CN102520038A - Method for preparing graphene biosensor - Google Patents
Method for preparing graphene biosensor Download PDFInfo
- Publication number
- CN102520038A CN102520038A CN201110425479XA CN201110425479A CN102520038A CN 102520038 A CN102520038 A CN 102520038A CN 201110425479X A CN201110425479X A CN 201110425479XA CN 201110425479 A CN201110425479 A CN 201110425479A CN 102520038 A CN102520038 A CN 102520038A
- Authority
- CN
- China
- Prior art keywords
- electrode
- graphene
- drying
- room temperature
- biology sensor
- 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
Abstract
The invention relates to a method for preparing a graphene biosensor, belonging to the technical field of electrochemistry. The method comprises the following steps of: immersing a processed gold electrode into graphene oxide and a sodium sulphate solution, electrically depositing the electrode through a control electric potential, taking out the electrode, washing the electrode by using water, after drying the electrode at room temperature, putting the electrode in a chloroauric acid solution, electrically depositing the electrode through the control electric potential, taking out the electrode, washing the electrode by using water, and drying the electrode at room temperature; putting a modified electrode in a conductive polymer monomer and a supporting electrolyte solution, polymerizing the electrode through the control electric potential by adopting a cyclic voltammetry, taking out the electrode, washing the electrode by using water, and drying the electrode at room temperature; and activating the modified electrode in an EDC/NHS (Dichloroethane/N-Hydroxysuccinimide) solution, and immersing the modified electrode in a vomiting toxin antibody. The method disclosed by the invention is used for fixing graphene, gold nanoparticles and conducting polymers through electro-deposition; therefore, the method is very green and environment-friendly; furthermore, the thickness of a coating and sizes and distribution densities of the gold nanoparticles can be precisely controlled, thus, the batch production repeatability of the modified electrode is good.
Description
Technical field
The present invention relates to a kind of preparation method of Graphene biology sensor, belong to technical field of electrochemistry.
Background technology
Graphene is the crystal of six side's honeycomb crystalline networks of the tightly packed formation of monolayer carbon atom; Unique two-dimensional structure makes it have excellent electricity, calorifics, mechanics and chemical property; But there is bigger Van der Waals force in the graphene film interlayer; Be prone to take place to pile up and assemble, thereby limited its application in many aspects.In order to overcome the above problems, people are at metal nanoparticles such as graphene film interlayer doping gold, and this is not only avoided the Graphene lamella to come back to graphite crystal because of gathering effectively, and has improved electronic conductivity (Zhong, the Z.Y. of grapheme material greatly; Wu, W., Wang, D., Wang; D., Shan, J.L., Qing, Y.; Zhang, Z.M., Biosensors and Bioelectronics, 2010,25:2379-2382).Recently, the application of Graphene/metallic composite in biology sensor receive extensive concern (Wan, Y., Wang, Y., Wu, J.J., Zhang, D., Anal.Chem., 2011,83:648-652).
Grapheme material and enzyme fixing is to graphene-based performance of biosensor and use most important.At present, fixing physisorphtions that adopt of grapheme material and enzyme more.Normally adopt earlier the synthetic graphite oxide of Hummer method, more ultrasonic being dispersed in of graphite oxide processed the graphene oxide dispersion liquid in the water, mixes with metal precursor then, add strong reductant such as sodium borohydride and make graphene oxide prepare Graphene/metallic composite with the metal precursor in-situ reducing, compound substance is scattered in later of water again and is applied to electrode surface (Gu under stabilizer function; Z.G., Yang, S.P., Li; Z.J., Sun, X.L., Wang; G.L., Fang, Y.J., Liu; J.K., Anal.Chim.Acta, 2011,701:75-80).Drop-coating is consuming time more, needs to use poisonous chemical reagent, the products obtained therefrom bad dispersibility, and coating is coarse, and thickness is difficult to accurate control, thereby causes the electrocatalysis characteristic of material to descend.Recently, the researchist has proposed a kind of new electrochemical method.Electrode is inserted the mixed solution of graphene oxide and gold chloride, adopt cyclic voltammetry scan once accomplish compound substance preparation and fixing (Liu, C.B., Wang, K., Luo, S.L., Tang, Y.H., Chen, L.Y., Small, 2011,7:1203-1206).Method has simply, fast and distinguishing feature such as green, but be prone to take place redox reaction between graphite oxide and the noble metal precursor body, cause mixed solution soon rotten and electrode modification layer that obtain is more coarse.Shitosan is a kind of biological material, and its excellent film forming ability often is used to fixing (Yang, Y.C., Dong, S.W., the Shen of enzyme at electrode surface; T., Jian, C.X., Chang, H.J., Li; Y., Zhou, J.X., Electrochim.Acta, 2011,56:6021-6025).But the enzyme that this physisorphtion is fixed is prone to come off, and makes the stability of sensor and reappearance be difficult to satisfy the requirement of real work to detection accuracy.In addition, the use of non-conductive material such as shitosan also can influence the electrochemical response of electrode.In order to address this problem, people attempt utilizing graphene oxide to contain and enrich the characteristics of carboxyl, with DHC/NHS be active agent with covalently bound on modified electrode, but graphene oxide poorly conductive, prepared biosensor analysis performance is undesirable.Therefore it is imperative to set up preparation method green, easy and reliable Graphene biology sensor.
Pass through extensive studies and test repeatedly and find, employing electrochemical process electro-deposition Graphene, nm of gold and electrochromic conducting polymer successively is deposited on electrode surface, and the enzyme or the antibody of inciting somebody to action with the covalent bonding mode then are fixed on the conducting polymer film.Electrochemical process has not only realized the fixing completion simultaneously on electrode of electrochemical reaction and material; Can also realize the particle diameter of Graphene and conducting polymer coating thickness and golden nanometer particle and the accurate control of distribution density, and the preparation process of material does not have " three wastes " to produce.The inventor further is optimized selection to electrodeposition condition, has realized improving the purpose of stability, sensitivity and the precision of Graphene biology sensor finally.
Summary of the invention
The objective of the invention is to have to existing Graphene biology sensor that Graphene and enzyme are prone to come off, sensitivity is not high and the deficiency of the poor reproducibility of sensor production, a kind of preparation method of new Graphene biology sensor is provided.Method has been improved stability, sensitivity and the precision of Graphene biology sensor significantly, and also environmental protection can not cause environmental pollution.
According to technical scheme provided by the invention, a kind of preparation method of Graphene biology sensor, step is:
1) preparation of Graphene modified electrode: be scattered in that the stable concentration of formation is 0.0001～0.1mg/mL graphene oxide dispersion liquid in the deionized water with graphite oxide is ultrasonic; Ultrasonic frequency is 55kHz-60kHz; Add supporting electrolyte, being adjusted to supporting electrolyte concentration is 0～1mol/L; With the platinized platinum is basic electrode, on the electricity workstation CONTROLLED POTENTIAL-0.9～-1.2V place electro-deposition 10～50s, take out electrode, use deionized water wash, drying at room temperature;
2) gold chloride is handled: the Graphene modified electrode that step 1) makes is put into 0.002～0.2mmol/L chlorauric acid solution; CONTROLLED POTENTIAL is at-0.25～0.4V place electro-deposition 10～50s on electrochemical workstation; Take out electrode, use deionized water wash, drying at room temperature;
3) cyclic voltammetry scan: multiple weigh 1) and 2) operation 5～50 times, then resulting electrode is put into the solution that contains 0.01～0.2mol/L conductive high polymer monomer and 0.001～0.005mol/L supporting electrolyte and carries out cyclic voltammetry scan, the cyclic voltammetry scan voltage range is 0～1.0V; Sweep speed is 10～400mV/s; Cycle index is 2～10 times, and temperature is 0～40 ℃, takes out electrode after scanning is accomplished; Use deionized water wash, drying at room temperature;
4) preparation of Graphene biology sensor: with the resulting electrode of step 3) activation 4～6h in 18～22mMEDC/NHS solution; In 8～12mg/mL hydrogen peroxidase, soak 22～26h then; Use deionized water wash; 4 ℃ dry down, then the analytical performance of test Graphene biology sensor on electrochemical workstation.
Said conductive polymer high polymer monomer is as shown in the formula the compound shown in 12,5-two (2-thiophene)-1-R-pyrroles;
Wherein, R is a substituting group, for alkane, alkene, alkynes base or the aromatic radical of carbon number between 1～20, connects 1～3 carboxyl again thereafter.
The described supporting electrolyte of step 1) is with K
+Or Na
+Be kation, with SO
4 2-, CO
3 2-, CH
3COO
-, Cl
-, ClO
4 -, ClO
3 -Or NO
3 -Any in the compound of forming for negative ion.
Step 3) is described multiple to weigh 1) and 2) the number of times of operation be 10～20 times.
The described supporting electrolyte of step 3) is to be kation with the quaternary amine base, is the compound that negative ion is formed with chlorion, bromide ion, chlorate anions, perchlorate, tetrafluoroborate or hexafluoro-phosphate radical, perhaps their potpourri.
The present invention has following advantage: one embodiment of the present of invention are presoma with the graphite oxide, adopt CONTROLLED POTENTIAL at gold electrode surfaces electro-deposition Graphene, are that presoma adopts CONTROLLED POTENTIAL at Graphene surface electrical deposited gold nano particle then with the gold chloride.After operating 20 times more than repeating, electrode is put into 2, in 5-two (2-thiophene)-1-para Toluic Acid pyrrole monomer solution, adopt cyclic voltammetry to carry out electropolymerization, multiple scanning 6 times.At last, be that active agent is combined in hydrogen peroxidase covalent bonding mode on the conducting polymer film with EDC/NHS, and on electrochemical workstation, test the analytical performance of this biology sensor.Research shows that resulting hydrogen peroxide bio-sensing has very sensitive electrochemical response to hydrogen peroxide, and its detection limit reaches 2 * 10
-8Mol/L, concrete advantage is following:
1) fixedly Graphene, gold nano and conducting polymer of electro-deposition, the size of not only very environmental protection, and coating thickness and golden nanometer particle and distribution density can precisely be controlled, thereby make the good reproducibility of batch producing of modified electrode.
2) resulting Graphene/metal/composite material favorable dispersibility shows significant electro catalytic activity, and the sensitivity of its Electrochemical Detection is apparently higher than prior art.
3) covalent bonding mode immobilizing biologically active macromolecular substances, the enzyme or the antibody that have overcome drop-coating are prone to the deficiency that comes off, and have improved the stability and the accuracy of detection of biology sensor greatly.
Description of drawings
Fig. 1 process chart of the present invention.
Embodiment
Further specify the present invention with embodiment below, but the present invention is not limited.The experimental technique of unreceipted actual conditions in the following example, usually according to normal condition, or the condition of advising according to manufacturer." room temperature " described in the present invention, " normal pressure " are meant temperature and the air pressure between regular job, are generally 25 ℃, an atmospheric pressure.
Among the following embodiment, used working electrode is gold electrode (φ=1mm).Electrode uses particle diameter to carry out polishing as the alumina powder of 50nm before use, in the second absolute alcohol, embathes 10min, ultrasonic cleaning then, and drying is weighed.The working electrode that electro-deposition and electro-chemical test are used and all be naked gold electrode or various modified electrode to electrode, participating in electrode is the AgCl/Ag normal electrode.Electro-chemical test adopts cyclic voltammetry, and operating voltage is-0.8～0.8V, and sweep speed is 100mV/s, and test end liquid is that pH is 7 phosphate buffer solution.
Embodiment 1
Gold electrode after handling is immersed in the 0.05mg/mL graphene oxide dispersion liquid, 20 ℃ of following CONTROLLED POTENTIAL at-1.2V place electro-deposition 50s, taking-up electrode; Use water washing; Be placed on after the drying at room temperature in the chlorauric acid solution of 0.05mmol/L, at-0.25V place electro-deposition 50s, take out electrode 20 ℃ of following CONTROLLED POTENTIAL; Use water washing, drying at room temperature.After the above electro-deposition operation cycle 20 times; Modified electrode is inserted 3mL contain 2, in the dichloromethane solution of 5-two (2-thiophene)-1-para Toluic Acid pyrroles (1mmol/L) and tetrabutylammonium perchlorate amine (0.1mol/L), CONTROLLED POTENTIAL adopts cyclic voltammetry to carry out polymerization between 0～1V; With the rate scanning of 100mV/s six times; Take out electrode, use water washing, drying at room temperature.Modified electrode soaks 24h then at 20mmol/L EDC/NHS solution activation 4h in the 10mg/mL hydrogen peroxidase, the detection limit that resulting hydrogen peroxide biology sensor detects hydrogen peroxide reaches 2.0 * 10
-8Mol/L, 20 times the replication relative standard deviation is 1.8%.
Embodiment 2
Gold electrode after handling is immersed in the 0.02mg/mL graphene oxide dispersion liquid, 0 ℃ of following CONTROLLED POTENTIAL at-1.0V place electro-deposition 20s, taking-up electrode; Use water washing; Be placed on after the drying at room temperature in the chlorauric acid solution of 0.01mmol/L, at-0.3V place electro-deposition 40s, take out electrode 25 ℃ of CONTROLLED POTENTIAL; Use water washing, drying at room temperature.After the above electro-deposition operation cycle 30 times; Modified electrode is inserted 3mL contain 2, in the dichloromethane solution of 5-two (2-thiophene)-1-para Toluic Acid pyrroles (1mmol/L) and tetrabutylammonium chloride (0.1mol/L), CONTROLLED POTENTIAL adopts cyclic voltammetry to carry out polymerization between 0～1V; With the rate scanning of 200mV/s six times; Take out electrode, use water washing, drying at room temperature.Modified electrode soaks 24h then at 20mmol/L EDC/NHS solution activation 4h in the 10mg/mL glucose oxidase, the detection limit that resulting glucose biological sensor detects glucose reaches 1.0 * 10
-9Mol/L, 20 times the replication relative standard deviation is 1.0%.
Embodiment 3
Gold electrode after handling immersed contains 0.02mg/mL graphene oxide and 0.1mol/L Klorvess Liquid, 40 ℃ of following CONTROLLED POTENTIAL at-1.0V place electro-deposition 20s, taking-up electrode; Use water washing; Be placed on after the drying at room temperature in the chlorauric acid solution of 0.01mmol/L, at-0.4V place electro-deposition 20s, take out electrode 0 ℃ of following CONTROLLED POTENTIAL; Use water washing, drying at room temperature.After the above electro-deposition operation cycle 50 times; Modified electrode is inserted 3mL contain 2, in the dichloromethane solution (0.1mol/L) of 5-two (2-thiophene)-1-para Toluic Acid pyrroles (1.0mmol/L) and four octyl amine tetrafluoroborates, CONTROLLED POTENTIAL adopts cyclic voltammetry to carry out polymerization between 0～1V; With the rate scanning of 300mV/s six times; Take out electrode, use water washing, drying at room temperature.Modified electrode is at 20mmol/L EDC/NHS solution activation 4h, then at the 20mg/mL AFB
1Soak 24h in the antibody, the detection limit of resulting glucose biological sensor reaches 1.0 * 10
-10Mol/L, 20 times the replication relative standard deviation is 1.8%.
Embodiment 4
Gold electrode after handling immersed contains 0.01mg/mL graphene oxide and 0.1mol/L potassium sulfate solution, 0 ℃ of following CONTROLLED POTENTIAL at-1.2V place electro-deposition 10s, taking-up electrode; Use water washing; Be placed on after the drying at room temperature in the chlorauric acid solution of 0.02mmol/L, at-0.25V place electro-deposition 30s, take out electrode 0 ℃ of following CONTROLLED POTENTIAL; Use water washing, drying at room temperature.After the above electro-deposition operation cycle 30 times; Modified electrode is inserted 3mL contain 2, in the dichloromethane solution (0.2mol/L) of 5-two (2-thiophene)-1-o-benzoic acid pyrroles (1mmol/L) and four octyl group ammonium bromides, CONTROLLED POTENTIAL adopts cyclic voltammetry to carry out polymerization between 0～1V; With the rate scanning of 50mV/s 2 times; Take out electrode, use water washing, drying at room temperature.Modified electrode soaks 24h then at 20mMEDC/NHS solution activation 4h in the 20mg/mL hydrogen peroxidase, the detection limit of resulting hydrogen peroxide biology sensor reaches 1.0 * 10
-7Mol/L, 20 times the replication relative standard deviation is 1.1%.
Embodiment 5
Gold electrode after handling immersed contains 0.05mg/mL graphene oxide and 0.1mol/L metabisulfite solution, 10 ℃ of following CONTROLLED POTENTIAL at-1.0V place electro-deposition 20s, taking-up electrode; Use water washing; Be placed on after the drying at room temperature in the chlorauric acid solution of 0.01mmol/L, at-0.35V place electro-deposition 10s, take out electrode 0 ℃ of following CONTROLLED POTENTIAL; Use water washing, drying at room temperature.After the above electro-deposition operation cycle 15 times; Modified electrode is inserted 3mL contain 2, in the dichloromethane solution (0.2mol/L) of 5-two (2-thiophene)-1-propionic acid pyrroles (1mmol/L) and four octyl group ammonium bromides, CONTROLLED POTENTIAL adopts cyclic voltammetry to carry out polymerization between 0～1V; With the rate scanning of 20mV/s 8 times; Take out electrode, use water washing, drying at room temperature.Modified electrode soaks 24h then at 20mM EDC/NHS solution activation 4h in 20mg/mL vomitoxin antibody, the detection limit of resulting vomitoxin biology sensor reaches 2.5 * 10
-11Mol/L, 20 times the replication relative standard deviation is 1.0%.
Embodiment 6
Gold electrode after handling immersed contains 0.1mg/mL graphene oxide and 0.3mol/L metabisulfite solution, 0 ℃ of following CONTROLLED POTENTIAL at-0.9V place electro-deposition 20s, taking-up electrode; Use water washing; Be placed on after the drying at room temperature in the chlorauric acid solution of 0.02mmol/L, at-0.25V place electro-deposition 20s, take out electrode 10 ℃ of following CONTROLLED POTENTIAL; Use water washing, drying at room temperature.After the above electro-deposition operation cycle 15 times; Modified electrode is inserted 3mL contain 2, in the dichloromethane solution (0.2mol/L) of 5-two (2-thiophene)-1-acrylic acid pyrroles (1mmol/L) and four octyl group ammonium bromides, CONTROLLED POTENTIAL adopts cyclic voltammetry to carry out polymerization between 0～1V; With the rate scanning of 20mV/s 6 times; Take out electrode, use water washing, drying at room temperature.Modified electrode soaks 24h then at 20mM EDC/NHS solution activation 4h in the 20mg/mL shrimp allergen, the detection limit of resulting shrimp allergen biology sensor reaches 3.3 * 10
-8Mol/L, 20 times the replication relative standard deviation is 2.1%.
Claims (5)
1. the preparation method of a Graphene biology sensor is characterized in that step is:
1) preparation of Graphene modified electrode: be scattered in that the stable concentration of formation is 0.0001～0.1mg/mL graphene oxide dispersion liquid in the deionized water with graphite oxide is ultrasonic; Ultrasonic frequency is 55kHz-60kHz; Add supporting electrolyte, being adjusted to supporting electrolyte concentration is 0～1mol/L; With the platinized platinum is basic electrode, on the electricity workstation CONTROLLED POTENTIAL-0.9～-1.2V place electro-deposition 10～50s, take out electrode, use deionized water wash, drying at room temperature;
2) gold chloride is handled: the Graphene modified electrode that step 1) makes is put into 0.002～0.2mmol/L chlorauric acid solution; CONTROLLED POTENTIAL is at-0.25～0.4V place electro-deposition 10～50s on electrochemical workstation; Take out electrode, use deionized water wash, drying at room temperature;
3) cyclic voltammetry scan: multiple weigh 1) and 2) operation 5～50 times, then resulting electrode is put into the solution that contains 0.01～0.2mol/L conductive high polymer monomer and 0.001～0.005mol/L supporting electrolyte and carries out cyclic voltammetry scan, the cyclic voltammetry scan voltage range is 0～1.0V; Sweep speed is 10～400mV/s; Cycle index is 2～10 times, and temperature is 0～40 ℃, takes out electrode after scanning is accomplished; Use deionized water wash, drying at room temperature;
4) preparation of Graphene biology sensor: with the resulting electrode of step 3) activation 4～6h in 18～22mMEDC/NHS solution; In 8～12mg/mL hydrogen peroxidase, soak 22～26h then; Use deionized water wash; 4 ℃ dry down, then the analytical performance of test Graphene biology sensor on electrochemical workstation.
2. the preparation method of Graphene biology sensor according to claim 1, it is characterized in that: said conductive polymer high polymer monomer is as shown in the formula the compound shown in 12,5-two (2-thiophene)-1-R-pyrroles;
Wherein, R is a substituting group, for alkane, alkene, alkynes base or the aromatic radical of carbon number between 1～20, connects 1～3 carboxyl again thereafter.
3. the preparation method of Graphene biology sensor according to claim 1, it is characterized in that: the described supporting electrolyte of step 1) is with K
+Or Na
+Be kation, with SO
4 2-, CO
3 2-, CH
3COO
-, Cl
-, ClO
4 -, ClO
3 -Or NO
3 -Any in the compound of forming for negative ion.
4. the preparation method of Graphene biology sensor according to claim 1 is characterized in that: step 3) is described to weigh 1 again) and 2) the number of times of operation be 10～20 times.
5. the preparation method of Graphene biology sensor according to claim 1; It is characterized in that: the described supporting electrolyte of step 3) is to be kation with the quaternary amine base; With chlorion, bromide ion, chlorate anions, perchlorate, tetrafluoroborate or hexafluoro-phosphate radical is the compound that negative ion is formed, perhaps their potpourri.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110425479 CN102520038B (en) | 2011-12-16 | 2011-12-16 | Method for preparing graphene biosensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110425479 CN102520038B (en) | 2011-12-16 | 2011-12-16 | Method for preparing graphene biosensor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102520038A true CN102520038A (en) | 2012-06-27 |
| CN102520038B CN102520038B (en) | 2013-09-18 |
Family
ID=46291027
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110425479 Active CN102520038B (en) | 2011-12-16 | 2011-12-16 | Method for preparing graphene biosensor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102520038B (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102944598A (en) * | 2012-11-29 | 2013-02-27 | 江南大学 | Preparation method and application of cell based sensor based on electrochemical reduction graphite oxide/gold nanoparticle composite membrane |
| CN103033544A (en) * | 2012-12-11 | 2013-04-10 | 常州大学 | Electrochemical DNA sensor based on graphene-precious metal composite and preparation method thereof |
| CN103063715A (en) * | 2012-11-03 | 2013-04-24 | 福建医科大学 | Method for detecting surviving gene based on graphene-gold composite material electrochemical DNA (Deoxyribose Nucleic Acid) biosensor |
| CN103630574A (en) * | 2013-11-14 | 2014-03-12 | 江苏大学 | Preparation method of graphene DNA (deoxyribonucleic acid) sensor |
| WO2014101193A1 (en) * | 2012-12-31 | 2014-07-03 | Jiangnan University | Dithienylpyrrole-based biosensors and methods for their preparation and use |
| CN104142393A (en) * | 2013-10-30 | 2014-11-12 | 张治红 | Biosensor sensitive membrane and application in detection of clenbuterol hydrochloride |
| CN105136890A (en) * | 2015-10-15 | 2015-12-09 | 田野 | N-doped graphene biosensor |
| CN105891289A (en) * | 2014-12-05 | 2016-08-24 | 江南大学 | Electrochemical method for measuring oxidation inducing time of grease |
| CN105911123A (en) * | 2016-06-30 | 2016-08-31 | 重庆医科大学 | Electrochemical detection method for vomitoxin |
| CN106053557A (en) * | 2016-05-23 | 2016-10-26 | 济南大学 | Preparation method of human fibroblast growth factor immunosensor based on flaked black phosphorus |
| 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 |
| CN106290494A (en) * | 2015-06-01 | 2017-01-04 | 江南大学 | A kind of electrochemical method evaluating oil oxidative stability |
| CN107014883A (en) * | 2015-10-15 | 2017-08-04 | 爱科来株式会社 | The manufacture method of biology sensor and biology sensor |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102051651A (en) * | 2011-01-11 | 2011-05-11 | 湖南大学 | Preparation method of graphene film |
-
2011
- 2011-12-16 CN CN 201110425479 patent/CN102520038B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102051651A (en) * | 2011-01-11 | 2011-05-11 | 湖南大学 | Preparation method of graphene film |
Non-Patent Citations (4)
| Title |
|---|
| 《Microchimica Acta》 20110426 Yuling Cui et al "Sensitive detection of hydrogen peroxide in foodstuff using an organic-inorganic hybrid multilayer-functionalized graphene biosensing platform" 第137-144页 1-5 第174卷, * |
| 《云南师范大学学报》 20110731 杨云慧等 "基于石墨烯／铂纳米颗粒复合材料的过氧化氢无酶传感器的研制" 第11-15页 1-5 第31卷, 第4期 * |
| YULING CUI ET AL: ""Sensitive detection of hydrogen peroxide in foodstuff using an organic–inorganic hybrid multilayer-functionalized graphene biosensing platform"", 《MICROCHIMICA ACTA》 * |
| 杨云慧等: ""基于石墨烯／铂纳米颗粒复合材料的过氧化氢无酶传感器的研制"", 《云南师范大学学报》 * |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103063715B (en) * | 2012-11-03 | 2015-07-01 | 福建医科大学 | Method for detecting surviving gene based on graphene-gold composite material electrochemical DNA (Deoxyribose Nucleic Acid) biosensor |
| CN103063715A (en) * | 2012-11-03 | 2013-04-24 | 福建医科大学 | Method for detecting surviving gene based on graphene-gold composite material electrochemical DNA (Deoxyribose Nucleic Acid) biosensor |
| CN102944598A (en) * | 2012-11-29 | 2013-02-27 | 江南大学 | Preparation method and application of cell based sensor based on electrochemical reduction graphite oxide/gold nanoparticle composite membrane |
| CN103033544A (en) * | 2012-12-11 | 2013-04-10 | 常州大学 | Electrochemical DNA sensor based on graphene-precious metal composite and preparation method thereof |
| US9891184B2 (en) | 2012-12-31 | 2018-02-13 | Jiangnan University | Dithienylpyrrole-based biosensors and methods for their preparation and use |
| WO2014101193A1 (en) * | 2012-12-31 | 2014-07-03 | Jiangnan University | Dithienylpyrrole-based biosensors and methods for their preparation and use |
| CN104142393A (en) * | 2013-10-30 | 2014-11-12 | 张治红 | Biosensor sensitive membrane and application in detection of clenbuterol hydrochloride |
| CN104142393B (en) * | 2013-10-30 | 2016-03-30 | 郑州轻工业学院 | A kind of biological sensor sensing film and the application in detection clenobuterol hydrochloride thereof |
| CN103630574A (en) * | 2013-11-14 | 2014-03-12 | 江苏大学 | Preparation method of graphene DNA (deoxyribonucleic acid) sensor |
| CN105891289A (en) * | 2014-12-05 | 2016-08-24 | 江南大学 | Electrochemical method for measuring oxidation inducing time of grease |
| CN105891289B (en) * | 2014-12-05 | 2019-04-09 | 江南大学 | A kind of electrochemical method measuring Oxidation of Fat and Oils induction time |
| CN106290494A (en) * | 2015-06-01 | 2017-01-04 | 江南大学 | A kind of electrochemical method evaluating oil oxidative stability |
| CN106290494B (en) * | 2015-06-01 | 2018-11-16 | 江南大学 | A kind of electrochemical method for evaluating oil oxidative stability |
| CN105136890A (en) * | 2015-10-15 | 2015-12-09 | 田野 | N-doped graphene biosensor |
| CN107014883A (en) * | 2015-10-15 | 2017-08-04 | 爱科来株式会社 | The manufacture method of biology sensor and biology sensor |
| CN105136890B (en) * | 2015-10-15 | 2018-09-04 | 河北北方学院 | A kind of N doped graphenes biosensor |
| CN106053557B (en) * | 2016-05-23 | 2018-10-26 | 济南大学 | A kind of preparation method of the human fibroblastic growth factor immunosensor based on sheet black phosphorus |
| CN106053557A (en) * | 2016-05-23 | 2016-10-26 | 济南大学 | Preparation method of human fibroblast growth factor immunosensor based on flaked black phosphorus |
| CN105911123A (en) * | 2016-06-30 | 2016-08-31 | 重庆医科大学 | Electrochemical detection method for vomitoxin |
| 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 |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102520038B (en) | 2013-09-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102520038B (en) | Method for preparing graphene biosensor | |
| Bilal et al. | Polyaniline@ CuNi nanocomposite: A highly selective, stable and efficient electrode material for binder free non-enzymatic glucose sensor | |
| Li et al. | Assembly of ultrathin NiOOH nanosheets on electrochemically pretreated glassy carbon electrode for electrocatalytic oxidation of glucose and methanol | |
| Rinaldi et al. | Impedimetric non-enzymatic glucose sensor based on nickel hydroxide thin film onto gold electrode | |
| Hui et al. | Nickel nanoparticles modified conducting polymer composite of reduced graphene oxide doped poly (3, 4-ethylenedioxythiophene) for enhanced nonenzymatic glucose sensing | |
| Babu et al. | Freestanding and binder free PVdF-HFP/Ni-Co nanofiber membrane as a versatile platform for the electrocatalytic oxidation and non-enzymatic detection of urea | |
| Liu et al. | Three-dimensional porous NiO nanosheets vertically grown on graphite disks for enhanced performance non-enzymatic glucose sensor | |
| Tang et al. | Carbon nanotube template synthesis of hierarchical NiCoO2 composite for non-enzyme glucose detection | |
| CN102329424B (en) | Method for preparing polypyrrole/graphene composite film material | |
| Ni et al. | In-situ growth of Co 3 O 4 nanoparticles on mesoporous carbon nanofibers: a new nanocomposite for nonenzymatic amperometric sensing of H 2 O 2 | |
| Jia et al. | Electrodeposition of hydroxyapatite on nickel foam and further modification with conductive polyaniline for non-enzymatic glucose sensing | |
| Wang et al. | Enhanced conductivity of a glassy carbon electrode modified with a graphene-doped film of layered double hydroxides for selectively sensing of dopamine | |
| Cui et al. | Hollow mesoporous CuCo2O4 microspheres derived from metal organic framework: a novel functional materials for simultaneous H2O2 biosensing and glucose biofuel cell | |
| Li et al. | 3D electrochemical sensor based on poly (hydroquinone)/gold nanoparticles/nickel foam for dopamine sensitive detection | |
| Ciszewski et al. | Nanoparticles of Ni (OH) 2 embedded in chitosan membrane as electrocatalyst for non-enzymatic oxidation of glucose | |
| Xu et al. | Ordered mesoporous polyaniline film as a new matrix for enzyme immobilization and biosensor construction | |
| Khan | Graphene oxide modified electrodes for dopamine sensing | |
| Roushani et al. | Hydrogen peroxide sensor based on riboflavin immobilized at the nickel oxide nanoparticle-modified glassy carbon electrode | |
| Lu et al. | A novel nonenzymatic hydrogen peroxide sensor based on three-dimensional porous Ni foam modified with a Pt electrocatalyst | |
| Qiu et al. | Graphene oxide directed in-situ synthesis of Prussian blue for non-enzymatic sensing of hydrogen peroxide released from macrophages | |
| Zhan et al. | Ni3 (PO4) 2 nanoparticles decorated carbon sphere composites for enhanced non-enzymatic glucose sensing | |
| Li et al. | An electrochemical sensor based on platinum nanoparticles and mesoporous carbon composites for selective analysis of dopamine | |
| Zou et al. | Construction of a highly sensitive signal electrochemical sensor based on self-assembled cobalt oxide-hydroxylated single-walled carbon nanotubes composite for detection of dopamine in bovine serum samples | |
| CN103506161B (en) | Graphene complex, its catalysis methanol oxidation in application, chemically modified electrode and preparation method thereof | |
| Ramírez-García et al. | Carbon composite microelectrodes: charge percolation and electroanalytical performance |
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 | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201228 Address after: 224362 Tongyang town industrial concentration area, Sheyang County, Yancheng City, Jiangsu Province Patentee after: Yancheng Fuwanjia Thermal Insulation Board Co.,Ltd. Address before: 1800 No. 214122 Jiangsu city of Wuxi Province Li Lake Avenue Patentee before: Jiangnan University |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230913 Address after: No. 1 Science and Technology Innovation Park, Siming Town, Sheyang County, Yancheng City, Jiangsu Province, 224363 Patentee after: Yancheng Kezhiyuan Industrial Development Co.,Ltd. Address before: 224362 Tongyang town industrial concentration area, Sheyang County, Yancheng City, Jiangsu Province Patentee before: Yancheng Fuwanjia Thermal Insulation Board Co.,Ltd. |
|
| TR01 | Transfer of patent right |