CN105223244A - A kind of preparation method and application detecting the trace electrochemical sensor of vanillic aldehyde - Google Patents
A kind of preparation method and application detecting the trace electrochemical sensor of vanillic aldehyde Download PDFInfo
- Publication number
- CN105223244A CN105223244A CN201510613865.XA CN201510613865A CN105223244A CN 105223244 A CN105223244 A CN 105223244A CN 201510613865 A CN201510613865 A CN 201510613865A CN 105223244 A CN105223244 A CN 105223244A
- Authority
- CN
- China
- Prior art keywords
- vanillic aldehyde
- cnts
- preparation
- electrochemical sensor
- template molecule
- 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.)
- Pending
Links
Abstract
The invention discloses a kind of molecular imprinting electrochemical sensor detecting vanillic aldehyde.This molecular imprinting electrochemical sensor utilizes electrode face finish technology, and the graphene oxide/carbon nano-tube/ionic liquid/golden nanometer particle compound of preparation is covered to glassy carbon electrode surface, strengthens to reach the object that electric signal improves sensor detection sensitivity.Again by the mode of electropolymerization, will be function monomer with pyrroles, be that the molecularly imprinted polymer of template molecule modifies electrode surface with vanillic aldehyde, after washing away template molecule, forms molecular imprinting electrochemical sensor.After template molecule elution, form hole at sensor surface, this hole can reach specificity with the structure of vanillic aldehyde and mate.Be that working electrode is connected to electrochemical workstation by the electrochemical sensor of preparation, by the specific binding in electrode surface template molecule and hole, generation current changes, and utilizes the detection that the change of electric current can realize vanillic aldehyde.Molecular imprinting electrochemical sensor selectivity prepared by the present invention is strong, highly sensitive, fast simple to operate, is applicable to the detection of vanillic aldehyde in food.
Description
Technical field
The invention belongs to nano material and food additives detection field, particularly adopt a kind of trace electrochemical process to detect vanillic aldehyde, may be used for the detection of vanillic aldehyde in food.
Background technology
Vanillic aldehyde is that a kind of phenolic compound is widely used in the food industry such as candy beverage, whipping prods.Appropriate interpolation vanillic aldehyde not only can keep desirable taste and the fragrance of food, is also of value to healthy.But the excessive absorption of vanillic aldehyde can cause headache, nausea and vomiting, and more severe patient can affect liver and renal function.Therefore, prepare a kind of simple, sensitive, detect the sensor of vanillic aldehyde fast highly significant.The detection method of current vanillic aldehyde mainly contains thin-layered chromatography, spectrophotometric method, high performance liquid chromatography etc., and these methods have complex operation, instrument price expensive, need technical professional, and is not suitable for the shortcomings such as on-the-spot large-scale detection fast.
Nanometer technology, molecular imprinting and electrochemical sensing assays technology three organically combine by this research, achieve the detection utilizing molecular engram sensor to vanillic aldehyde, this sensor have highly sensitive, analysis speed is fast, the feature such as simple to operate and with low cost.By modifying the compound and molecularly imprinted polymer that strengthen electrochemical signals on glass-carbon electrode, washing away template molecule, building electrochemical sensor.Template molecule can be formed a series of hole at sensor surface by after wash-out, these holes can with template molecule specific binding, utilize vanillic aldehyde in sample solution be combined with sensor before and after the curent change that causes to analyze the content of vanillic aldehyde in testing sample solution.
Summary of the invention
One of content of the present invention there is provided a kind of preparation of graphene oxide/carbon nano-tube/ionic liquid/golden nanometer particle (GO/CNTs/IL/AuNPs) compound substance.
Two of content of the present invention there is provided a kind of preparation method detecting the molecular imprinting electrochemical sensor of vanillic aldehyde in food.
Three of content of the present invention is to provide the detection of a kind of molecular imprinting electrochemical sensor application vanillic aldehyde in food.Technical scheme of the present invention, it specifically comprises the following steps:
1. detect a preparation for the molecular imprinting electrochemical sensor of vanillic aldehyde in food, it is characterized in that:
(1) preparation of graphene oxide/carbon nano-tube/ionic liquid/golden nanometer particle compound (GO/CNTs/IL/AuNPs);
(2) preparation of molecularly imprinted polymer (MIPs);
(3) preparation of the molecular imprinting electrochemical sensor of vanillic aldehyde is detected;
2. the preparation of GO/CNTs/IL/AuNPs as above, concrete steps are as follows:
Graphene oxide (GO) and carbon nano-tube (CNTs) are placed in the ultrasonic 3h of solution that ethanol and water volume ratio are 1:1 ~ 2, transfer to afterwards in autoclave and react 6 ~ 7h at 150 ~ 200 DEG C, obtain GO/CNTs compound; In this compound, add 15mg1-butyl-3-methylimidazole hydrobromate ionic liquid (IL), ultrasonic 30min, obtain GO/CNTs/IL compound; Get 0.15gGO/CNTs/IL and 3.65mL0.01mol/L chlorauric acid solution to be dispersed in 100mL ultrapure water, be heated to micro-boiling, then add rapidly the sodium citrate solution of 3.0 ~ 6.0mL1%, stir 30min; Eccentric cleaning obtains GO/CNTs/IL/AuNPs compound substance more than 3 ~ 5 times, dry;
3. the preparation of molecularly imprinted polymer (MIPs) as above, step is as follows:
Preparation 0.1mol/LKCl solution, add appropriate template molecule (vanillic aldehyde) and function monomer (pyrroles), under room temperature, 2 ~ 4h completes the pre-assembled process of template molecule and function monomer; For subsequent use;
4. a kind of molecular imprinting electrochemical sensor detecting vanillic aldehyde as above, the detecting step for vanillic aldehyde is as follows:
(1) 5 ~ 7 μ LGO/CNTs/IL/AuNPs uniform solution modifies glass-carbon electrode (GCE) surface, drying at room temperature; Adopt the mode of electropolymerization that MIPs is aggregated to GO/CNTs/IL/AuNPs/GCE surface, room temperature is dried; Adopt the template molecule vanillic aldehyde of the phosphate buffer solution wash-out sensor surface of the 0.05mol/L of pH=6.0 ~ 7.0;
(2) take Ag/AgCl as contrast electrode, be to electrode with Pt electrode, molecular imprinting electrochemical sensor is working electrode, be connected to electrochemical workstation, scan in potassium ferricyanide solution, detect the relation of electrochemical sensor wash-out and the change in electric of adsorbing before and after template molecule and vanillic aldehyde concentration, drawing curve;
(3) testing sample solution is substituted vanillic aldehyde standard solution, detect according to the method for drafting of working curve.
Determinand described above, is selected from the food such as candy, beverage, biscuit being added with vanillic aldehyde.
The molecular imprinting electrochemical sensor of described detection vanillic aldehyde, raw materials is all bought in chemical reagents corporation.
Advantage of the present invention and feature are:
(1) the GO/CNTs/IL/AuNPs composite conductivity of the present invention's employing is good, becomes the excellent material building electrochemical sensor;
(2) the molecular imprinting electrochemical transducer sensitivity prepared of the present invention is high, detection speed is fast, selectivity good, can realize the specific detection to measuring thing;
(3) the present invention detects the method for vanillic aldehyde, simple to operate, quick, convenient, sensitive, is convenient to Site Detection.
Accompanying drawing explanation
Fig. 1 GO/CNTs/IL/AuNPs modify molecular imprinting electrochemical sensor preparation and the response of vanillic aldehyde is illustrated.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition, after should also be understood that the content lectured in reading the present invention, those skilled in the art can make various change or amendment to the present invention, and these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
The preparation of graphene oxide/carbon nano-tube/ionic liquid/golden nanometer particle compound (GO/CNTs/IL/AuNPs)
Graphene oxide (GO) and carbon nano-tube (CNTs) are placed in the ultrasonic 3h of solution that ethanol and water volume ratio are 1:1, transfer to afterwards in autoclave and react 6h at 200 DEG C; Obtain GO/CNTs compound; In this compound, add 15mg1-butyl-3-methylimidazole hydrobromate ionic liquid (IL), ultrasonic 30min, obtain GO/CNTs/IL compound; Get 0.15gGO/CNTs/IL and 3.65mL0.01mol/L chlorauric acid solution to be dispersed in 100mL ultrapure water, be heated to micro-boiling, then add rapidly the sodium citrate solution of 3.0mL1%, stir 30min; Eccentric cleaning obtains GO/CNTs/IL/AuNPs compound substance 5 times, dry.
Embodiment 2
The preparation of graphene oxide/carbon nano-tube/ionic liquid/golden nanometer particle compound (GO/CNTs/IL/AuNPs)
Graphene oxide (GO) and carbon nano-tube (CNTs) are placed in the ultrasonic 3h of solution that ethanol and water volume ratio are 1:2, transfer to afterwards in autoclave and react 7h at 150 DEG C; Obtain GO/CNTs compound.In this compound, add 15mg1-butyl-3-methylimidazole hydrobromate ionic liquid (IL), ultrasonic 30min, obtain GO/CNTs/IL compound; Get 0.15gGO/CNTs/IL and 3.65mL0.01mol/L chlorauric acid solution to be dispersed in 100mL ultrapure water, be heated to micro-boiling, then add rapidly the sodium citrate solution of 6.0mL1%, stir 30min; Eccentric cleaning obtains GO/CNTs/IL/AuNPs compound substance 3 times, dry.
Embodiment 3
Detect a preparation method for the molecular imprinting electrochemical sensor of vanillic aldehyde, step is as follows:
(1) drip 5 μ LGO/CNTs/IL/AuNPs uniform solution to glassy carbon electrode surface, room temperature is dried;
(2) prepare 0.1mol/LKCl solution, add appropriate template molecule (vanillic aldehyde) and function monomer (pyrroles), under room temperature, 2h completes the pre-assembled process of template molecule and function monomer; Adopt electropolymerization mode to be polymerized by MIPs in (1) gained GO/CNTs/IL/AuNPs/GCE surface, room temperature is dried;
(3) phosphate buffer solution of the 0.05mol/L of pH=7.0 is adopted to wash away the template molecule vanillic aldehyde of sensor surface, drying at room temperature;
(4) taking Ag/AgCl as contrast electrode, is to electrode with Pt electrode, with (3) gained sensor in conjunction with template molecule it
After electrode be working electrode, connect electrochemical workstation scanning, adopt differential pulse method to detect the electric current of equilibration time.
Embodiment 4
Detect a preparation method for the molecular imprinting electrochemical sensor of vanillic aldehyde, step is as follows:
(1) drip 7 μ LGO/CNTs/IL/AuNPs uniform solution to glassy carbon electrode surface, room temperature is dried;
(2) prepare 0.1mol/LKCl solution, add appropriate template molecule (vanillic aldehyde) and function monomer (pyrroles), under room temperature, 3h completes the pre-assembled process of template molecule and function monomer; Adopt electropolymerization mode to be polymerized by MIPs in (1) gained GO/CNTs/IL/AuNPs/GCE surface, room temperature is dried;
(3) phosphate buffer solution of the 0.05mol/L of pH=6.0 is adopted to wash away the template molecule vanillic aldehyde of sensor surface, drying at room temperature;
(4) taking Ag/AgCl as contrast electrode, is to electrode with Pt electrode, with (3) gained sensor in conjunction with template molecule it
After electrode be working electrode, connect electrochemical workstation scanning, adopt differential pulse method to detect the electric current of equilibration time.
Embodiment 5
The detection of vanillic aldehyde in candy
(1) drip 6 μ LGO/CNTs/IL/AuNPs uniform solution to glassy carbon electrode surface, room temperature is dried;
(2) prepare 0.1mol/LKCl solution, add appropriate template molecule (vanillic aldehyde) and function monomer (pyrroles), under room temperature, 3h completes the pre-assembled process of template molecule and function monomer; Adopt electropolymerization mode to be polymerized by MIPs in (1) gained GO/CNTs/IL/AuNPs/GCE surface, room temperature is dried;
(3) phosphate buffer solution of the 0.05mol/L of pH=6.0 is adopted to wash away the template molecule vanillic aldehyde of sensor surface, drying at room temperature;
(4) take Ag/AgCl as contrast electrode, be to electrode with Pt electrode, with above-mentioned the electrode obtained for working electrode, be connected to and connect electrochemical workstation scanning, detect the change in electric of electrochemical sensor before and after wash-out and absorption template molecule and the relation of vanillic aldehyde concentration, drawing curve;
(5) candy is processed into sample solution to substitute vanillic aldehyde standard solution and detect, recording the range of linearity is 0.5ng/mL ~ 2500ng/mL, detects and is limited to 0.167ng/mL.
Embodiment 6
The detection of vanillic aldehyde in biscuit
(1) drip 6 μ LGO/CNTs/IL/AuNPs uniform solution to glassy carbon electrode surface, room temperature is dried;
(2) prepare 0.1mol/LKCl solution, add appropriate template molecule (vanillic aldehyde) and function monomer (pyrroles), under room temperature, 3h completes the pre-assembled process of template molecule and function monomer; Adopt electropolymerization mode to be polymerized by MIPs in (1) gained GO/CNTs/IL/AuNPs/GCE surface, room temperature is dried;
(3) phosphate buffer solution of the 0.05mol/L of pH=6.5 is adopted to wash away the template molecule vanillic aldehyde of sensor surface, drying at room temperature;
(4) take Ag/AgCl as contrast electrode, be to electrode with Pt electrode, with above-mentioned the electrode obtained for working electrode, be connected to and connect electrochemical workstation scanning, detect the change in electric of electrochemical sensor before and after wash-out and absorption template molecule and the relation of vanillic aldehyde concentration, drawing curve;
(5) biscuit is processed into sample solution to substitute vanillic aldehyde standard solution and detect, recording the range of linearity is 0.5ng/mL ~ 2500ng/mL, detects and is limited to 0.167ng/mL.
Claims (4)
1. detect a preparation for the molecular imprinting electrochemical sensor of vanillic aldehyde in food, it is characterized in that:
(1) preparation of graphene oxide/carbon nano-tube/ionic liquid/golden nanometer particle compound (GO/CNTs/IL/AuNPs);
(2) preparation of molecularly imprinted polymer (MIPs);
(3) preparation of the molecular imprinting electrochemical sensor of vanillic aldehyde is detected.
2. the preparation of GO/CNTs/IL/AuNPs according to claim 1, step is as follows:
Graphene oxide (GO) and carbon nano-tube (CNTs) are placed in the ultrasonic 3h of solution that ethanol and water volume ratio are 1:1 ~ 2, transfer to afterwards in autoclave and react 6 ~ 7h at 150 ~ 200 DEG C, obtain GO/CNTs compound; In this compound, add 15mg1-butyl-3-methylimidazole hydrobromate ionic liquid (IL), ultrasonic 30min, obtain GO/CNTs/IL compound; Get 0.15gGO/CNTs/IL and 3.65mL0.01mol/L chlorauric acid solution to be dispersed in 100mL ultrapure water, be heated to micro-boiling, then add rapidly the sodium citrate solution of 3.0 ~ 6.0mL1%, stir 30min; Clean and obtain GO/CNTs/IL/AuNPs compound substance more than 3 times.
3. the preparation of molecularly imprinted polymer according to claim 1 (MIPs), step is as follows:
Preparation 0.1mol/LKCl solution, add appropriate template molecule (vanillic aldehyde) and function monomer (pyrroles), under room temperature, 2 ~ 4h completes the pre-assembled process of template molecule and function monomer, for subsequent use.
4. a kind of molecular imprinting electrochemical sensor detecting vanillic aldehyde according to claim 1, for the detection of vanillic aldehyde, step is as follows:
(1) 5 ~ 7 μ LGO/CNTs/IL/AuNPs uniform solution are modified glassy carbon electrode surface, drying at room temperature; Adopt the mode of electropolymerization that MIPs is aggregated to GO/CNTs/IL/AuNPs/GCE surface, room temperature is dried; With the template molecule vanillic aldehyde of the phosphate buffer solution wash-out sensor surface of pH=6.0 ~ 7.0, this sensor is successfully prepared;
(2) take Ag/AgCl as contrast electrode, be to electrode with Pt electrode, molecular imprinting electrochemical sensor is working electrode, be connected to electrochemical workstation, scan in potassium ferricyanide solution, detect the relation of electrochemical sensor wash-out and the change in electric of adsorbing before and after template molecule and vanillic aldehyde concentration, drawing curve;
(3) testing sample solution is substituted vanillic aldehyde standard solution, detect according to the method for drafting of working curve.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510613865.XA CN105223244A (en) | 2015-09-24 | 2015-09-24 | A kind of preparation method and application detecting the trace electrochemical sensor of vanillic aldehyde |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510613865.XA CN105223244A (en) | 2015-09-24 | 2015-09-24 | A kind of preparation method and application detecting the trace electrochemical sensor of vanillic aldehyde |
Publications (1)
Publication Number | Publication Date |
---|---|
CN105223244A true CN105223244A (en) | 2016-01-06 |
Family
ID=54992316
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201510613865.XA Pending CN105223244A (en) | 2015-09-24 | 2015-09-24 | A kind of preparation method and application detecting the trace electrochemical sensor of vanillic aldehyde |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN105223244A (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105738448A (en) * | 2016-03-24 | 2016-07-06 | 肇庆学院 | Molecularly imprinted electrochemical sensor for detecting trace olaquindox |
CN106018519A (en) * | 2016-07-12 | 2016-10-12 | 青岛科技大学 | Ionic liquid functional composite membrane modified electrode and preparation method and application thereof to detection of chlorophenol |
CN106226370A (en) * | 2016-08-08 | 2016-12-14 | 中国农业科学院农业质量标准与检测技术研究所 | A kind of preparation method of glyphosate molecular imprinting electrochemical sensor |
CN109001280A (en) * | 2018-08-16 | 2018-12-14 | 广东工业大学 | A kind of preparation of thiabendazole molecular imprinting electrochemical sensor and application method |
WO2019168901A1 (en) * | 2018-02-27 | 2019-09-06 | University Of Massachusetts | Electrochemical sensor for detection and quantification of heavy metals |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103499655A (en) * | 2013-10-11 | 2014-01-08 | 浙江塔牌绍兴酒有限公司 | Detection method of vanillin in wine |
CN103575783A (en) * | 2013-11-01 | 2014-02-12 | 济南大学 | Preparation method of molecularly-imprinted electrochemical transducer for detecting propylgallate as well as application thereof |
-
2015
- 2015-09-24 CN CN201510613865.XA patent/CN105223244A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103499655A (en) * | 2013-10-11 | 2014-01-08 | 浙江塔牌绍兴酒有限公司 | Detection method of vanillin in wine |
CN103575783A (en) * | 2013-11-01 | 2014-02-12 | 济南大学 | Preparation method of molecularly-imprinted electrochemical transducer for detecting propylgallate as well as application thereof |
Non-Patent Citations (4)
Title |
---|
JUNHUA LI ET.AL: "Bimetallic Ag-Pd nanoparticles-decorated graphene oxide: a fascinating three-dimensional nanohybrid as an efficient electrochemical sensing platform for vanillin determination", 《ELECTROCHIMICA ACTA》 * |
LEI SHANG ET.AL: "Sensitive voltammetric determination of vanillin with an AuPd nanoparticles graphene composite modified electrode", 《FOOD CHEMISTRY》 * |
LIJUAN ZHAO ET.AL: "Electrochemical determinationoftartrazineusingamolecularly imprinted polymer–multiwalledcarbonnanotubes-ionicliquid supported Ptnanoparticlescompositefilmcoatedelectrode", 《ELECTROCHIMICA ACTA》 * |
王彩虹 等: "香兰素在玻碳电极上的电化学行为及其循环伏安测定", 《理化检验-化学分册》 * |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105738448A (en) * | 2016-03-24 | 2016-07-06 | 肇庆学院 | Molecularly imprinted electrochemical sensor for detecting trace olaquindox |
CN105738448B (en) * | 2016-03-24 | 2018-11-30 | 肇庆学院 | It is a kind of for detecting the molecular imprinting electrochemical sensor of micro olaquindox |
CN106018519A (en) * | 2016-07-12 | 2016-10-12 | 青岛科技大学 | Ionic liquid functional composite membrane modified electrode and preparation method and application thereof to detection of chlorophenol |
CN106018519B (en) * | 2016-07-12 | 2019-04-05 | 青岛科技大学 | The application of complex film modified electrode of ion liquid functionalization and preparation method thereof and detection chlorophenol |
CN106226370A (en) * | 2016-08-08 | 2016-12-14 | 中国农业科学院农业质量标准与检测技术研究所 | A kind of preparation method of glyphosate molecular imprinting electrochemical sensor |
CN106226370B (en) * | 2016-08-08 | 2018-04-27 | 中国农业科学院农业质量标准与检测技术研究所 | A kind of preparation method of glyphosate molecular imprinting electrochemical sensor |
WO2019168901A1 (en) * | 2018-02-27 | 2019-09-06 | University Of Massachusetts | Electrochemical sensor for detection and quantification of heavy metals |
US11592414B2 (en) | 2018-02-27 | 2023-02-28 | University Of Massachusetts | Electrochemical sensor for detection and quantification of heavy metals |
CN109001280A (en) * | 2018-08-16 | 2018-12-14 | 广东工业大学 | A kind of preparation of thiabendazole molecular imprinting electrochemical sensor and application method |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN105223243A (en) | The preparations and applicatio of the trace electrochemical sensor that a kind of carbon point compound substance is modified | |
CN105223244A (en) | A kind of preparation method and application detecting the trace electrochemical sensor of vanillic aldehyde | |
CN104459124B (en) | A kind of preparation method of the electrochemical immunosensor based on HS-β-CD-Ag-GOD conjugate and application | |
CN102778571B (en) | Ionic liquid-graphene nanocomposite, preparation method and electrochemical immunodetection method thereof | |
Hu et al. | A highly selective amperometric sensor for ascorbic acid based on mesopore-rich active carbon-modified pyrolytic graphite electrode | |
CN103558271B (en) | Electrochemical biosensor for detecting penicillin and preparation method and application thereof | |
CN109115850B (en) | Chemically modified electrode for sensitively detecting doxycycline and preparation method and application thereof | |
CN108645903B (en) | The preparation and application of molecular engram sensor based on the chitosan-modified glass-carbon electrode of carbon dots- | |
CN105675683A (en) | Preparation method and application of electrochemical sensor for detecting sunset yellow | |
Mei et al. | Electrochemical biosensors for foodborne pathogens detection based on carbon nanomaterials: Recent advances and challenges | |
CN105738448B (en) | It is a kind of for detecting the molecular imprinting electrochemical sensor of micro olaquindox | |
CN103698373A (en) | Preparation method of molecular-imprinting electrochemical sensor for detecting 2,6-butylated hydroxytoluene and application thereof | |
CN108020587A (en) | The detection method of the staphylococcus aureus in milk of dual signal amplification | |
CN103575783A (en) | Preparation method of molecularly-imprinted electrochemical transducer for detecting propylgallate as well as application thereof | |
CN108732218B (en) | Electrochemical sensor for measuring 2,4, 6-trichlorophenol and preparation and application thereof | |
CN103926294A (en) | Preparation and application of CS/IL-GR modified bovine serum albumin molecular imprinting electrode | |
CN103713026A (en) | Preparation method and applications of aptamer electrochemical sensor for detecting malachite green (MG) | |
CN103499619A (en) | Method for manufacturing acetylcholin esterase sensor detecting organophosphorus pesticide | |
CN103822949A (en) | Preparation method and application of electrochemical immunosensor for detecting escherichia coli | |
Moradi | A review on nanomaterial-based electrochemical sensors for determination of vanillin in food samples | |
CN102680549A (en) | Method for measuring 9-hydroxy fluorine based on electrochemistry hairpin DNA biosensor | |
CN105973956A (en) | Graphene-cuprous oxide composite film modified acetylene black electrode and detection method for detection of vanillin in food | |
CN109085225A (en) | A kind of preparation method of the protein electrochemistry trace sensor of step sedimentation modification carbon electrode | |
CN105403612A (en) | Method for rapidly detecting pesticide residue based on plant esterase | |
CN104407132A (en) | Electrochemical sensor for detection of Escherichia coli and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20160106 |
|
WD01 | Invention patent application deemed withdrawn after publication |