CN102645469A - Preparation method of laccase/multihole nanometer titanium dioxide modified electrode - Google Patents
Preparation method of laccase/multihole nanometer titanium dioxide modified electrode Download PDFInfo
- Publication number
- CN102645469A CN102645469A CN201110041863XA CN201110041863A CN102645469A CN 102645469 A CN102645469 A CN 102645469A CN 201110041863X A CN201110041863X A CN 201110041863XA CN 201110041863 A CN201110041863 A CN 201110041863A CN 102645469 A CN102645469 A CN 102645469A
- Authority
- CN
- China
- Prior art keywords
- laccase
- porous nano
- preparation
- titanium dioxide
- electrode
- 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
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
- Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
Abstract
The invention relates to a preparation method of a laccase/multihole nanometer titanium dioxide modified electrode. The preparation method comprises the steps of material preparation, preparation for combine use of hydrothermal method and calcination method of a multihole nanometer titanium dioxide carrier, adsorption and immobilization of laccase on the carrier and electrode modification. Immobilized laccase is uniformly scattered in Nafion dilute solution so as to modify a glassy carbon electrode which is used as a work electrode, so that a three-electrode system is established, and the three-electrode system is connected with an electrochemistry work station so as to detect the electrochemistry response of the three-electrode system on water pollutant hydroquinone through cyclic voltammetry. Compared with the prior art, the method disclosed by the invention has the advantages that the cost is low, the preparation is simple, the enzyme activity of the immobilized laccase is high, the sensibility is high, and the like.
Description
Technical field
The present invention relates to field of biosensors, especially relate to a kind of preparation method with laccase/porous nano titania modified electrode.
Background technology
Aldehydes matter exists in environment widely, as a kind of noxious material, human beings'health has been caused great harm, so the detection of aldehydes matter just becomes problem demanding prompt solution, also environmental monitoring is had great significance simultaneously.P-dihydroxy-benzene is widely used in industrial circle; It is one of phenolic comp ' ds pollution of the very strong and degraded that is difficult to of a kind of toxicity; Existing p-dihydroxy-benzene detection method mainly adopts chromatography, has analytical instrument costliness, complicated operation, the in time defective of on-line monitoring.Biology sensor is meant with immobilized biological component (as: enzyme, antigen, antibody, hormone etc.) or biosome itself (like cell, organelle, tissue etc.) as molecular recognition elements, test analyte to be had the analytical instrument of high selectivity.Biology sensor is one and interpenetrates the new subject of growing up by multiple subjects such as biology, chemistry, physics, medical science, electronics, material technologies.Enzyme electrode is a first generation biology sensor; It is with the electrochemica biological sensor of enzyme as the molecular recognition device; The energy converting system of forming by an immobilised enzymes sensitive membrane and married with it electrode; It combines immobilised enzymes and electrode, thereby has unique advantage: the advantage of (1) its existing insoluble enzyme system has the high sensitivity of electro-chemical systems again; (2) because the exclusive reaction property of enzyme makes it have very high selectivity; Characteristics such as (3) enzyme electrode is safe and reliable, highly sensitive, analysis speed fast, operation is simple and easy, instrument and equipment simple and be easy to carry.The main absorption method of the method for immobilised enzymes, covalent bond method and crosslinked combined techniques, wherein absorption method possesses skills simply, and process conditions are gentle, but the characteristics that alternative carrier is various and the carrier activation cycle is utilized again.At present, enzyme electrode successfully is applied to fields such as medical science, national defence, environment, food industry and agricultural, becomes a kind of strong analysis tool.
Summary of the invention
The object of the invention is exactly to provide a kind of technology simple, with low cost, easy to detect, portable preparation method with laccase/porous nano titania modified electrode for the defective that overcomes above-mentioned prior art existence.
The object of the invention can be realized through following technical scheme:
A kind of preparation method with laccase/porous nano titania modified electrode is characterized in that this method may further comprise the steps:
(1) adopt hydro-thermal method to combine preparation porous nano titanium dioxide microballoon sphere carrier with calcination method;
(2) the porous nano titanium dioxide microballoon sphere carrier that step (1) is prepared mixes the back in vibration tank adsorption of immobilization with rare laccase solution, obtain laccase/porous nano titanium dioxide immobilized enzyme;
(3) laccase that step (2) is prepared/porous nano titanium dioxide immobilized enzyme; After evenly spreading to multipolymer (Nafion) lean solution of tetrafluoroethene and perfluor-2-(sulfonic acid ethoxy) propyl vinyl ether; The mixed solution that obtains is evenly dropped on the glass-carbon electrode, and air dry gets final product at normal temperatures then.
Hydro-thermal method described in the step (1) may further comprise the steps: in the WS of cyclopentadienyl titanium dichloride, drip ethylenediamine, the control temperature of reaction is 100-150 ℃, and the reaction time is 5-8h, and the first sample that obtains is used deionized water, each centrifuge washing of absolute ethyl alcohol three times successively.
The concentration of the WS of described cyclopentadienyl titanium dichloride is 1-3mg/mL, and the volume ratio of the ethylenediamine of dropping and the WS of cyclopentadienyl titanium dichloride is (0.01-0.015): 1.
Calcination method described in the step (1) may further comprise the steps: adopt control to heat up; To place tubular furnace through the synthetic product that obtains of hydro-thermal method; The control heating rate is 3-4 ℃/s, and calcining heat is 400 ℃, and calcination time is 2h; Controlling then warm speed is that 3-4 ℃/s cools the temperature to room temperature, promptly obtains porous nano titanium dioxide microballoon sphere carrier.
The concentration of the rare laccase solution described in the step (2) is 0.01g/ml, in rare laccase solution of every milliliter, contains porous nano titanium dioxide microballoon sphere carrier 4mg.
The temperature of the adsorption of immobilization described in the step (2) is 4 ℃, and adsorption time is 12h, clean with deionized water is centrifugal after the immobilization, and dry at normal temperatures.
The concentration of multipolymer (Nafion) lean solution of the tetrafluoroethene described in the step (3) and perfluor-2-(sulfonic acid ethoxy) propyl vinyl ether is 0.05wt%; The content of controlling laccase in every milliliter of Nafion lean solution/porous nano titanium dioxide immobilized enzyme is 1mg; The control mixing temperature is 6 ℃, ultrasonic mixing 6min.
Glass-carbon electrode described in the step (3) uses particle diameter respectively on polishing cloth be the Al of 0.3 μ m and 0.05 μ m
2O
3The powder polishing, dry under infrared lamp behind each ultrasonic cleaning 5min in red fuming nitric acid (RFNA), distilled water and absolute ethyl alcohol successively again.
The laccase that utilization prepares/porous nano titania modified electrode is set up three electrode work systems, adopts sodium hydrogen phosphate-citric acid to detect p-dihydroxy-benzene electrochemical response situation in the water body respectively for liquid of the blank end.
Described three-electrode system comprises working electrode laccase/porous nano titania modified electrode; To electrode Pt electrode, contrast electrode Ag/NaCl electrode, the sodium hydrogen phosphate of employing-citric acid solution pH is 5.6; Concentration is 0.1mol/L, and the concentration of p-dihydroxy-benzene is 0.05mol/L.
Detect p-dihydroxy-benzene electrochemical response situation and measure through the response of cyclic voltammetry, the scope of scanning voltage is-1.4V～1.4V that sweep velocity is 0.05mv/s.
Compared with prior art, the present invention has the following advantages:
(1) the application is based on a kind of preparation method of laccase/porous nano titania modified electrode; With low cost, preparation is simple; Can more attachment site be provided for laccase by means of the porous nanometer material higher specific surface area, carry enzyme amount height, and owing to only adopt absorption method to fix; Enzyme loss of activity in immobilization process is little, and laccase electrode is active strong;
(2) the application's laccase/porous nano titania modified electrode has stronger electronic conduction ability, for the water pollutant p-dihydroxy-benzene tangible electrochemical response is arranged, and on the catechol pollutant detects, great application potential is arranged.
Description of drawings
Fig. 1 is the SEM photo of porous nano titanium dioxide microballoon sphere carrier;
Fig. 2 is a porous nano titanium dioxide microballoon sphere carrier XRD figure;
Fig. 3 is the fourier infrared figure of pure laccase, porous nano titanium dioxide microballoon sphere carrier and laccase/porous nano titanium dioxide immobilized enzyme;
Fig. 4 is the cyclic voltammetry curve of naked glass-carbon electrode to water body phenolic comp ' ds pollution p-dihydroxy-benzene;
Fig. 5 is the cyclic voltammetry curve of porous nano titanium dioxide microballoon sphere modified electrode to water body phenolic comp ' ds pollution p-dihydroxy-benzene;
Fig. 6 is the cyclic voltammetry curve of laccase/porous nano titania modified electrode to water body phenolic comp ' ds pollution p-dihydroxy-benzene.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment the present invention is elaborated.
Embodiment 1
The preparation method of a kind of laccase/porous nano titania modified electrode, this method may further comprise the steps:
The preparation of porous nano titanium dioxide microballoon sphere carrier
(1) hydrothermal synthesis method preparation, 20mg Ti (CP)
2Cl
2Be scattered in the 10ml deionized water in agitated reactor, and drip 2～3 ethylenediamines.Hydro-thermal reaction 6h under 120 ℃ of conditions, the cooling room temperature is with water, each centrifuge washing of absolute ethyl alcohol three times;
(2) step (1) gained sample is obtained after calcining 2h under 400 ℃ of conditions through tubular furnace, control heats up, rate of temperature fall is 3～4 ℃/s, promptly gets porous nano titanium dioxide microballoon sphere carrier.Prepared porous nano titanium dioxide microballoon sphere carrier S EM figure and XRD figure are respectively like Fig. 1, shown in Figure 2.
Embodiment 2
The preparation method of a kind of laccase/porous nano titania modified electrode, this method may further comprise the steps:
The preparation of laccase/porous nano titanium dioxide immobilized enzyme
(1) take by weighing the 20mg carrier and mix with rare laccase solution of 5ml, (about 6 ℃) ultrasonic 10min under the room temperature, after put into down adsorption of immobilization 12 hours of vibration tank normal temperature (about 4 ℃).
(2) with deionized water prepared immobilised enzymes 6 times in the cleaning step (1) repeatedly, normal temperature is down to drying, and seals with discolour silica gel and to be stored under 4 ℃ of temperature conditions.Pure laccase, porous nano titanium dioxide microballoon sphere carrier and laccase/porous nano titanium dioxide immobilized enzyme fourier infrared figure comparison diagram is as shown in Figure 3; Wherein a is a porous nano titanium dioxide microballoon sphere carrier; B is laccase/porous nano titanium dioxide immobilized enzyme, and c is pure laccase.
Embodiment 3
The preparation method of a kind of laccase/porous nano titania modified electrode, this method may further comprise the steps:
The preparation of laccase/porous nano titania modified electrode
(1) laccase/porous nano titanium dioxide immobilized enzyme that takes by weighing 1mg is dissolved in the tetrafluoroethene of 5ml 0.05wt% and multipolymer (Nafion) solution of perfluor-2-(sulfonic acid ethoxy) propyl vinyl ether, and (about 6 ℃) ultrasonic 3min mixes it under the room temperature;
(2) glass-carbon electrode being used particle diameter respectively on polishing cloth is 0.3 μ m and 0.05 μ m Al
2O
3The powder polishing, and, get the homodisperse laccase of 10 μ l/porous nano TiO successively with dry down behind the difference ultrasonic cleaning 5min in red fuming nitric acid (RFNA), distilled water and the absolute ethyl alcohol in infrared lamp
2/ Nafion mixed liquor drops on the clean glass-carbon electrode, and air dry under the normal temperature promptly gets laccase/porous nano TiO
2Modified electrode.
Embodiment 4
Laccase/porous nano titania modified electrode may further comprise the steps the electrochemical response of water body phenolic comp ' ds pollution p-dihydroxy-benzene:
(1) modified electrode is to the mensuration of the cyclic voltammetry electrochemical response of water body phenolic comp ' ds pollution p-dihydroxy-benzene; Adopt three-electrode system (modified electrode; The Pt electrode; The Ag/NaCl electrode) detects, earlier with modified electrode scan round to baseline stability state in liquid of the blank end of 0.1mol/l sodium hydrogen phosphate-citric acid (PH=5.6);
(2) in liquid of the blank end, add certain density p-dihydroxy-benzene solution, the whole solubility that makes p-dihydroxy-benzene is 1 * 10
-5, it is 0.05mv/s that sweep velocity is set, the scanning voltage scope is-1.4V～1.4V that the employing cyclic voltammetry is noted empirical curve, and background correction.Naked glass-carbon electrode, porous nano titanium dioxide microballoon sphere modified electrode and laccase/porous nano titania modified electrode to the cyclic voltammetry curve of water body phenolic comp ' ds pollution p-dihydroxy-benzene shown in Fig. 4～6.
Embodiment 5
A kind of preparation method with laccase/porous nano titania modified electrode may further comprise the steps:
(1) adopt hydro-thermal method to combine preparation porous nano titanium dioxide microballoon sphere carrier with calcination method; Hydro-thermal method may further comprise the steps: in concentration is the WS of cyclopentadienyl titanium dichloride of 1mg/mL, drip ethylenediamine; The volume ratio of the ethylenediamine that drips and the WS of cyclopentadienyl titanium dichloride is 0.01: 1; The control temperature of reaction is 100 ℃, and the reaction time is 8h, and the first sample that obtains is used deionized water, each centrifuge washing of absolute ethyl alcohol three times successively; Calcination method may further comprise the steps: adopt control to heat up; To place tubular furnace through the synthetic product that obtains of hydro-thermal method; The control heating rate is 3 ℃/s, and calcining heat is 400 ℃, and calcination time is 2h; Controlling then warm speed is that 3 ℃/s cools the temperature to room temperature, promptly obtains porous nano titanium dioxide microballoon sphere carrier;
(2) the porous nano titanium dioxide microballoon sphere carrier that step (1) is prepared and concentration are that rare laccase solution of 0.01g/mL mixes the back in vibration tank adsorption of immobilization; In rare laccase solution of every milliliter, contain porous nano titanium dioxide microballoon sphere carrier 4mg; The control temperature is 4 ℃; Adsorption time is 12h, clean with deionized water is centrifugal after the immobilization, and drying obtains laccase/porous nano titanium dioxide immobilized enzyme at normal temperatures;
(3) laccase that step (2) is prepared/porous nano titanium dioxide immobilized enzyme; Evenly spreading to concentration is the Nafion lean solution of 0.05wt%; The content of controlling laccase in every milliliter of Nafion lean solution/porous nano titanium dioxide immobilized enzyme is 1mg, and the control mixing temperature is 6 ℃, ultrasonic mixing 6min; The mixed solution that obtains is evenly dropped on the glass-carbon electrode, and this glass-carbon electrode uses particle diameter respectively on polishing cloth be the Al of 0.3 μ m and 0.05 μ m
2O
3The powder polishing, dry under infrared lamp behind each ultrasonic cleaning 5min in red fuming nitric acid (RFNA), distilled water and absolute ethyl alcohol successively again, air dry gets final product at normal temperatures then.
The laccase that utilization prepares/porous nano titania modified electrode is set up three electrode work systems, comprises working electrode laccase/porous nano titania modified electrode, to electrode Pt electrode; Contrast electrode Ag/NaCl electrode; Adopt sodium hydrogen phosphate-citric acid to detect p-dihydroxy-benzene electrochemical response situation in the water body respectively for liquid of the blank end, the sodium hydrogen phosphate of employing-citric acid solution pH is 5.6, and concentration is 0.1mol/L; The concentration of p-dihydroxy-benzene is 0.05mol/L; Detect p-dihydroxy-benzene electrochemical response situation and measure through the response of cyclic voltammetry, the scope of scanning voltage is-1.4V～1.4V that sweep velocity is 0.05mv/s.
Embodiment 6
A kind of preparation method with laccase/porous nano titania modified electrode may further comprise the steps:
(1) adopt hydro-thermal method to combine preparation porous nano titanium dioxide microballoon sphere carrier with calcination method; Hydro-thermal method may further comprise the steps: in concentration is the WS of cyclopentadienyl titanium dichloride of 3mg/mL, drip ethylenediamine; The volume ratio of the ethylenediamine that drips and the WS of cyclopentadienyl titanium dichloride is 0.015: 1; The control temperature of reaction is 150 ℃, and the reaction time is 5h, and the first sample that obtains is used deionized water, each centrifuge washing of absolute ethyl alcohol three times successively; Calcination method may further comprise the steps: adopt control to heat up; To place tubular furnace through the synthetic product that obtains of hydro-thermal method; The control heating rate is 4 ℃/s, and calcining heat is 400 ℃, and calcination time is 2h; Controlling then warm speed is that 4 ℃/s cools the temperature to room temperature, promptly obtains porous nano titanium dioxide microballoon sphere carrier;
(2) the porous nano titanium dioxide microballoon sphere carrier that step (1) is prepared and concentration are that rare laccase solution of 0.01g/mL mixes the back in vibration tank adsorption of immobilization; In rare laccase solution of every milliliter, contain porous nano titanium dioxide microballoon sphere carrier 4mg; The control temperature is 4 ℃; Adsorption time is 12h, clean with deionized water is centrifugal after the immobilization, and drying obtains laccase/porous nano titanium dioxide immobilized enzyme at normal temperatures;
(3) laccase that step (2) is prepared/porous nano titanium dioxide immobilized enzyme; Evenly spreading to concentration is the Nafion lean solution of 0.05wt%; The content of controlling laccase in every milliliter of Nafion lean solution/porous nano titanium dioxide immobilized enzyme is 1mg, and the control mixing temperature is 6 ℃, ultrasonic mixing 6min; The mixed solution that obtains is evenly dropped on the glass-carbon electrode, and this glass-carbon electrode uses particle diameter respectively on polishing cloth be the A1 of 0.3 μ m and 0.05 μ m
2O
3The powder polishing, dry under infrared lamp behind each ultrasonic cleaning 5min in red fuming nitric acid (RFNA), distilled water and absolute ethyl alcohol successively again, air dry gets final product at normal temperatures then.
The laccase that utilization prepares/porous nano titania modified electrode is set up three electrode work systems, comprises working electrode laccase/porous nano titania modified electrode, to electrode Pt electrode; Contrast electrode Ag/NaCl electrode; Adopt sodium hydrogen phosphate-citric acid to detect p-dihydroxy-benzene electrochemical response situation in the water body respectively for liquid of the blank end, the sodium hydrogen phosphate of employing-citric acid solution pH is 5.6, and concentration is 0.1mol/L; The concentration of p-dihydroxy-benzene is 0.05mol/L; Detect p-dihydroxy-benzene electrochemical response situation and measure through the response of cyclic voltammetry, the scope of scanning voltage is-1.4V～1.4V that sweep velocity is 0.05mv/s.
Claims (8)
1. preparation method with laccase/porous nano titania modified electrode is characterized in that this method may further comprise the steps:
(1) adopt hydro-thermal method to combine preparation porous nano titanium dioxide microballoon sphere carrier with calcination method;
(2) the porous nano titanium dioxide microballoon sphere carrier that step (1) is prepared mixes the back in vibration tank adsorption of immobilization with rare laccase solution, obtain laccase/porous nano titanium dioxide immobilized enzyme;
(3) laccase that step (2) is prepared/porous nano titanium dioxide immobilized enzyme; After evenly spreading to the lean solution of multipolymer (Nafion) of tetrafluoroethene and perfluor-2-(sulfonic acid ethoxy) propyl vinyl ether; The mixed solution that obtains is evenly dropped on the glass-carbon electrode, and air dry gets final product at normal temperatures then.
2. a kind of preparation method according to claim 1 with laccase/porous nano titania modified electrode; It is characterized in that; Hydro-thermal method described in the step (1) may further comprise the steps: in the WS of cyclopentadienyl titanium dichloride, drip ethylenediamine; The control temperature of reaction is 100-150 ℃, and the reaction time is 5-8h, and the first sample that obtains is used deionized water, each centrifuge washing of absolute ethyl alcohol three times successively.
3. a kind of preparation method according to claim 2 with laccase/porous nano titania modified electrode; It is characterized in that; The concentration of the WS of described cyclopentadienyl titanium dichloride is 1-3mg/mL, and the volume ratio of the ethylenediamine of dropping and the WS of cyclopentadienyl titanium dichloride is (0.01-0.015): 1.
4. a kind of preparation method with laccase/porous nano titania modified electrode according to claim 1 is characterized in that the calcination method described in the step (1) may further comprise the steps: adopt control to heat up; To place tubular furnace through the synthetic product that obtains of hydro-thermal method; The control heating rate is 3-4 ℃/s, and calcining heat is 400 ℃, and calcination time is 2h; Controlling then warm speed is that 3-4 ℃/s cools the temperature to room temperature, promptly obtains porous nano titanium dioxide microballoon sphere carrier.
5. a kind of preparation method according to claim 1 with laccase/porous nano titania modified electrode; It is characterized in that; The concentration of the rare laccase solution described in the step (2) is 0.01g/mL, in rare laccase solution of every milliliter, contains porous nano titanium dioxide microballoon sphere carrier 4mg.
6. a kind of preparation method according to claim 1 with laccase/porous nano titania modified electrode; It is characterized in that the temperature of the adsorption of immobilization described in the step (2) is 4 ℃, adsorption time is 12h; Clean with deionized water is centrifugal after the immobilization, and dry at normal temperatures.
7. a kind of preparation method according to claim 1 with laccase/porous nano titania modified electrode; It is characterized in that; The concentration of multipolymer (Nafion) lean solution of the tetrafluoroethene described in the step (3) and perfluor-2-(sulfonic acid ethoxy) propyl vinyl ether is 0.05wt%; The content of controlling laccase in every milliliter of Nafion lean solution/porous nano titanium dioxide immobilized enzyme is 1mg, and the control mixing temperature is 6 ℃, ultrasonic mixing 6min.
8. a kind of preparation method with laccase/porous nano titania modified electrode according to claim 1 is characterized in that the glass-carbon electrode described in the step (3) uses particle diameter respectively on polishing cloth be the Al of 0.3 μ m and 0.05 μ m
2O
3The powder polishing, dry under infrared lamp behind each ultrasonic cleaning 5min in red fuming nitric acid (RFNA), distilled water and absolute ethyl alcohol successively again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110041863.XA CN102645469B (en) | 2011-02-21 | 2011-02-21 | Preparation method of laccase/multihole nanometer titanium dioxide modified electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110041863.XA CN102645469B (en) | 2011-02-21 | 2011-02-21 | Preparation method of laccase/multihole nanometer titanium dioxide modified electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102645469A true CN102645469A (en) | 2012-08-22 |
| CN102645469B CN102645469B (en) | 2014-07-16 |
Family
ID=46658424
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110041863.XA Expired - Fee Related CN102645469B (en) | 2011-02-21 | 2011-02-21 | Preparation method of laccase/multihole nanometer titanium dioxide modified electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102645469B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN117752558A (en) * | 2023-12-22 | 2024-03-26 | 广州亿彩生物科技有限公司 | Moisturizing anti-inflammatory magnetic lip balm and preparation process thereof |
| CN117752558B (en) * | 2023-12-22 | 2024-06-07 | 广州亿彩生物科技有限公司 | Moisturizing anti-inflammatory magnetic lip balm and preparation process thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101393160A (en) * | 2008-10-29 | 2009-03-25 | 北京化工大学 | Biological functional multilayer film modified electrode and method for making same |
| CN101456569A (en) * | 2008-07-22 | 2009-06-17 | 绍兴纳诺气凝胶新材料研发中心有限公司 | Method for quick-speed preparing aerogel by hydro-thermal synthesis at low cost |
| CN101603940A (en) * | 2009-07-16 | 2009-12-16 | 南京工业大学 | MWCNTs-TiO 2The preparation method of the enzyme electrode of/Nafion complex media |
| CN101813660A (en) * | 2010-04-02 | 2010-08-25 | 北京工业大学 | Method for preparing fixed enzyme electrode by using TiO2 as carrier |
-
2011
- 2011-02-21 CN CN201110041863.XA patent/CN102645469B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101456569A (en) * | 2008-07-22 | 2009-06-17 | 绍兴纳诺气凝胶新材料研发中心有限公司 | Method for quick-speed preparing aerogel by hydro-thermal synthesis at low cost |
| CN101393160A (en) * | 2008-10-29 | 2009-03-25 | 北京化工大学 | Biological functional multilayer film modified electrode and method for making same |
| CN101603940A (en) * | 2009-07-16 | 2009-12-16 | 南京工业大学 | MWCNTs-TiO 2The preparation method of the enzyme electrode of/Nafion complex media |
| CN101813660A (en) * | 2010-04-02 | 2010-08-25 | 北京工业大学 | Method for preparing fixed enzyme electrode by using TiO2 as carrier |
Non-Patent Citations (1)
| Title |
|---|
| HAN NIM CHOI,ET AL.: "Amperometric glucose biosensor based on sol-gel-derived metal oxide/Nafion composite films", 《ANALYTICA CHIMICA ACTA》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN117752558A (en) * | 2023-12-22 | 2024-03-26 | 广州亿彩生物科技有限公司 | Moisturizing anti-inflammatory magnetic lip balm and preparation process thereof |
| CN117752558B (en) * | 2023-12-22 | 2024-06-07 | 广州亿彩生物科技有限公司 | Moisturizing anti-inflammatory magnetic lip balm and preparation process thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102645469B (en) | 2014-07-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102928488B (en) | Method for detecting phenol compounds in water body environment through enzyme electrochemical biosensor | |
| CN110057882B (en) | Electrochemical biosensor based on two-dimensional titanium-carbon compound and application thereof | |
| CN104118904B (en) | The preparation method of three-dimensional hollow multilevel hierarchy stannic oxide gas sensitive and application thereof | |
| CN106324065B (en) | A kind of preparation and organophosphorus insecticide detection of the photic electrochemical sensor of chemiluminescence | |
| CN103940867B (en) | A kind of preparation method of the photoelectricity aptamer sensor for detecting 17 beta estradiols | |
| CN107727858B (en) | A kind of preparation method and application based on Rh@Pt nanodendrites composite material immunosensor | |
| CN106770544A (en) | Ni MOF ultrathin nanometers band, synthetic method and its application | |
| CN107202828B (en) | A kind of estradiol optical electro-chemistry sensor and its preparation and application based on boron doping iron cobalt/cobalt oxide two-dimensional nano composite material | |
| CN106111196A (en) | A kind of preparation method and application of iron porphyrin chloride/methylene blue@metallic organic framework composite electrode | |
| CN107345931B (en) | It is a kind of based on carbonitride-binary metal boron oxide compound composite material bisphenol-A optical electro-chemistry sensor and its preparation and application | |
| CN106596651B (en) | A kind of molybdenum disulfide/hydroxide nanoparticle composite material and preparation method and application | |
| CN103743805A (en) | Biosensor based on nitrogen-hybridized mesoporous carbon as well as preparation method and application of biosensor | |
| CN109490385A (en) | Biosensor and preparation method thereof based on Au-ZIF-8/OMC mesoporous carbon | |
| CN101539525B (en) | Method for measuring formaldehyde in aqueous solution by electrochemical luminescence of terpyridyl ruthenium | |
| CN101750442B (en) | Monodispersive bimetal Au/Pt nano-particle modified electrode for detecting mercury in water and preparation method thereof | |
| CN108872343A (en) | A kind of Dopamine Sensor and its preparation and application based on nitrogen-doped graphene | |
| CN104370943A (en) | Preparation method and application of [Cu2(HL)2(Mu2-OH)2(H2O)5] | |
| CN109406599A (en) | A kind of preparation and application of the novel Electrochemical enzyme biosensor based on MOFs composite material | |
| CN103630587A (en) | Method for rapidly and sensitively detecting organophosphorus pesticide chlorpyrifos | |
| CN102645469B (en) | Preparation method of laccase/multihole nanometer titanium dioxide modified electrode | |
| CN101576530A (en) | Method for measuring dopamine by utilizing graphite nano-sheet/Nafion composite film to modify electrode | |
| CN103969307A (en) | Preparation method for titanium dioxide-graphene/screen-printed electrode for detecting parachlorophenol | |
| CN106324050B (en) | A kind of based single crystal TiO2The Polychlorinated biphenyls photoelectrochemical assay method of nanometer rods | |
| CN108152346A (en) | The preparation method and application of norfloxacin molecular imprinted electrochemical sensor based on nanometer modified by silver | |
| CN103558269A (en) | Preparation method of enzyme sensor for detecting chlorpyrifos pesticide residues |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140716 Termination date: 20170221 |