CN101839883A - Laminated film enzyme electrode and preparation method thereof - Google Patents
Laminated film enzyme electrode and preparation method thereof Download PDFInfo
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- CN101839883A CN101839883A CN200910080302A CN200910080302A CN101839883A CN 101839883 A CN101839883 A CN 101839883A CN 200910080302 A CN200910080302 A CN 200910080302A CN 200910080302 A CN200910080302 A CN 200910080302A CN 101839883 A CN101839883 A CN 101839883A
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Abstract
The invention discloses a laminated film enzyme electrode and a preparation method thereof, which belongs to the technical field of biological sensors. The laminated film enzyme electrode consists of a substrate electrode, an electric stem grafting poly N-mercapto ethyl-acrylamide, gold nanoparticles with negative charges, and enzyme molecules with positive charges. The enzyme molecule is horseradish peroxidase or cytochrome C. The preparation method comprises the steps of preparing the poly N-mercapto ethyl-acrylamide in an electric stem grafting method, then covalently linking the gold nanoparticles with the negative charges, and finally fixing the enzyme molecules with the positive charges. The laminated film prepared by the invention realizes the direct electrochemistry action of the enzyme molecules, the enzyme molecules show excellent electric catalytic activity, and the laminated film enzyme electrode has good catalytic activity and wider linear range. The invention has simple process, can effectively immobilize enzyme bio-molecules, and has great significance on the direct electrochemical property of the enzyme biosensor and research on the application thereof.
Description
Technical field
The invention belongs to the biosensor technology field, particularly a kind of laminated film enzyme electrode and preparation method thereof.
Background technology
The current mode enzyme biologic sensor has caused extensive concern in recent years, obtain a large amount of achievements in research and partly realized commercialization, it aspect fundamental research and the applied research all is being a crucial research topic, wherein, the main problem of existence is the direct electron transfer between effectively fixing of enzyme molecule and enzyme and the electrode.The fixing physics or the chemical method of adopting usually of current enzyme molecule.Physisorption mainly is based on interaction between enzyme molecule and the transducer such as Van der Waals force and electrostatic interaction.And realized control and adjusting to thicknesses of layers, structure and composition being widely used in preparing the functional living being laminated film by simple relatively preparation process based on the static layer-by-layer (LbL) of organic template.When the substrate neutral, this method need immerse substrate in the solution of the polyelectrolyte that has electric charge usually, and pre-service is carried out on the surface, thereby can assemble by electrostatic force absorption.But this method exists a big problem to need to solve: the acting force between polyelectrolyte and the substrate is more weak and stable poor.In long preparation process often is uncontrollable.Therefore, in order to improve the stability of pre-service film, the covalent bonds between the interface is very necessary.
The electricity grafting then is a kind of straightforward procedure for preparing strong adsorption thin polymer film on solid substrate.Thereby covalently bound at substrate surface by the electron transfer between monomer and the conductive substrates, therefore electric grafting can improve stability for next step modification of substrate.Monomer generally include can cleavable electric active molecule, such as vinyl monomer, acrylic monomer and diazo salt etc.
The research of nano material has greatly promoted biomedicine, the development of biology sensor and living things catalysis.Nano material with biocompatibility can keep its active and realization Direct Electrochemistry behavior for the enzyme molecule provides gentle microenvironment.Especially the nano particle of noble metal, because it has great specific surface area, good electrical conductivity and high catalytic activity have been widely used in field of biosensors.
Summary of the invention
The purpose of this invention is to provide a kind of laminated film enzyme electrode and preparation method thereof.
A kind of laminated film enzyme electrode is characterized in that, by the poly-N-mercapto ethyl acrylamide of basal electrode, electro-grafted films, have the nanogold particle of negative charge and have the enzyme molecular composition of positive charge.
Described enzyme molecule is horseradish peroxidase or cromoci.
A kind of preparation method of laminated film enzyme electrode is characterized in that, adopts electric grafting method to prepare poly-N-mercapto ethyl acrylamide, and the covalently bound then nanogold particle that has negative charge fixedly has the enzyme molecule of positive electricity at last, and this method step is as follows,
(1) preparation has the solution of nanogold particle of negative charge: sodium citrate and the concentration that with concentration is 0.15～0.35mmol/L is that the chlorauric acid solution of 0.15～0.35mmol/L mixes according to volume ratio (2: 3)～(3: 2), stir, adding concentration then is 0.05～0.2mmol/L sodium borohydride aqueous solution, the volume and the sodium citrate volume ratio of the sodium borohydride aqueous solution that adds are 0.15～0.6, stir that solution becomes claret after 5～10 minutes, left standstill 2～5 hours, and obtained having the solution of the nanogold particle of negative charge;
(2) adopt electric grafting method to prepare poly-N-mercapto ethyl acrylamide film on basal electrode: clean basal electrode, preparation contains the dimethyl formamide solution of N-acryloyl-oxy succinimide and 4-butyl amine tetrafluoroborate, logical N
2Deoxygenation 15～30 minutes, clean basal electrode is placed the dimethyl formamide solution that contains N-acryloyl-oxy succinimide and 4-butyl amine tetrafluoroborate, potential range 0 and-scan 2～6 circles between the 2.7V, then the electrode after the poly-N-acryloyl-oxy succinimide of electric grafting is immersed in 1～20mmol/L mercaptoethylmaine solution, soak time is 10～25 hours, make it become poly-N-mercapto ethyl acrylamide by amino ester appended, thereby on basal electrode, prepared poly-N-mercapto ethyl acrylamide film;
(3) preparation of laminated film enzyme electrode: the electrode that will prepare poly-N-mercapto ethyl acrylamide film on basal electrode places the solution of the nanogold particle that has negative charge, soaked 2～12 hours, gold nano grain is by covalently bound at electrode surface with the sulfydryl effect, then, electrode is placed the enzyme molecular solution that has positive charge, described enzyme molecule is horseradish peroxidase or cromoci, soaked 5～12 hours, enzyme molecule Electrostatic Absorption is on the gold grain surface, thereby is prepared into the laminated film enzyme electrode.
Described basal electrode is indium-tin oxide electrode, glass-carbon electrode or pyrolytic graphite electrode.
In the described cleaning basal electrode, glass-carbon electrode or pyrolytic graphite electrode cleaning step are for being the Al of 1.0 μ m, 0.3 μ m successively with diameter with substrate glass-carbon electrode or pyrolytic graphite electrode
2O
3Slurry is polished to minute surface on chamois leather, each polishing back moves into and uses ethanol and each ultrasonic cleaning 1～3min of deionized water in the ultrasonic device successively earlier with deionized water flush away surface contaminants, uses N
2Basal electrode is dried up; The indium-tin oxide electrode cleaning step is used N for using each ultrasonic cleaning 5～10min of ethanol and deionized water successively
2Indium-tin oxide electrode is dried up.
In the described dimethyl formamide solution that contains N-acryloyl-oxy succinimide and 4-butyl amine tetrafluoroborate, 4-butyl amine tetrafluoro boric acid salinity is 0.4～1mol/L in the dimethyl formamide solution, and N-acryloyl-oxy succinimide concentration is 0.05～1mol/L.
Beneficial effect of the present invention is:
The employing electricity grafting method of success of the present invention gathers the covalently bound nanogold particle of N-mercapto ethyl acrylamide in order to the immobilized enzyme molecule in the grafting of basal electrode surface electrical, adopt electric grafting method that electrode is modified, the pre-service film of high stability is provided for next step modification, make fixing enzyme molecule keep good active with combining of nanogold particle and have good catalytic property, the laminated film of preparation, realized the Direct Electrochemistry behavior of enzyme molecule, and the enzyme molecule shows good electro catalytic activity, and this laminated film enzyme electrode has the range of linearity of good catalytic activity and broad.Technology of the present invention is simple, and the immobilized enzyme biomolecule has great importance to the Direct Electrochemistry character of enzyme biologic sensor and the research of application thereof effectively.
Description of drawings
Fig. 1 is the preparation process synoptic diagram of the laminated film enzyme electrode of embodiment 1.
Embodiment
The invention will be further described below in conjunction with embodiment and accompanying drawing:
Embodiment 1
A kind of laminated film enzyme electrode is made up of the poly-N-mercapto ethyl acrylamide of glass-carbon electrode, electro-grafted films, the horseradish peroxidase (HRP) that has the nanogold particle of negative charge and have a positive charge.
A kind of preparation method of laminated film enzyme electrode adopts electric grafting method to prepare poly-N-mercapto ethyl acrylamide, and the covalently bound then nanogold particle that has negative charge fixedly has the horseradish peroxidase of positive electricity at last, and this method step is as follows,
(1) preparation has the solution of the nanogold particle of negative charge: the sodium citrate that with concentration is 0.25mmol/L is that the 0.25mmol/L chlorauric acid solution mixes according to volume ratio at 1: 1 with concentration, stir, adding concentration then is the 0.1mmol/L sodium borohydride aqueous solution, the volume and the sodium citrate volume ratio of the sodium borohydride aqueous solution that adds are 0.3, stir that solution becomes claret after 5 minutes, left standstill 2～5 hours, and obtained having the solution of the nanogold particle of negative charge;
(2) adopt electric grafting method to prepare poly-N-mercapto ethyl acrylamide film on glass-carbon electrode: clean glass-carbon electrode, the step of cleaning glass-carbon electrode is to be the Al of 1.0 μ m, 0.3 μ m successively with diameter with glass-carbon electrode
2O
3Slurry is polished to minute surface on chamois leather, each polishing back moves into and uses ethanol and each ultrasonic cleaning 2min of distilled water in the ultrasonic device successively earlier with deionized water flush away surface contaminants, uses N
2Glass-carbon electrode is dried up, and preparation contains the dimethyl formamide solution of 0.1mol/L N-acryloyl-oxy succinimide and 0.05mol/L 4-butyl amine tetrafluoroborate, logical N in above-mentioned solution
2Deoxygenation 20 minutes, clean glass-carbon electrode is placed the dimethyl formamide solution that contains N-acryloyl-oxy succinimide and 4-butyl amine tetrafluoroborate, potential range 0 and-2.7V between scanning 4 the circle, then poly-N-acryloyl-oxy succinimide (PNSA) electrode afterwards of electric grafting is immersed in the 1mmol/L mercaptoethylmaine solution, soak time is 24h, make it become poly-N-mercapto ethyl acrylamide by amino ester appended, thereby on glass-carbon electrode, prepared poly-N-mercapto ethyl acrylamide film;
(3) preparation of laminated film enzyme electrode: the electrode that will prepare poly-N-mercapto ethyl acrylamide film on glass-carbon electrode places the solution of the nanogold particle that has negative charge, soak 12h, nanogold particle is by covalently bound at electrode surface with the sulfydryl effect, then, electrode is placed the horseradish peroxidase solution (pH=7) that has positive charge, soak 12h, the horseradish peroxidase Electrostatic Absorption is on the gold grain surface, thereby is prepared into the laminated film enzyme electrode.Fig. 1 has represented the preparation process synoptic diagram of laminated film enzyme electrode in the present embodiment.
Adopt cyclic voltammetric (CV) and electrochemical impedance spectroscopy (EIS) to study the organic/inorganic film assembling process in the present embodiment, its catalytic property is then studied by the electrochemical workstation CHI630B of Shanghai occasion China.In the electrochemical properties test process, we adopt three-electrode system, and wherein platinum electrode is to electrode, and Ag/AgCl (saturated KCl) electrode is a contrast electrode, and the organic/inorganic composite film enzyme electrode of assembling is as working electrode.The result shows that horseradish peroxidase shows good electro catalytic activity, and lower Michaelis constant (0.48mM) shows that horseradish peroxidase has kept good active in the microenvironment that modified electrode provides, within the specific limits to H
2O
2Response have tangible linear relationship, and stable performance.
Embodiment 2
A kind of laminated film enzyme electrode is made up of the poly-N-mercapto ethyl acrylamide of glass-carbon electrode, electro-grafted films, the cromoci that has the nanogold particle of negative charge and have a positive charge.
A kind of preparation method of laminated film enzyme electrode adopts electric grafting method to prepare poly-N-mercapto ethyl acrylamide, and the covalently bound then nanogold particle that has negative charge fixedly has the cromoci of positive electricity at last, and this method step is as follows,
(1) preparation has the solution of nanogold particle of negative charge: sodium citrate and the concentration that with concentration is 0.3mmol/L is that the chlorauric acid solution of 0.3mmol/L mixes according to volume ratio at 1.1: 1, stir, adding concentration then is the 0.05mmol/L sodium borohydride aqueous solution, the volume and the sodium citrate volume ratio of the sodium borohydride aqueous solution that adds are 0.6, stir that solution becomes claret after 10 minutes, left standstill 2～5 hours, and obtained having the solution of the nanogold particle of negative charge;
(2) adopt electric grafting method to prepare poly-N-mercapto ethyl acrylamide film on glass-carbon electrode: clean glass-carbon electrode, the step of cleaning glass-carbon electrode is to be the Al of 1.0 μ m, 0.3 μ m successively with diameter with glass-carbon electrode
2O
3Slurry is polished to minute surface on chamois leather, each polishing back moves into and uses ethanol and each ultrasonic cleaning 1min of deionized water in the ultrasonic device successively earlier with deionized water flush away surface contaminants, uses N
2Glass-carbon electrode is dried up, and preparation contains the dimethyl formamide solution of 0.1mol/L N-acryloyl-oxy succinimide and 0.1mol/L 4-butyl amine tetrafluoroborate, logical N in above-mentioned solution
2Deoxygenation 25 minutes, clean glass-carbon electrode is placed the dimethyl formamide solution that contains N-acryloyl-oxy succinimide and 4-butyl amine tetrafluoroborate, potential range 0 and-2.7V between scanning 4 the circle, then poly-N-acryloyl-oxy succinimide (PNSA) electrode afterwards of electric grafting is immersed in the 10mmol/L mercaptoethylmaine solution, soak time is 15h, make it become poly-N-mercapto ethyl acrylamide by amino ester appended, thereby on glass-carbon electrode, prepared poly-N-mercapto ethyl acrylamide film;
(3) preparation of laminated film enzyme electrode: the electrode that will prepare poly-N-mercapto ethyl acrylamide film on glass-carbon electrode places the solution of the nanogold particle that has negative charge, soak 5h, gold nano grain is by covalently bound at electrode surface with the sulfydryl effect, then, electrode is placed the cytochrome c solution (pH=7) that has positive charge, soak 10h, the cromoci Electrostatic Absorption is on the gold grain surface, thereby is prepared into the laminated film enzyme electrode.
The result shows that cromoci shows good electro catalytic activity, and it has kept good active in the microenvironment that modified electrode provides, within the specific limits to H
2O
2Response have tangible linear relationship, and stable performance.
Embodiment 3
A kind of laminated film enzyme electrode is made up of the poly-N-mercapto ethyl acrylamide of indium-tin oxide electrode, electro-grafted films, the cromoci that has the nanogold particle of negative charge and have a positive charge.
A kind of preparation method of laminated film enzyme electrode adopts electric grafting method to prepare poly-N-mercapto ethyl acrylamide, and the covalently bound then nanogold particle that has negative charge fixedly has the cromoci of positive electricity at last, and this method step is as follows,
(1) preparation has the solution of the nanogold particle of negative charge: the sodium citrate that with concentration is 0.21mmol/L is that the 0.21mmol/L chlorauric acid solution mixes according to volume ratio at 1: 1.1 with concentration, stir, adding concentration then is the 0.1mmol/L sodium borohydride aqueous solution, the volume and the sodium citrate volume ratio of the sodium borohydride aqueous solution that adds are 0.3, stir that solution becomes claret after 8 minutes, left standstill 2～5 hours, and obtained having the solution of the nanogold particle of negative charge;
(2) adopt electric grafting method on indium-tin oxide electrode, to prepare poly-N-mercapto ethyl acrylamide film: to clean indium-tin oxide electrode, the step of cleaning indium-tin oxide electrode is, indium-tin oxide electrode is used ethanol and each ultrasonic cleaning 5min of deionized water successively, use N
2Indium-tin oxide electrode is dried up, and preparation contains the dimethyl formamide solution of 0.2mol/LN-acryloyl-oxy succinimide and 0.1mol/L 4-butyl amine tetrafluoroborate, logical N in above-mentioned solution
2Deoxygenation 25 minutes, clean indium-tin oxide electrode is placed the dimethyl formamide solution that contains N-acryloyl-oxy succinimide and 4-butyl amine tetrafluoroborate, potential range 0 and-2.7V between scanning 4 the circle, then poly-N-acryloyl-oxy succinimide (PNSA) electrode afterwards of electric grafting is immersed in the 1mmol/L mercaptoethylmaine solution, soak time is 20h, make it become poly-N-mercapto ethyl acrylamide by amino ester appended, thereby on indium-tin oxide electrode, prepared poly-N-mercapto ethyl acrylamide film;
(3) preparation of laminated film enzyme electrode: the electrode that will prepare poly-N-mercapto ethyl acrylamide film on indium-tin oxide electrode places the solution of the nanogold particle that has negative charge, soak 8h, nanogold particle is by covalently bound at electrode surface with the sulfydryl effect, then, electrode is placed the cytochrome c solution (pH=7) that has positive charge, soak 12h, the cromoci Electrostatic Absorption is on the gold grain surface, thereby is prepared into the laminated film enzyme electrode.
The result shows that horseradish peroxidase shows good electro catalytic activity, within the specific limits to H
2O
2Response have tangible linear relationship, and stable performance.
Embodiment 4
A kind of laminated film enzyme electrode is made up of indium-tin oxide electrode, the poly-N-mercapto ethyl acrylamide of electro-grafted films, the nanogold particle that has negative charge and horseradish peroxidase.
A kind of preparation method of laminated film enzyme electrode adopts electric grafting method to prepare poly-N-mercapto ethyl acrylamide, the covalently bound then nanogold particle that has negative charge, and fixing horseradish peroxidase at last, this method step is as follows,
(1) preparation has the solution of the nanogold particle of negative charge: the sodium citrate that with concentration is 0.2mmol/L is that the 0.2mmol/L chlorauric acid solution mixes according to volume ratio at 1: 1 with concentration, stir, adding concentration then is the 0.1mmol/L sodium borohydride aqueous solution, the volume and the sodium citrate volume ratio of the sodium borohydride aqueous solution that adds are 0.3, stir that solution becomes claret after 6 minutes, left standstill 2～5 hours, and obtained having the solution of the nanogold particle of negative charge;
(2) adopt electric grafting method on indium-tin oxide electrode, to prepare poly-N-mercapto ethyl acrylamide film: to clean indium-tin oxide electrode, the step of cleaning indium-tin oxide electrode is, indium-tin oxide electrode is used ethanol and each ultrasonic cleaning 10min of deionized water successively, use N
2Indium-tin oxide electrode is dried up, and preparation contains the dimethyl formamide solution of 0.05mol/LN-acryloyl-oxy succinimide and 0.5mol/L 4-butyl amine tetrafluoroborate, logical N in above-mentioned solution
2Deoxygenation 30 minutes, clean indium-tin oxide electrode is placed the dimethyl formamide solution that contains N-acryloyl-oxy succinimide and 4-butyl amine tetrafluoroborate, potential range 0 and-2.7V between scanning 6 the circle, then the electrode after the poly-N-acryloyl-oxy succinimide PNSA of electric grafting is immersed in the 1mmol/L mercaptoethylmaine solution, soak time is 24h, make it become poly-N-mercapto ethyl acrylamide by amino ester appended, thereby on indium-tin oxide electrode, prepared poly-N-mercapto ethyl acrylamide film;
(3) preparation of laminated film enzyme electrode: the electrode that will prepare poly-N-mercapto ethyl acrylamide film on indium-tin oxide electrode places the solution of the nanogold particle that has negative charge, soak 11h, nanogold particle is by covalently bound at electrode surface with the sulfydryl effect, then, electrode is placed the horseradish peroxidase solution (pH=7) that has positive charge, soak 13h, the horseradish peroxidase Electrostatic Absorption is on the gold grain surface, thereby is prepared into the laminated film enzyme electrode.
The result shows that horseradish peroxidase shows good electro catalytic activity, and it has kept good active in the microenvironment that modified electrode provides, within the specific limits to H
2O
2Response have tangible linear relationship, and stable performance.
Claims (6)
1. a laminated film enzyme electrode is characterized in that, by the poly-N-mercapto ethyl acrylamide of basal electrode, electro-grafted films, have the nanogold particle of negative charge and have the enzyme molecular composition of positive charge.
2. a kind of laminated film enzyme electrode according to claim 1 is characterized in that described enzyme molecule is horseradish peroxidase or cromoci.
3. the preparation method of a laminated film enzyme electrode is characterized in that, adopts electric grafting method to prepare poly-N-mercapto ethyl acrylamide, and the covalently bound then nanogold particle that has negative charge fixedly has the enzyme molecule of positive electricity at last, and this method step is as follows,
(1) preparation has the solution of nanogold particle of negative charge: sodium citrate and the concentration that with concentration is 0.15～0.35mmol/L is that the chlorauric acid solution of 0.15～0.35mmol/L mixes according to volume ratio (2: 3)～(3: 2), stir, adding concentration then is 0.05～0.2mmol/L sodium borohydride aqueous solution, the volume and the sodium citrate volume ratio of the sodium borohydride aqueous solution that adds are 0.15～0.6, stir that solution becomes claret after 5～10 minutes, left standstill 2～5 hours, and obtained having the solution of the nanogold particle of negative charge;
(2) adopt electric grafting method to prepare poly-N-mercapto ethyl acrylamide film on basal electrode: clean basal electrode, preparation contains the dimethyl formamide solution of N-acryloyl-oxy succinimide and 4-butyl amine tetrafluoroborate, logical N
2Deoxygenation 15～30 minutes, clean basal electrode is placed the dimethyl formamide solution that contains N-acryloyl-oxy succinimide and 4-butyl amine tetrafluoroborate, potential range 0 and-scan 2～6 circles between the 2.7V, then the electrode after the poly-N-acryloyl-oxy succinimide of electric grafting is immersed in 1～20mmol/L mercaptoethylmaine solution, soak time is 10～25 hours, make it become poly-N-mercapto ethyl acrylamide by amino ester appended, thereby on basal electrode, prepared poly-N-mercapto ethyl acrylamide film;
(3) preparation of laminated film enzyme electrode: the electrode that will prepare poly-N-mercapto ethyl acrylamide film on basal electrode places the solution of the nanogold particle that has negative charge, soaked 2～12 hours, gold nano grain is by covalently bound at electrode surface with the sulfydryl effect, then, electrode is placed the enzyme molecular solution that has positive charge, described enzyme molecule is horseradish peroxidase or cromoci, soaked 5～12 hours, enzyme molecule Electrostatic Absorption is on the gold grain surface, thereby is prepared into the laminated film enzyme electrode.
4. the preparation method of a kind of laminated film enzyme electrode according to claim 3 is characterized in that, described basal electrode is indium-tin oxide electrode, glass-carbon electrode or pyrolytic graphite electrode.
5. the preparation method of a kind of laminated film enzyme electrode according to claim 3, it is characterized in that, in the described cleaning basal electrode, glass-carbon electrode or pyrolytic graphite electrode cleaning step are for being the Al of 1.0 μ m, 0.3 μ m successively with diameter with substrate glass-carbon electrode or pyrolytic graphite electrode
2O
3Slurry is polished to minute surface on chamois leather, each polishing back moves into and uses ethanol and each ultrasonic cleaning 1～3min of deionized water in the ultrasonic device successively earlier with deionized water flush away surface contaminants, uses N
2Basal electrode is dried up; The indium-tin oxide electrode cleaning step is used N for using each ultrasonic cleaning 5～10min of ethanol and deionized water successively
2Indium-tin oxide electrode is dried up.
6. the preparation method of a kind of laminated film enzyme electrode according to claim 3, it is characterized in that, in the described dimethyl formamide solution that contains N-acryloyl-oxy succinimide and 4-butyl amine tetrafluoroborate, 4-butyl amine tetrafluoro boric acid salinity is 0.4～1mol/L in the dimethyl formamide solution, and N-acryloyl-oxy succinimide concentration is 0.05～1mol/L.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105738451A (en) * | 2016-02-01 | 2016-07-06 | 大连理工大学 | Direct electron transfer type glucose biosensor and preparation method and application |
| CN107583102A (en) * | 2017-10-01 | 2018-01-16 | 刘云晖 | A kind of amphion aerogel dressing and its preparation and application |
| CN109234259A (en) * | 2018-11-23 | 2019-01-18 | 南京工业大学 | The process for fixation of pyruvate oxidase |
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| CN1578705A (en) * | 2001-08-28 | 2005-02-09 | 法国原子能委员会 | Method for grafting and growing a conductive organic film on a surface |
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2009
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1578705A (en) * | 2001-08-28 | 2005-02-09 | 法国原子能委员会 | Method for grafting and growing a conductive organic film on a surface |
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| C.JÉROME等: "Preparation of reactive surfaces by electrografting", 《CHEM.COMMUN.》 * |
| JENNIFER A. HARNISCH等: "Attachment of Gold Nanoparticles to Glassy Carbon Electrodes via a Mercaptobenzene Film", 《J. AM. CHEM. SOC.》 * |
| JIANBO JIA等: "A Method to Construct a Third-Generation Horseradish Peroxidase Biosensor: Self-Assembling Gold Nanoparticles to Three-Dimensional Sol-Gel Network", 《ANALYTICAL CHEMISTRY》 * |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105738451A (en) * | 2016-02-01 | 2016-07-06 | 大连理工大学 | Direct electron transfer type glucose biosensor and preparation method and application |
| CN107583102A (en) * | 2017-10-01 | 2018-01-16 | 刘云晖 | A kind of amphion aerogel dressing and its preparation and application |
| CN107583102B (en) * | 2017-10-01 | 2020-05-05 | 山东朱氏药业集团有限公司 | Zwitterion hydrogel dressing and preparation and use methods thereof |
| CN109234259A (en) * | 2018-11-23 | 2019-01-18 | 南京工业大学 | The process for fixation of pyruvate oxidase |
| CN109234259B (en) * | 2018-11-23 | 2022-02-22 | 南京工业大学 | Method for immobilizing pyruvate oxidase |
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