CN101915797A - Method for preparing electrostatic spinning immobilized laccase electrode - Google Patents
Method for preparing electrostatic spinning immobilized laccase electrode Download PDFInfo
- Publication number
- CN101915797A CN101915797A CN 201010237624 CN201010237624A CN101915797A CN 101915797 A CN101915797 A CN 101915797A CN 201010237624 CN201010237624 CN 201010237624 CN 201010237624 A CN201010237624 A CN 201010237624A CN 101915797 A CN101915797 A CN 101915797A
- Authority
- CN
- China
- Prior art keywords
- electrode
- laccase
- solution
- preparation
- electrostatic spinning
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
Abstract
The invention belongs to the field of electrochemical detection of chlorophenol substances using an electrostatic spinning fiber immobilized enzyme electrode, and relates to preparation of a laccase electrode with response to chlorophenols and the detection of the chlorophenol substances by using the electrode. Particularly, environment-friendly macromolecular polymer polyvinyl alcohol is used as a raw material, and the laccase electrode is prepared by performing laccase immobilization by in-situ electrostatic spinning technology. The immobilized laccase electrode has response to 2,4-dichlorophenol, 4-chlorophenol, 2-dichlorophenol, 2,4,6-trichlorophenol and pentachlorophenol with low concentration; and the detection of the chlorophenol substances can be performed according to the position of reduction current peak of the response of the laccase electrode.
Description
Technical field
The present invention relates to a kind of preparation method of enzyme electrode, and this enzyme electrode is used for the Electrochemical Detection field that water pollutant detects.Be specifically related to a kind of method for making of the enzyme electrode that is used for detecting water pollutant and the detection that prepared enzyme electrode is applied to water low-level chlorinated aldehydes matter.
Background technology
The characteristics of the selectivity of immobilised enzymes set of sensors enzyme reaction, the long-time stability of immobilised enzymes, electrochemical analysis rapid sensitive cause people's attention just day by day in one, and many have the enzyme electrode of theoretical meaning and practical value constantly to be developed.It mainly is detection for aldehydes matter in environmental applications.Just there is the nineties scholar to use laccase and tyrosinase dual-enzyme system modified glassy carbon to be used for the continuous stream analysis of phenolic compound jointly.Subsequently, there is research report tyrosinase to be fixed in the 3-mercaptopropionic acid and can under continuous flow mode, measures 10 kinds of phenolic compounds simultaneously from the enzyme electrode for preparing on the assembled monolayer film by cross-linking method.Wang and Hasebe use eight kinds of crosslinking chemicals with the tyrosinase Covalent Immobilization in amidized carbon electrodes, the wherein sensitivity that demonstrates of glutaraldehyde cross-linking method, operational stability and storage stability, and the detection that this method is applied to catechol and 4-chlorophenol demonstrates low detectability and reuse.Jarosz-Wilkolazka etc. discover based on the biology sensor of the laccase modified electrode preparation that derives from C.unicolor rapid for the dynamic variation response of catechol concentration, can well be applied to detect under the continuous flow mode phenolic compound.Korkut etc. are being fixed in horseradish peroxidase by the electropolymerization process under the situation of not using crosslinking chemical on the electrode of carbon nano-tube/poly pyrroles nano meter biomaterial modification, studied the range of linearity, sensitivity and the detectability of biology sensor to 18 kinds of phenol derivatives, find that biology sensor all has low detectability to these phenol derivatives of being tested, and the response time fast (less than 2s).
At present, traditional enzyme immobilization method mainly contains: absorption method, covalent bond method, cross-linking method and investment.Absorption fixedly is the simplest method, is by physical force such as hydrogen bond, hydrophobic bond and π-electron affinities enzyme to be directly fixed on a kind of process for fixation on the insoluble carrier.The method has enzyme active center and is difficult for destroyed and enzyme higher structure advantage with low uncertainty, but the enzyme of this method load and carrier interaction force are weak, enzyme easily comes off.During covalent bond by electrode is carried out chemical modification, utilize again can carry out in the zymoprotein molecule combination-NH ,-OH ,-SH ,-form covalent bond between the reactive group on COOH isoreactivity group and the electrode surface to be connected.Being connected between fast, the good stability of the enzyme electrode response speed of this method preparation, enzyme and carrier is very firm, and be generally can be because of concentration of substrate not high or exist salt etc. former thereby come off easily, is beneficial to continuous use.But owing to adopted relatively fiercer reaction conditions, thereby can not obtain the immobilised enzymes higher than vigor.After investment is meant the monomer of polymkeric substance and enzyme solutions mixed, make monomer carry out polymerization, thereby enzyme is embedded in process for fixation in the polymkeric substance by the effect of polymerization accelerant (comprising crosslinking chemical).This method is inapplicable to macromolecule substrate, and storage stability and poor heat stability.Cross-linking method promptly utilize difunctional or poly functional reagent carrying out cross-linking reaction between the enzyme molecule or between enzyme molecule and carrier, prepare immobilised enzymes with covalent bond.This method is easy and simple to handle, but the enzyme recovery is not high.
Electrostatic spinning technique is that a kind of applying high voltage electricity flows charged Polymer Solution or melt or distortion in electrostatic field, then because solvent evaporation or melt cool off solidifies, finally produces the process of the uniform fiber of diameter tens nanometer to tens millimeter.The electrostatic spinning nano tunica fibrosa is considered to a kind of comparatively desirable enzyme immobilization carrier owing to having big specific surface area, high porosity and high absorption property.Up to now, two kinds of main methods are used to by electrostatic spinning enzyme and polymkeric substance be formed nanofiber.A kind of method is to be fixed on the surface of electro spinning nano fiber behind the enzyme.Another kind method is directly enzyme to be mixed with different polymer solutions, together carries out electrostatic spinning, i.e. related original position electrospinning among the present invention.The advantage that this method can make the protective enzyme molecule avoid the fibrous inside space of extreme condition restriction is not fully exerted, and lives thereby improve enzyme.Construct the detection that biology sensor is used for pollutant by the method immobilization laccase of original position electrostatic spinning and do not see bibliographical information as yet.Therefore, the preparation of the method by the original position electrostatic spinning ultrafine fiber that is fixed with enzyme will have very realistic meanings aspect the preparation of biology sensor.
Summary of the invention
Thereby the object of the present invention is to provide a kind of directly laccase is fixed in electrode surface by electrostatic spinning technique can be efficient, the method for chlorophenols material in the stable detection environment.Preparation method's mild condition of enzyme electrode provided by the present invention, simple, good stability is beneficial to quick arrangement especially, and uses the detection of the laccase electrode parachlorphenol class material of this method preparation to have sensitivity, stable, advantage accurately.
1. a first aspect of the present invention relates to a kind of preparation method of electrostatic spinning immobilized enzyme electrode, specifically comprises the following steps:
1) pre-service of electrode:
α-Al of particle diameter 0.05 μ m behind the thick porphyrize mill of emery paper, is used earlier again in the glass-carbon electrode surface
2O
3Powder polishes on sheet glass, and the first flush away surface contaminants in each polishing back moves in the ultrasonic water bath and cleans, each 2～3min, and triplicate is until cleaning up; Use ethanol, V at last
Nitric acid: V
WaterThe nitric acid and the water that are 1: 1 thoroughly wash, and obtain fresh electrode surface, and are placed on 0.2mol/L H
2SO
4In through cyclic voltammetry scan to stable;
2) preparation of material solution:
With molecular weight is that 100,000 granule of polyvinyl alcohol and segmented copolymer are dissolved in the ultrapure water, evenly mixes the back heated and stirred to clarification; Be dissolved in the fresh ultrapure water the 1g gold chloride is disposable, be made into 1% aqueous solution with the 100mL volumetric flask; Be dissolved in the fresh ultrapure water the 1g sodium citrate is disposable, be made into 1% aqueous solution with the 100mL volumetric flask; To massfraction is to add a certain amount of 1% citric acid three sodium solution in 0.1% the gold chloride with preparation nm of gold aqueous solution; With the pH value is that 4.4 phosphate buffer is a solvent, the laccase solution that compound concentration is certain;
3) the original position electrostatic spinning prepares immobilized laccase electrode:
In the aqueous solution of polyvinyl alcohol (PVA)/segmented copolymer, add certain amount of nano Jinsui River solution and fresh laccase solution, after stirring, this mixed solution is injected the 5mL glass syringe that has syringe needle, syringe is fixed on the syringe pump, ground connection links to each other with glass-carbon electrode to electrode and forms 14.4kV voltage, and syringe needle is 9cm to the distance setting of dash receiver, and control spinning flow velocity is 0.2mL/h, spinning time 5h promptly obtains described electrostatic spinning immobilized laccase electrode.
Above-mentioned steps 2) employed segmented copolymer is a kind of of P123, F108, F127 in.Wherein, the molecular formula of P123 is PEO20-PPO70-PEO20, and molecular weight is 5750 gram/moles; The molecular formula of F108 is PEO132-PPO50-PEO132, and molecular weight is 15500 gram/moles; The molecular formula of F127 is PEO106-PPO70-PEO106, and molecular weight is 14600 gram/moles; The three is the polyoxyethylene-poly-oxypropylene polyoxyethylene block polyether.
Preferred above-mentioned steps 2) alcoholysis degree of polyvinyl alcohol (PVA) is 98～99% in, and average degree of polymerization is 2400～2500, and its massfraction in aqueous solution is 6%.
Preferred above-mentioned steps 2) consumption of 1% gold chloride is 0.5mL in, and the consumption of 1% citric acid is 0.25～4.0mL, and the particle diameter of the nm of gold of preparation is 5～120nm, more preferably 25nm.
Among the present invention, employed laccase is that present technique field personnel are familiar with, its acquisition also is by conventional microbial fermentation, as taking from the secretion of white-rot fungi (T.gallica), pleurotus florida (Pleurotus florida), variegated rainbow conk microorganisms such as (Polystictusversicoloy).Laccase can also obtain by supplier.
2. another aspect of the present invention relates to the electrostatic spinning immobilized laccase electrode by above-mentioned preparation method's preparation.
3. of the present invention more on the one hand, relate to the purposes in the detection of above-mentioned electrostatic spinning immobilized laccase electrode chlorophenols material in water.
Wherein, described chlorophenols material is 2,4-two chlorophenols, 4-chlorophenol, 2-chlorophenol, 2,4,6-trichlorophenol and/or pentachloro-phenol.Its detection method is: with described immobilized laccase electrode is working electrode, with the saturated calomel electrode is contrast electrode, platinum electrode is for to construct three-electrode system to electrode, placing with the pH value is the certain density chlorophenol solution of 6.0 0.2mol/L sodium hydrogen phosphate-sodium dihydrogen phosphate buffer preparation, and reaction 3～5min carries out cyclic voltammetry scan.
The invention has the advantages that:
1. polyvinyl alcohol (PVA) of the present invention is a kind of Biodegradable material, is used for environmental contaminants improvement field and can introduce secondary pollution;
2. the mechanical property of polyvinyl alcohol (PVA) of the present invention its film after the electrostatic spinning film forming is good, and is thermally-stabilised good;
3. the present invention utilizes the original position electrostatic spinning technique that laccase is directly fixed on the glass-carbon electrode surface, can not well protect the enzyme molecule that is wrapped in fibrous inside to avoid the performance of the fibrous inside space advantage of extreme condition restriction thereby solved back immobilization;
4. prepare laccase electrode with electrospinning anchored in place laccase, method is simple, limited by environmental baseline, can be placed in multiple interface, and adaptability is strong;
5. characteristics such as the detection of the laccase electrode parachlorphenol class material of this preparation has in real time, response speed is fast, highly sensitive and cost is lower.
Description of drawings
Fig. 1 is the scanning electron microscope image of polyvinyl alcohol (PVA) electrospinning fibre immobilized laccase;
Fig. 2 is for using in the polyvinyl alcohol (PVA) electrospinning fibre immobilized laccase electrode detection water of the present invention 2, the cyclic voltammetry curve figure of 4-two chlorophenols, wherein, the horizontal ordinate representative is with respect to the current potential of saturated calomel electrode (SCE), unit is V, and on behalf of response current unit, ordinate be microampere (μ A);
Fig. 3 is for using the cyclic voltammetry curve figure of 4-chlorophenol in the polyvinyl alcohol (PVA) electrospinning fibre immobilized laccase electrode detection water of the present invention, wherein, the horizontal ordinate representative is with respect to the current potential of saturated calomel electrode (SCE), and unit is V, and on behalf of response current unit, ordinate be microampere (μ A).
Embodiment
Following embodiment is done more detailed description to the present invention, but described enforcement is not construed as limiting the invention.
Embodiment 1
1) α-Al of particle diameter 0.05 μ m behind the thick porphyrize mill of emery paper, is used earlier again in the glass-carbon electrode surface
2O
3Powder polishes on sheet glass, and the first flush away surface contaminants in each polishing back moves in the ultrasonic water bath and cleans, each 2～3min, and triplicate is until cleaning up.Use ethanol, V at last
Nitric acid: V
WaterThe nitric acid and the water that are 1: 1 thoroughly wash, and obtain fresh electrode surface, and are placed on 0.2mol/L H
2SO
4In through cyclic voltammetry scan to stable;
2) be that 100,000 granule of polyvinyl alcohol and segmented copolymer F108 are dissolved in the ultrapure water with molecular weight, evenly mix the back heated and stirred to clarification, wherein the massfraction of polyvinyl alcohol (PVA) is 6%, and the massfraction of segmented copolymer F108 is 0.3%;
3) be dissolved in the fresh ultrapure water the 1g gold chloride is disposable, be made into 1% aqueous solution with the 100mL volumetric flask; Be dissolved in the fresh ultrapure water the 1g sodium citrate is disposable, be made into 1% aqueous solution with the 100mL volumetric flask; To massfraction is to add 1% the citric acid three sodium solution of 0.5mL in 0.1% the gold chloride with preparation nm of gold aqueous solution;
4) be that 4.4 phosphate buffer is a solvent with the pH value, compound concentration is the laccase solution of 5mg/mL;
5) the laccase solution of the 5mg/mL that adding 400 μ L nm of gold aqueous solution and 400 μ L are fresh in the aqueous solution of 5mL polyvinyl alcohol (PVA)/segmented copolymer, after stirring, this mixed solution is injected the 5mL glass syringe that has syringe needle, syringe is fixed on the syringe pump, ground connection links to each other with glass-carbon electrode to electrode and forms 14.4kV voltage, and syringe needle is 9cm to the distance setting of dash receiver, and control spinning flow velocity is 0.2mL/h, spinning time 5h promptly obtains described electrostatic spinning immobilized enzyme electrode.
6) with this laccase electrode for preparing as working electrode, with the saturated calomel electrode is contrast electrode, platinum electrode is for to construct three-electrode system to electrode, electrolytic solution is that the concentration of the 0.2mol/L sodium hydrogen phosphate-sodium dihydrogen phosphate buffer preparation of pH value 6.0 is respectively 25 μ mol/L, 50 μ mol/L, 60 μ mol/L, 70 μ mol/L, 80 μ mol/L, 2 of 100 μ mol/L and 200 μ mol/L, in the 4-dichloro phenol solution, use CHI660D (Beijing China science popularization sky) electrochemical workstation and carry out cyclic voltammetry scan, experiment shows, this enzyme electrode has excellent performance, response time fast (50s), to 2, the detection range of linearity of 4-two chlorophenols: 1～200 μ mol/L.
Embodiment 2
4-chlorophenol solution with 80 μ mol/L replaces 2 among the embodiment 1,4-dichloro phenol solution, and other conditions are with embodiment 1, and experiment shows that this laccase electrode has good response to the 4-chlorophenol.
Embodiment 3
2-chlorophenol solution with 50 μ mol/L replaces 2 among the embodiment 1,4-dichloro phenol solution, and other conditions are with embodiment 1, and experiment shows that this laccase electrode has good response to the 2-chlorophenol.
Embodiment 4
With 2,4 of 50 μ mol/L, 6-trichlorophenol solution replaces 2 among the embodiment 1,4-dichloro phenol solution, and other conditions are with embodiment 1, and experiment shows that this laccase electrode is to 2,4, and the 6-trichlorophenol has good response.
Pentachlorophenol solution with 50 μ mol/L replaces 2 among the embodiment 1,4-dichloro phenol solution, and other conditions are with embodiment 1, and experiment shows that this laccase electrode has good response to pentachloro-phenol.
Claims (7)
1. the preparation method of electrostatic spinning immobilized enzyme electrode is characterized in that comprising the following steps:
1) pre-service of glass-carbon electrode:
α-Al of particle diameter 0.05 μ m behind the thick porphyrize mill of emery paper, is used earlier again in the glass-carbon electrode surface
2O
3Powder polishes on sheet glass, and the first flush away surface contaminants in each polishing back moves in the ultrasonic water bath and cleans, each 2～3min, and triplicate is until cleaning up; Use ethanol, V at last
Nitric acid: V
WaterThe nitric acid and the water that are 1: 1 thoroughly wash, and obtain fresh electrode surface, and are placed on 0.2mol/L H
2SO
4In through cyclic voltammetry scan to stable;
2) preparation of material solution:
With molecular weight is that 100,000 granule of polyvinyl alcohol and segmented copolymer are dissolved in the ultrapure water, evenly mixes the back heated and stirred to clarification; Be dissolved in the fresh ultrapure water the 1g gold chloride is disposable, be made into 1% aqueous solution with the 100mL volumetric flask; Be dissolved in the fresh ultrapure water the 1g sodium citrate is disposable, be made into 1% aqueous solution with the 100mL volumetric flask; To massfraction is to add a certain amount of 1% citric acid three sodium solution in O.1% the gold chloride with preparation nm of gold aqueous solution; With the pH value is that 4.4 phosphate buffer is a solvent, the laccase solution that compound concentration is certain;
3) the original position electrostatic spinning prepares immobilized laccase electrode:
In the aqueous solution of polyvinyl alcohol (PVA)/segmented copolymer, add certain amount of nano Jinsui River solution and fresh laccase solution, after stirring, this mixed solution is injected the 5mL glass syringe that has syringe needle, syringe is fixed on the syringe pump, ground connection links to each other with glass-carbon electrode to electrode and forms 14.4kV voltage, and syringe needle is 9cm to the distance setting of dash receiver, and control spinning flow velocity is 0.2mL/h, spinning time 5h promptly obtains described electrostatic spinning immobilized laccase electrode.
2. according to the method described in the claim 1, it is characterized in that: the segmented copolymer described in the preparation steps of material solution is a kind of of P123, F108, F127; Wherein, the molecular formula of P123 is PEO20-PPO70-PEO20, and molecular weight is 5750 gram/moles; The molecular formula of F108 is PEO132-PPO50-PEO132, and molecular weight is 15500 gram/moles; The molecular formula of F127 is PEO106-PPO70-PEO106, and molecular weight is 14600 gram/moles; The three is the polyoxyethylene-poly-oxypropylene polyoxyethylene block polyether.
3. according to the method described in the claim 1, it is characterized in that: the alcoholysis degree of the polyvinyl alcohol (PVA) described in the preparation steps of material solution is 98～99%, and average degree of polymerization is 2400～2500, and its massfraction in aqueous solution is 6%～8%.
4. according to the method described in the claim 1, it is characterized in that: in the nm of gold aqueous solution described in the preparation steps of material solution, the consumption of 1% gold chloride is 0.5mL, and the consumption of 1% citric acid is 0.25～4.0mL, and the particle size range of the nm of gold of preparation is 5～120nm.
5. electrostatic spinning immobilized laccase electrode as the arbitrary described preparation method preparation of claim 1～4.
6. the purposes in the detection of electrostatic spinning immobilized laccase electrode as claimed in claim 5 chlorophenols material in water.
7. according to the purposes described in the claim 6, it is characterized in that: the chlorophenols material is 2,4-two chlorophenols, 4-chlorophenol, 2-chlorophenol, 2,4,6-trichlorophenol and/or pentachloro-phenol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102376247A CN101915797B (en) | 2010-07-27 | 2010-07-27 | Method for preparing electrostatic spinning immobilized laccase electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102376247A CN101915797B (en) | 2010-07-27 | 2010-07-27 | Method for preparing electrostatic spinning immobilized laccase electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101915797A true CN101915797A (en) | 2010-12-15 |
| CN101915797B CN101915797B (en) | 2011-09-28 |
Family
ID=43323358
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010102376247A Expired - Fee Related CN101915797B (en) | 2010-07-27 | 2010-07-27 | Method for preparing electrostatic spinning immobilized laccase electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101915797B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102251020A (en) * | 2011-06-20 | 2011-11-23 | 湖南大学 | Colloidal gold probe for detecting absorption characteristics of laccase and preparation method thereof |
| CN102645474A (en) * | 2012-04-24 | 2012-08-22 | 哈尔滨工程大学 | Method for building three-dimensional enzyme electrode surface by using coaxial nanofibers |
| CN103499625A (en) * | 2013-09-13 | 2014-01-08 | 同济大学 | Preparation method and application of two-dimensional nano rare earth borate laccase sensor |
| CN106848330A (en) * | 2016-12-09 | 2017-06-13 | 新乡医学院 | A kind of preparation method of oxygen reduction catalyst nano composite material |
| CN107356655A (en) * | 2017-06-28 | 2017-11-17 | 东南大学 | A kind of preparation method and application of nanofiber modified electrode |
| CN107817284A (en) * | 2017-10-24 | 2018-03-20 | 中国地质大学（北京） | Electrospun for DBPs detection fixes imitative enzyme electrode and preparation method thereof |
| CN108872336A (en) * | 2018-06-22 | 2018-11-23 | 上海烟草集团有限责任公司 | A kind of detection method for pentachlorophenol content in paper wrapper |
| CN109612986A (en) * | 2018-12-04 | 2019-04-12 | 聚光科技(杭州)股份有限公司 | Test paper, manufacturing method and detection method |
| CN111020871A (en) * | 2019-12-31 | 2020-04-17 | 苏州卫生职业技术学院 | Nanofiber membrane for enzyme immobilization and preparation method thereof |
| CN111157592A (en) * | 2019-12-16 | 2020-05-15 | 河南牧业经济学院 | Electrostatic spinning glucose detection membrane and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107843638B (en) * | 2017-10-18 | 2021-03-16 | 广西壮族自治区农业科学院农产品质量安全与检测技术研究所 | Method for detecting pentachlorophenol by using aluminum-doped mesoporous foam material modified electrode |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001054667A1 (en) * | 2000-01-28 | 2001-08-02 | Smithkline Beecham Corporation | Electrospun pharmaceutical compositions |
| CN1737560A (en) * | 2005-09-02 | 2006-02-22 | 天津大学 | Static electricity spinning prepared fixed enzymic electrode and method thereof |
| CN101172164A (en) * | 2006-11-03 | 2008-05-07 | 中国科学院化学研究所 | Biopolymer nano tunica fibrosa material capable of being biological degraded and absorbed, preparing method and uses of the same |
| CN101285791A (en) * | 2008-05-23 | 2008-10-15 | 浙江大学 | Ampere type biosensor electrode and method for making same |
| CN101285792A (en) * | 2008-05-23 | 2008-10-15 | 浙江大学 | Mediator electrochemical enzyme electrode and method for making same |
| CN101290301A (en) * | 2008-05-23 | 2008-10-22 | 浙江大学 | Ampere enzyme electrode based on electrostatic spinning fiber membrane and method for making same |
| WO2008146169A2 (en) * | 2007-05-30 | 2008-12-04 | Philip Morris Products S.A. | Smoking articles enhanced to deliver additives incorporated within electroprocessed microcapsules and nanocapsules, and related methods |
| CN101407803A (en) * | 2008-07-01 | 2009-04-15 | 北京师范大学 | Polylactic acid electrospinning fibre immobilized laccase and preparation thereof |
-
2010
- 2010-07-27 CN CN2010102376247A patent/CN101915797B/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001054667A1 (en) * | 2000-01-28 | 2001-08-02 | Smithkline Beecham Corporation | Electrospun pharmaceutical compositions |
| CN1737560A (en) * | 2005-09-02 | 2006-02-22 | 天津大学 | Static electricity spinning prepared fixed enzymic electrode and method thereof |
| CN101172164A (en) * | 2006-11-03 | 2008-05-07 | 中国科学院化学研究所 | Biopolymer nano tunica fibrosa material capable of being biological degraded and absorbed, preparing method and uses of the same |
| WO2008146169A2 (en) * | 2007-05-30 | 2008-12-04 | Philip Morris Products S.A. | Smoking articles enhanced to deliver additives incorporated within electroprocessed microcapsules and nanocapsules, and related methods |
| CN101285791A (en) * | 2008-05-23 | 2008-10-15 | 浙江大学 | Ampere type biosensor electrode and method for making same |
| CN101285792A (en) * | 2008-05-23 | 2008-10-15 | 浙江大学 | Mediator electrochemical enzyme electrode and method for making same |
| CN101290301A (en) * | 2008-05-23 | 2008-10-22 | 浙江大学 | Ampere enzyme electrode based on electrostatic spinning fiber membrane and method for making same |
| CN101407803A (en) * | 2008-07-01 | 2009-04-15 | 北京师范大学 | Polylactic acid electrospinning fibre immobilized laccase and preparation thereof |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102251020A (en) * | 2011-06-20 | 2011-11-23 | 湖南大学 | Colloidal gold probe for detecting absorption characteristics of laccase and preparation method thereof |
| CN102645474A (en) * | 2012-04-24 | 2012-08-22 | 哈尔滨工程大学 | Method for building three-dimensional enzyme electrode surface by using coaxial nanofibers |
| CN102645474B (en) * | 2012-04-24 | 2013-10-30 | 哈尔滨工程大学 | Method for building three-dimensional enzyme electrode surface by using coaxial nanofibers |
| CN103499625A (en) * | 2013-09-13 | 2014-01-08 | 同济大学 | Preparation method and application of two-dimensional nano rare earth borate laccase sensor |
| CN103499625B (en) * | 2013-09-13 | 2015-07-29 | 同济大学 | The preparation method of two-dimensional nano rare earth borate laccase sensor and application thereof |
| CN106848330A (en) * | 2016-12-09 | 2017-06-13 | 新乡医学院 | A kind of preparation method of oxygen reduction catalyst nano composite material |
| CN107356655A (en) * | 2017-06-28 | 2017-11-17 | 东南大学 | A kind of preparation method and application of nanofiber modified electrode |
| CN107356655B (en) * | 2017-06-28 | 2019-06-14 | 东南大学 | A kind of preparation method and application of nanofiber modified electrode |
| CN107817284A (en) * | 2017-10-24 | 2018-03-20 | 中国地质大学（北京） | Electrospun for DBPs detection fixes imitative enzyme electrode and preparation method thereof |
| CN108872336A (en) * | 2018-06-22 | 2018-11-23 | 上海烟草集团有限责任公司 | A kind of detection method for pentachlorophenol content in paper wrapper |
| CN109612986A (en) * | 2018-12-04 | 2019-04-12 | 聚光科技(杭州)股份有限公司 | Test paper, manufacturing method and detection method |
| CN111157592A (en) * | 2019-12-16 | 2020-05-15 | 河南牧业经济学院 | Electrostatic spinning glucose detection membrane and preparation method thereof |
| CN111020871A (en) * | 2019-12-31 | 2020-04-17 | 苏州卫生职业技术学院 | Nanofiber membrane for enzyme immobilization and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101915797B (en) | 2011-09-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101915797B (en) | Method for preparing electrostatic spinning immobilized laccase electrode | |
| Wang et al. | Direct, selective and ultrasensitive electrochemical biosensing of methyl parathion in vegetables using Burkholderia cepacia lipase@ MOF nanofibers-based biosensor | |
| Deng et al. | Electrochemical determination of bisphenol A in plastic bottled drinking water and canned beverages using a molecularly imprinted chitosan–graphene composite film modified electrode | |
| Yu et al. | Mediator-free phenol sensor based on titania sol–gel encapsulation matrix for immobilization of tyrosinase by a vapor deposition method | |
| Andriukonis et al. | From microorganism-based amperometric biosensors towards microbial fuel cells | |
| CN101329296B (en) | Glucolase electrode based on magnetic carbon nano-tube and preparation method thereof | |
| CN102173378B (en) | Nanometer material with biosensing function and preparation method thereof | |
| CN101931079B (en) | Dehydrogenase electrode, and preparation method and application thereof | |
| CN102147389A (en) | Method for testing hydrogen peroxide in cell based on horseradish peroxidase-attapulgite nanometer composite material | |
| CN101349667B (en) | Electrochemical detection device of physiological active substance and special-purpose electrochemical sensor preparation method thereof | |
| Fusco et al. | Evaluation of novel Fmoc-tripeptide based hydrogels as immobilization supports for electrochemical biosensors | |
| CN102565174A (en) | Ionic liquid polyaniline modified electrode-electro chemical analysis system | |
| CN106442667A (en) | Method for detecting blood glucose by virtue of persimmon tannin@graphene@Pt-Pd non-enzymatic sensor | |
| CN101545886B (en) | Composite sensing membrane preparation method with nano gold evenly distributed in conducting polymer | |
| CN103756992A (en) | Chocolate microbacterium magnetic cell as well as preparation method and application thereof | |
| CN100339703C (en) | Biosensor electrode used for detecting aflatoxin and variegated aspergillin and its preparation method | |
| Li et al. | Hierarchically porous copolymer film as immobilization matrix for phenol biosensor with high sensitivity | |
| CN105223262A (en) | Based on the biology sensor and preparation method thereof of aptamer specific detection tetracycline | |
| CN101285792B (en) | Mediator electrochemical enzyme electrode and method for making same | |
| Chen et al. | Three-mediator enhanced collisions on an ultramicroelectrode for selective identification of single Saccharomyces cerevisiae | |
| CN102183560B (en) | Methods for preparing and using peroxidase electrode | |
| CN101906459B (en) | Method for testing toxicity of phenols in water by immobilizing cells with electrostatic spinning fibrous membrane | |
| CN101290301A (en) | Ampere enzyme electrode based on electrostatic spinning fiber membrane and method for making same | |
| CN103901088A (en) | Electrostatic spinning method for preparing nanofiber membrane biosensor | |
| CN102830147A (en) | Modified electrode and applications of modified electrode on detecting micro/trace nitro aromatic compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110928 Termination date: 20130727 |