CN101839883B - Preparation method of laminated film enzyme electrode - Google Patents
Preparation method of laminated film enzyme electrode Download PDFInfo
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- CN101839883B CN101839883B CN 200910080302 CN200910080302A CN101839883B CN 101839883 B CN101839883 B CN 101839883B CN 200910080302 CN200910080302 CN 200910080302 CN 200910080302 A CN200910080302 A CN 200910080302A CN 101839883 B CN101839883 B CN 101839883B
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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 attracts wide attention 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 very important research topic, wherein, the main problem of existence is the Direct electron transfer between effectively fixing of enzyme molecule and enzyme and the electrode.Fixing physics or the chemical method of usually adopting 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 relatively simple preparation process based on the static layer-by-layer (LbL) of organic template.When the substrate neutral, this method usually need to be with in the solution of substrate immersion with the polyelectrolyte of electric charge, and effects on surface carries out pre-service, thereby can assemble by electrostatic force absorption.But this method exists a large problem to need to solve: the acting force between polyelectrolyte and the substrate is more weak and stable poor.In long preparation process, often be 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 at the strong adsorption thin polymer film of solid substrate preparation.Thereby covalently bound at substrate surface by the transfer of the electronics between monomer and the conductive substrates, therefore electric grafting can be next step modification raising stability 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 electric 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, with the nanogold particle of negative charge with 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 then covalently bound nanogold particle with negative charge is fixed the enzyme molecule with positive electricity at last, and the method step is as follows,
(1) preparation is with the solution of the 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, then adding concentration is 0.05～0.2mmol/L sodium borohydride aqueous solution, 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 the solution with the nanogold particle of negative charge;
(2) adopt electric grafting method to gather N-mercapto ethyl acrylamide film in the basal electrode preparation: 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 prepared poly-N-mercapto ethyl acrylamide film at basal electrode;
(3) preparation of laminated film enzyme electrode: will place at the electrode that basal electrode has prepared poly-N-mercapto ethyl acrylamide film the solution with the nanogold particle of negative charge, soaked 2～12 hours, gold nano grain is by covalently bound at electrode surface with the sulfydryl effect, then, electrode is placed enzyme molecular solution with positive charge, described enzyme molecule is horseradish peroxidase or cromoci, soaked 5～12 hours, enzyme molecule Electrostatic Absorption is surperficial at gold grain, thereby is prepared into 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 clean 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 at chamois leather, uses first deionized water flush away surface contaminants after each polishing, moves into and uses successively ethanol and each ultrasonic cleaning 1～3min of deionized water in the ultrasonic device, uses N
2Basal electrode is dried up; The indium-tin oxide electrode cleaning step is used N for using successively each ultrasonic cleaning 5～10min of ethanol and deionized water
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 activity with the combination 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 good catalytic activity and the wider range of linearity.Technique 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 schematic 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 by the poly-N-mercapto ethyl acrylamide of glass-carbon electrode, electro-grafted films, form with the nanogold particle of negative charge with the horseradish peroxidase (HRP) of positive charge.
A kind of preparation method of laminated film enzyme electrode adopts electric grafting method to prepare poly-N-mercapto ethyl acrylamide, and then covalently bound nanogold particle with negative charge is fixed the horseradish peroxidase with positive electricity at last, and the method step is as follows,
(1) preparation is with 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, then adding concentration is the 0.1mmol/L sodium borohydride aqueous solution, 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 the solution with the nanogold particle of negative charge;
(2) adopt electric grafting method to gather N-mercapto ethyl acrylamide film in the glass-carbon electrode preparation: 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 at chamois leather, uses first deionized water flush away surface contaminants after each polishing, moves into and uses successively ethanol and each ultrasonic cleaning 2min of distilled water in the ultrasonic device, 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 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 prepared poly-N-mercapto ethyl acrylamide film at glass-carbon electrode;
(3) preparation of laminated film enzyme electrode: will place at the electrode that glass-carbon electrode has prepared poly-N-mercapto ethyl acrylamide film the solution with the nanogold particle of negative charge, soak 12h, nanogold particle is by covalently bound at electrode surface with the sulfydryl effect, then, electrode is placed horseradish peroxidase solution (pH=7) with positive charge, soak 12h, the horseradish peroxidase Electrostatic Absorption is surperficial at gold grain, thereby is prepared into laminated film enzyme electrode.Fig. 1 has represented the preparation process schematic 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 contrast electrode, and the organic/inorganic composite film enzyme electrode of assembling is as working electrode.The result shows, horseradish peroxidase shows good electro catalytic activity, and lower Michaelis constant (0.48mM) shows that horseradish peroxidase has kept good activity in the microenvironment that modified electrode provides, within the specific limits to H
2O
2Response have obvious linear relationship, and stable performance.
Embodiment 2
A kind of laminated film enzyme electrode is by the poly-N-mercapto ethyl acrylamide of glass-carbon electrode, electro-grafted films, form with the nanogold particle of negative charge with the cromoci of positive charge.
A kind of preparation method of laminated film enzyme electrode adopts electric grafting method to prepare poly-N-mercapto ethyl acrylamide, and then covalently bound nanogold particle with negative charge is fixed the cromoci with positive electricity at last, and the method step is as follows,
(1) preparation is with the solution of the 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, then adding concentration is the 0.05mmol/L sodium borohydride aqueous solution, 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 the solution with the nanogold particle of negative charge;
(2) adopt electric grafting method to gather N-mercapto ethyl acrylamide film in the glass-carbon electrode preparation: 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 at chamois leather, uses first deionized water flush away surface contaminants after each polishing, moves into and uses successively ethanol and each ultrasonic cleaning 1min of deionized water in the ultrasonic device, 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 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 prepared poly-N-mercapto ethyl acrylamide film at glass-carbon electrode;
(3) preparation of laminated film enzyme electrode: will place at the electrode that glass-carbon electrode has prepared poly-N-mercapto ethyl acrylamide film the solution with the nanogold particle of negative charge, soak 5h, gold nano grain is by covalently bound at electrode surface with the sulfydryl effect, then, electrode is placed cytochrome c solution (pH=7) with positive charge, soak 10h, the cromoci Electrostatic Absorption is surperficial at gold grain, thereby is prepared into laminated film enzyme electrode.
The result shows, cromoci shows good electro catalytic activity, and it has kept good activity in the microenvironment that modified electrode provides, within the specific limits to H
2O
2Response have obvious linear relationship, and stable performance.
Embodiment 3
A kind of laminated film enzyme electrode is by the poly-N-mercapto ethyl acrylamide of indium-tin oxide electrode, electro-grafted films, form with the nanogold particle of negative charge with the cromoci of positive charge.
A kind of preparation method of laminated film enzyme electrode adopts electric grafting method to prepare poly-N-mercapto ethyl acrylamide, and then covalently bound nanogold particle with negative charge is fixed the cromoci with positive electricity at last, and the method step is as follows,
(1) preparation is with 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, then adding concentration is the 0.1mmol/L sodium borohydride aqueous solution, 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 the solution with the nanogold particle of negative charge;
(2) adopt electric grafting method to gather N-mercapto ethyl acrylamide film in the indium-tin oxide electrode preparation: 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 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 prepared poly-N-mercapto ethyl acrylamide film at indium-tin oxide electrode;
(3) preparation of laminated film enzyme electrode: will place at the electrode that indium-tin oxide electrode has prepared poly-N-mercapto ethyl acrylamide film the solution with the nanogold particle of negative charge, soak 8h, nanogold particle is by covalently bound at electrode surface with the sulfydryl effect, then, electrode is placed cytochrome c solution (pH=7) with positive charge, soak 12h, the cromoci Electrostatic Absorption is surperficial at gold grain, thereby is prepared into laminated film enzyme electrode.
The result shows, horseradish peroxidase shows good electro catalytic activity, within the specific limits to H
2O
2Response have obvious linear relationship, and stable performance.
Embodiment 4
A kind of laminated film enzyme electrode is by the poly-N-mercapto ethyl acrylamide of indium-tin oxide electrode, electro-grafted films, form with nanogold particle and the horseradish peroxidase of negative charge.
A kind of preparation method of laminated film enzyme electrode adopts electric grafting method to prepare poly-N-mercapto ethyl acrylamide, covalently bound nanogold particle with negative charge then, and last fixing horseradish peroxidase, the method step is as follows,
(1) preparation is with 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, then adding concentration is the 0.1mmol/L sodium borohydride aqueous solution, 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 the solution with the nanogold particle of negative charge;
(2) adopt electric grafting method to gather N-mercapto ethyl acrylamide film in the indium-tin oxide electrode preparation: 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 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 prepared poly-N-mercapto ethyl acrylamide film at indium-tin oxide electrode;
(3) preparation of laminated film enzyme electrode: will place at the electrode that indium-tin oxide electrode has prepared poly-N-mercapto ethyl acrylamide film the solution with the nanogold particle of negative charge, soak 11h, nanogold particle is by covalently bound at electrode surface with the sulfydryl effect, then, electrode is placed horseradish peroxidase solution (pH=7) with positive charge, soak 13h, the horseradish peroxidase Electrostatic Absorption is surperficial at gold grain, thereby is prepared into laminated film enzyme electrode.
The result shows, horseradish peroxidase shows good electro catalytic activity, and it has kept good activity in the microenvironment that modified electrode provides, within the specific limits to H
2O
2Response have obvious linear relationship, and stable performance.
Claims (4)
1. 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 then covalently bound nanogold particle with negative charge is fixed the enzyme molecule with positive electricity at last, and the method step is as follows,
(1) preparation is with the solution of the 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, then adding concentration is 0.05～0.2mmol/L sodium borohydride aqueous solution, 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 the solution with the nanogold particle of negative charge;
(2) adopt electric grafting method to gather N-mercapto ethyl acrylamide film in the basal electrode preparation: 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 0V 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 prepared poly-N-mercapto ethyl acrylamide film at basal electrode;
(3) preparation of laminated film enzyme electrode: will place at the electrode that basal electrode has prepared poly-N-mercapto ethyl acrylamide film the solution with the nanogold particle of negative charge, soaked 2～12 hours, nanogold particle is by covalently bound at electrode surface with the sulfydryl effect, then, electrode is placed enzyme molecular solution with positive charge, described enzyme molecule is horseradish peroxidase or cromoci, soaked 5～12 hours, enzyme molecule Electrostatic Absorption is surperficial at gold grain, thereby is prepared into laminated film enzyme electrode.
2. the preparation method of laminated film enzyme electrode according to claim 1 is characterized in that, described basal electrode is indium-tin oxide electrode, glass-carbon electrode or pyrolytic graphite electrode.
3. the preparation method of laminated film enzyme electrode according to claim 2, it is characterized in that, in the described basal electrode, glass-carbon electrode or pyrolytic graphite electrode clean 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 at chamois leather, uses first deionized water flush away surface contaminants after each polishing, moves into and uses successively ethanol and each ultrasonic cleaning 1～3min of deionized water in the ultrasonic device, uses N
2Basal electrode is dried up; The indium-tin oxide electrode cleaning step is used N for using successively each ultrasonic cleaning 5～10min of ethanol and deionized water
2Indium-tin oxide electrode is dried up.
4. the preparation method of laminated film enzyme electrode according to claim 1, 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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| 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 |
| 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 |
| CN109234259B (en) * | 2018-11-23 | 2022-02-22 | 南京工业大学 | Method for immobilizing 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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| 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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| Attachment of Gold Nanoparticles to Glassy Carbon Electrodes via a Mercaptobenzene Film;Jennifer A. Harnisch等;《J. Am. Chem. Soc.》;20010525;第123卷(第24期);第5829-5830页 * |
| C.Jérome等.Preparation of reactive surfaces by electrografting.《CHEM.COMMUN.》.2003,第2500-2501页. |
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| Marie Pellissier等.Improved stability of redox enzyme layers on glassy carbon electrodes via covalent grafting.《Electrochemistry Communications》.2008,(第10期),第835-838页. |
| Preparation of reactive surfaces by electrografting;C.Jérome等;《CHEM.COMMUN.》;20030826;第2500-2501页 * |
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