ethanolic solution contacts, and the back side contacts with copper sheet to draw and connects anode voltage, and solution connects cathode voltage, with constant-current electrolysis, and current density 3mA/cm
2, etching time was respectively 500 seconds, 600 seconds and 700 seconds.The porous silicon of preparing cleans with deionized water and ethanol immediately, flows down at nitrogen to dry up.
The porous silicon that dries up is heat-treated in constant temperature oven, carried out slow oxidation in 24 hours 150 ℃ of insulations; Porous silicon chip after the oxidation is put into acetone, cyclohexane, acetone and absolute ethyl alcohol respectively successively and was carried out ultrasonic cleaning 3 minutes, and the back that finishes is taken out nature and dried; Porous silicon chip after the cleaning places vacuum drying chamber, and 100 ℃ of vacuum drying are more than 12 hours; After the drying, porous silicon chip is put into there-necked flask, and add 150mL and contain the anhydrous N that massfraction is 1% γ-glycidyl ether oxygen propyl trimethoxy silicane, dinethylformamide solution, the protection of nitrogen stream was heated to 120 ℃ of stirring and refluxing 24 hours down; After reaction finished, silicon chip was used anhydrous N successively, dinethylformamide, acetone, absolute ethyl alcohol ultrasonic cleaning 3 minutes; Finishing is placed on vacuum drying chamber, and 50 ℃ of vacuum drying 1 hour obtain the porous silicon chip that epoxide group is modified, and it is for use to put into 4 ℃ of preservations of refrigerator.
The porous silicon chip of modifying with the epoxide group of preparation, brilliant core
the optical grade epoxy substrate that Bo Ao Bioisystech Co., Ltd in Beijing produces are carrier; Utilize SmartArrayer 48 biochip point sample system point samples; Making concentration gradient is 4-aminophenyl-β-D-gala pyranose monose chip of 10 μ M-200mM, and the point sample amount is the 1nL/ point.In order to obtain the activity of good array point shape uniformly and maintenance biomolecule, the sampling liquid of selecting for use also comprises except 4-aminophenyl-β-D-gala pyranose solution: the 0.3mol/L PBS that contains 0.15mol/L sodium chloride of the glycerine of volume fraction 20% and pH=7.5.Behind the point sample; At 25 ℃; Reaction is 12 hours under the vacuum environment, and selecting massfraction after the reaction for use is to obtain porous silicon carbohydrate biochip and brilliant core
epoxy carbohydrate biochip after 0.5% bovine serum albumin(BSA) seals unreacted epoxy groups group.
Fluorescence labeling porous silicon carbohydrate biochip: with the concentration gradient of making be 10 μ M-200mM 4-aminophenyl-β-D-gala pyranose monose chip respectively with the reaction of the fluorescein-labeled castor bean agglutinin (FITC-RCA 120) of 10ng/mL-200ug/mL, temperature of reaction is 30 ℃, 1 hour time.Use the PBS that contains 0.1% Tween-20 after finishing successively, PBS, the clean and centrifuge dripping of washed with de-ionized water obtains fluorescently-labeled carbohydrate biochip.
Fluoroscopic examination porous silicon carbohydrate biochip: the fluorescently-labeled carbohydrate biochip that will obtain is put into microarray scanner (LuxScan-10K/A type; Beijing Bo Ao Bioisystech Co., Ltd) detects; Obtain the fluorescence signal of carbohydrate biochip, the typical curve of fluoroscopic examination is seen Fig. 1.
According to the method for the invention with the castor bean agglutinin as sample; Utilize SmartArrayer 48 biochip point sample systems to make the castor bean agglutinin chip of variable concentrations gradient; With 4-aminophenyl-β-D-gala pyranose reaction of the variable concentrations of agglutinin mark, microarray scanner detects the typical curve of fluorescence signal fluoroscopic examination and sees Fig. 2 then.
The detection of embodiment 2:4-aminophenyl-α-D-mannopyranose
With resistivity is that acetone, cyclohexane are put into successively for the p type boron-doping monocrystalline silicon silicon chip of < 100>single-sided polishing in 1-10 Ω cm, crystal orientation, and acetone carries out ultrasonic cleaning in the absolute ethyl alcohol, and each scavenging period is 3 minutes, and the back that finishes is taken out nature and dried; Again silicon chip being put into concentrated sulphuric acid oxydol volume ratio is 3: 1 solution to silicon chip surface when no longer including bubble and producing, and takes out, and earlier with a large amount of cold deionized water rinsings, the reusable heat deionized water rinsing is clean; Silicon chip through above processing immerses 5% hydrofluoric acid aqueous solution, soaks and removes oxide layer in 1 minute, rinses well with deionized water, and it is for use to put into absolute ethyl alcohol.
With the polished surface of cleaned silicon chip and percent by volume is that 25% hydrofluorite ethanolic solution contacts, and the back side contacts with copper sheet to draw and connects anode voltage, and solution connects cathode voltage, with constant-current electrolysis, and current density 3mA/cm
2, etching time was respectively 500 seconds, 600 seconds and 700 seconds.The porous silicon of preparing cleans with deionized water and ethanol immediately, flows down at nitrogen to dry up.
The porous silicon that dries up is heat-treated in constant temperature oven, carried out slow oxidation in 24 hours 150 ℃ of insulations; Porous silicon chip after the oxidation is put into acetone, cyclohexane, acetone and absolute ethyl alcohol respectively successively and was carried out ultrasonic cleaning 3 minutes, and the back that finishes is taken out nature and dried; Porous silicon chip after the cleaning places vacuum drying chamber, and 100 ℃ of vacuum drying are more than 12 hours; After the drying, porous silicon chip is put into there-necked flask, and add 150mL and contain the anhydrous N that massfraction is 1% γ-glycidyl ether oxygen propyl trimethoxy silicane, dinethylformamide solution, the protection of nitrogen stream was heated to 120 ℃ of stirring and refluxing 24 hours down; After reaction finished, silicon chip was used anhydrous N successively, dinethylformamide, acetone, absolute ethyl alcohol ultrasonic cleaning 3 minutes; Finishing is placed on vacuum drying chamber, and 50 ℃ of vacuum drying 1 hour obtain the porous silicon chip that epoxide group is modified, and it is for use to put into 4 ℃ of preservations of refrigerator.
The porous silicon chip of modifying with the epoxide group of preparation, brilliant core
the optical grade epoxy substrate that Bo Ao Bioisystech Co., Ltd in Beijing produces are carrier; Utilize SmartArrayer 48 biochip point sample system point samples; Making concentration gradient is 4-aminophenyl-α-D-mannopyranose monose chip of 10 μ M-100mM, and the point sample amount is the 1nL/ point.In order to obtain the activity of good array point shape uniformly and maintenance biomolecule, the sampling liquid of selecting for use also comprises except 4-aminophenyl-α-D-mannopyranose solution: the 0.3mol/L PBS that contains 0.15mol/L sodium chloride of the glycerine of volume fraction 20% and pH=7.5.Behind the point sample; At 25 ℃; Reaction is 12 hours under the vacuum environment, and selecting massfraction after the reaction for use is to obtain porous silicon carbohydrate biochip and brilliant core
epoxy carbohydrate biochip after 0.5% bovine serum albumin(BSA) seals unreacted epoxy groups group.
Fluorescence labeling porous silicon carbohydrate biochip: with the concentration gradient of making be 10 μ M-100mM 4-aminophenyl-α-D-mannopyranose monose chip respectively with fluorescein-labeled concanavalin agglutinin (FITC-Con A) reaction, temperature of reaction is 30 ℃, 1 hour time.Use the PBS that contains 0.1% Tween-20 after finishing successively, PBS, the clean and centrifuge dripping of washed with de-ionized water obtains fluorescently-labeled carbohydrate biochip.
Fluoroscopic examination porous silicon carbohydrate biochip: the fluorescently-labeled carbohydrate biochip that will obtain is put into microarray scanner (LuxScan-10K/A type; Beijing Bo Ao Bioisystech Co., Ltd) detects; Obtain the fluorescence signal of carbohydrate biochip, the typical curve of fluoroscopic examination is seen Fig. 3.
According to the method for the invention with the concanavalin agglutinin as sample; Utilize SmartArrayer48 biochip point sample system to make the concanavalin agglutinin chip of variable concentrations gradient; With 4-aminophenyl-α-D-mannopyranose reaction of the variable concentrations of agglutinin mark, microarray scanner detects the typical curve of fluorescence signal fluoroscopic examination and sees Fig. 4 then.
Embodiment 3:
The porous silicon chip and existing brilliant core
the epoxy chip detection galactose (Gal-β) of the method preparation that the statistics embodiment of the invention 1 and embodiment 2 provide; Castor bean agglutinin (RCA 120); Mannose (Man-α); The testing result of concanavalin agglutinin (Con A) is seen table 1.
The range of linearity and the detectability of table 1. porous silicon carbohydrate chip and brilliant core
epoxy chip
Visible by table 1 result; The oxidization time that utilizes the embodiment of the invention 1 and embodiment 2 to provide is respectively the porous silicon chip detection of preparation method's preparation of 500 seconds, 600 seconds, 700 seconds, and the detection that the galactose detection is limited to 100～500 μ M, castor bean agglutinin is limited to 300ng/mL～5 μ g/mL, mannose detects the detection that is limited to 100～500 μ M, concanavalin agglutinin and is limited to 500ng/mL～5 μ g/mL.And the detection that utilizes existing brilliant core
epoxy chip detection, galactose detection to be limited to 5mM, castor bean agglutinin is limited to 5 μ g/mL, mannose detects the detection that is limited to 5mM, concanavalin agglutinin and is limited to 5 μ g/mL.The porous silicon biochip that shows preparation method's preparation according to the invention is highly sensitive, and selectivity is good.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
Claims (10)
1. the preparation method of a porous silicon biochip is characterized in that, comprising:
Step 1: the polished surface of single-sided polishing silicon chip is contacted with electrolytic solution and connects cathode voltage through electrolytic solution; The back side contacts with conductor and connects anode voltage through conductor; Carry out electrochemical anodic oxidation then and obtain porous silicon, wherein, said oxidation model is constant-current electrolysis, current density 3mA/cm
2, electrolysis time is 500～700 seconds;
Step 2: the porous silicon that step 1 is made carries out functional modification, utilizes the biochip point sample system evenly to drip the biomacromolecule titer then and promptly gets.
2. according to the said preparation method of claim 1, it is characterized in that said silicon chip is that resistivity is 1-10 Ω/cm, the crystal orientation is the p type boron-doping monocrystalline silicon of < 100>single-sided polishing.
3. according to the said preparation method of claim 1, it is characterized in that said electrolytic solution is that volume fraction is 25% hydrofluorite ethanolic solution.
4. according to the said preparation method of claim 1, it is characterized in that, also comprise the step of said single-sided polishing silicon chip being carried out surface clean before the step 1, specifically comprise:
Step a: the single-sided polishing silicon chip is put into acetone, cyclohexane, acetone, absolute ethyl alcohol successively carry out ultrasonic cleaning, each scavenging period is 3 minutes, dries naturally;
Step b: the silicon chip that will dry is put into the solution that volume ratio is 3: 1 concentrated sulphuric acids and oxydol, no longer includes bubble to silicon chip surface and produces and take out, and earlier with a large amount of cold deionized water rinsings, the reusable heat deionized water rinsing is clean;
Step c: clean silicon chip immersion volume fraction is 5% hydrofluoric acid aqueous solution, soaks 1 minute, rinses well with deionized water then, and it is subsequent use to put into absolute ethyl alcohol.
5. according to the said preparation method of claim 1, it is characterized in that the said electrolysis time of step 1 is 600 seconds.
6. according to the said preparation method of claim 1, it is characterized in that the said functional modification of step 2 is that epoxidation is modified.
7. according to the said preparation method of claim 6, it is characterized in that said epoxidation is modified to and utilizes silane coupling agent under the protection of nitrogen stream, 120 ℃, stirring and refluxing 24 hours promptly gets.
8. according to the said preparation method of claim 7, it is characterized in that said silane coupling agent is that massfraction is the anhydrous N of γ-glycidyl ether oxygen propyl trimethoxy silicane of 1%, dinethylformamide solution.
9. according to the said preparation method of claim 6, it is characterized in that the said biomacromolecule of step 2 is a carbohydrate.
10. the porous silicon biochip of any said preparation method preparation of claim 1～9.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103979543A (en) * | 2014-05-08 | 2014-08-13 | 新疆大学 | Porous silicon modification method and use of porous silicon as biosensor |
| CN107296802A (en) * | 2017-08-03 | 2017-10-27 | 南京师范大学 | One kind has hydrophobic porous micro- glue of silicon curcumin of antioxidation activity and preparation method thereof |
| CN107375936A (en) * | 2017-06-21 | 2017-11-24 | 南京师范大学 | A kind of curcumin porous silicon and preparation method thereof |
| CN107473175A (en) * | 2017-08-15 | 2017-12-15 | 薛宁 | A kind of nerve electrode and its manufacture craft and application based on porous silicon and polymer |
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| CN114524622A (en) * | 2022-03-07 | 2022-05-24 | 北京康敏生物科技有限公司 | Preparation method of epoxy modified substrate, microarray chip and application of microarray chip |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009066275A1 (en) * | 2007-11-22 | 2009-05-28 | Dublin City University | A method of immobilising biological molecules to a support and products thereof |
-
2011
- 2011-10-11 CN CN201110306647.3A patent/CN102507671B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009066275A1 (en) * | 2007-11-22 | 2009-05-28 | Dublin City University | A method of immobilising biological molecules to a support and products thereof |
Non-Patent Citations (7)
| Title |
|---|
| 《中国优秀硕士学位论文全文数据库 基础科学辑》 20080815 南刚 用于制备糖芯片新方法的研究 正文第20-25页 1-10 , * |
| IVO RENDINA ET AL: "Porous silicon-based optical biosensors and biochips", 《PHYSICA E》, vol. 38, 31 December 2007 (2007-12-31), pages 188 - 192, XP022040514, DOI: doi:10.1016/j.physe.2006.12.050 * |
| JINGQING GAO ET AL: "Microarray-Based Study of Carbohydrate-Protein Binding by Gold Nanoparticle Probes", 《ANAL.CHEM.》, vol. 80, 31 December 2008 (2008-12-31), pages 8822 - 8827 * |
| M.NADDAF ET AL: "Porous silicon as a platform for immobilization of biotin anti-human IL-6;rat IgG2a antibody onto p-type porous silicon via physical absorption method", 《SENSORS AND ACTUATORS B:CHEMICAL》, 31 August 2011 (2011-08-31), pages 835 - 839, XP028110976, DOI: doi:10.1016/j.snb.2011.08.069 * |
| PRAJAKTA S.CHAUDHARI ET AL: "Porous silicon as an entrapping matrix for the immobilization of urease", 《SENSORS AND ACTUATORS B》, vol. 107, 31 December 2005 (2005-12-31), pages 258 - 263 * |
| 南刚: "用于制备糖芯片新方法的研究", 《中国优秀硕士学位论文全文数据库 基础科学辑》, 15 August 2008 (2008-08-15), pages 20 - 25 * |
| 田斌等: "用电化学方法制备多孔硅", 《天津大学学报》, vol. 37, no. 9, 30 September 2004 (2004-09-30), pages 823 - 826 * |
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| CN107296802B (en) * | 2017-08-03 | 2020-11-20 | 南京师范大学 | Hydrophobic porous silicon curcumin micro-gel with antioxidant activity and preparation method thereof |
| CN107473175A (en) * | 2017-08-15 | 2017-12-15 | 薛宁 | A kind of nerve electrode and its manufacture craft and application based on porous silicon and polymer |
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| CN114524622A (en) * | 2022-03-07 | 2022-05-24 | 北京康敏生物科技有限公司 | Preparation method of epoxy modified substrate, microarray chip and application of microarray chip |
| CN114524622B (en) * | 2022-03-07 | 2023-09-08 | 安吉世纪康敏生物科技有限公司 | Preparation method of epoxy modified substrate, microarray chip and application of microarray chip |
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Effective date of registration: 20161214 Address after: Changzhou City, Jiangsu province Hehai road 213000 No. 9 Patentee after: Changzhou Institute of Energy Storage Materials & Devices Address before: 130000 Jilin City, Changchun province people's street, No. 5625 Patentee before: Changchun Applied Chemistry Inst., Chinese Academy of Sciences |