CN104655698A - Graphene/graphene oxide microarray electrode as well as preparation method and application thereof - Google Patents
Graphene/graphene oxide microarray electrode as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN104655698A CN104655698A CN201510080785.2A CN201510080785A CN104655698A CN 104655698 A CN104655698 A CN 104655698A CN 201510080785 A CN201510080785 A CN 201510080785A CN 104655698 A CN104655698 A CN 104655698A
- Authority
- CN
- China
- Prior art keywords
- graphene
- electrode
- graphene oxide
- hydrogen peroxide
- concentration
- 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
Landscapes
- Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)
Abstract
The invention discloses a preparation method of a graphene/graphene oxide microarray and application of the graphene/graphene oxide microarray used as a chemical and cell-based sensor. A graphene/graphene oxide microarray electrode is prepared on an ITO glass substrate by combining a micro processing technology and an electrochemical method. By utilizing the electrochemical catalytic oxidation of the microelectrode prepared by the invention on hydrogen peroxide, the in vitro and intravital quantitative analysis and detection of hydrogen peroxide are realized by a timing amperometry. The preparation method is simple and feasible, the sensitivity is high, the response time is short, the biocompatibility is good, and the concentration of hydrogen peroxide can be quickly detected.
Description
Technical field
The invention belongs to micro Process and field of biological detection, relate to a kind of graphene/graphene oxide tiny array electrode and preparation method thereof and application.
Background technology
Hydrogen peroxide is ubiquity and the most stable reactivity keto (ROS) in cell, to important roles such as DNA Damage, Apoptosis, protein synthesis.Research shows, in cell, the disease such as exception and senile dementia, parkinsonism, artery sclerosis, cancer of hydrogen peroxide concentration exists certain contacting.Detect the concentration of emiocytosis hydrogen peroxide, the research for the diagnosis of disease pathology, disease and prevention etc. has important meaning.At present, be mainly divided into for the electrochemical sensor of hydrogen peroxide and have enzyme and non-enzymatic two kinds.Enzyme sensor is expensive, and service condition is strict; Non-enzyme sensor is many is catalytic center based on metal nano catalyzer, and the release of metallic ion produces certain toxicity to cell.Therefore the electrochemical sensor of non-loaded, self-catalysis, because of advantages such as its good stability, cost are low, good biocompatibilities, receives great concern.
Graphene is a kind of Two-dimensional Carbon atomic crystal that the A.Gaim of Univ Manchester UK in 2004 etc. finds, being the schistose texture of single or multiple lift, is the also the hardest the thinnest material found so far.Due to the character of its uniqueness, comprising: high strength (130GPa), the electron mobility (20000cm/Vs) of high speed under room temperature, high transmission rate (95%), high-specific surface area (2600m
2/ g), possess good electro catalytic activity and biocompatibility simultaneously.Scientist thinks, Graphene is expected to thoroughly change material science, be expected to replace silicon future and become materials of electronic components, be widely used in the numerous areas such as supercomputer, flexible touch screen, environmental protection and Medical Devices, photon sensor and organic solar batteries.The preparation of laboratory Graphene generally adopts with low cost, the simple oxidation-reduction method of preparation technology, by preparing graphene oxide, then through the cheaper alternative of redox graphene as Graphene.
Research shows that Graphene has certain catalytic oxidation effect to hydrogen peroxide, but catalytic activity does not have metallic catalyst activity high.And micro-array sensors has higher sensitivity, signal to noise ratio (S/N ratio), the advantages such as the response time is low, therefore graphene/graphene oxide micro-array biosensor is developed, not only increase catalytic activity, the biocompatibility of holding electrode simultaneously, significant for cell detection, and this design have not been reported at present.
Summary of the invention
The object of the design is the deficiency for existing application, a kind of graphene/graphene oxide tiny array electrode and preparation method thereof and application are provided, this tiny array electrode, while maintenance cytoactive, quick, sensitive, stably can detect the hydrogen peroxide of emiocytosis.
The object of the invention is to be achieved through the following technical solutions: be made up of ito glass and the conductive layer be deposited on ito glass, described conductive layer is by graphene oxide and be embedded in ordered arrangement RGO array in graphene oxide and form.
A preparation method for graphene/graphene oxide tiny array electrode, comprises the following steps:
(1) adopt photoetching technique to build array pattern on ito glass, be specially: be spun on by positive photoresist on ito glass, gluing rotating speed is 5000rpm, spin-coating time 10s; After spin coating, ito glass is dried 90s at 100 DEG C, obtains lithography layer; Then Lithographic template is placed on lithography layer, uv-exposure 60s; At 100 DEG C, dry 90s after exposure, finally develop 24s; Described Lithographic template has the figure of ordered arrangement;
(2) be that the graphene oxide water solution of 4mg/mL is spun in substrate prepared by step 1 further by concentration, rotating speed 3000 rpm, spin-coating time 30s;
(3) substrate after processing using step 2 is as working electrode, and silver/silver chloride electrode is contrast electrode, and platinized platinum is to electrode, with the Na of 0.2M
2hPO
4the NaH of solution and 0.2M
2pO
4solution is electrolytic solution according to the mixed solution that volume ratio 4:1 forms, under-1.1V constant potential, and electrochemical reduction 7 ~ 60s; After electrochemical reducting reaction terminates, substrate acetone is soaked 2h, remove photoresist, obtain graphene/graphene oxide tiny array electrode.
An application for graphene/graphene oxide tiny array electrode, this is applied as: graphene/graphene oxide tiny array electrode is used for the concentration detecting hydrogen peroxide solution.
Graphene/graphene oxide tiny array electrode is used for the concentration detecting hydrogen peroxide solution, be specially: be that working electrode, silver/silver chloride electrode are as contrast electrode, platinum plate electrode as to electrode using graphene/graphene oxide microarray according to claim 1, composition three-electrode system, measure the current-responsive value J of hydrogen peroxide solution sample to be measured, C=(J-1.5)/26.7; Wherein, J is current density response, C concentration value.
An application for graphene/graphene oxide tiny array electrode, this is applied as: concentration graphene/graphene oxide tiny array electrode being used for the hydrogen peroxide detecting emiocytosis.
Graphene/graphene oxide tiny array electrode is used for the concentration of the hydrogen peroxide detecting emiocytosis, be specially: on the graphene/graphene oxide tiny array electrode that cell is inoculated in, using postvaccinal graphene/graphene oxide tiny array electrode be working electrode, silver/silver chloride electrode as contrast electrode, platinum plate electrode as to electrode, take PBS solution as electrolytic solution; Stimulate the cell on working electrode to produce secretion hydrogen peroxide with PMA, measure current-responsive value J; According to C=(J-1.5)/26.7, calculate the concentration of emiocytosis hydrogen peroxide; Wherein, J is current density response, C concentration value.
The present invention has following beneficial effect: adopt photoetching technique to combine with galvanochemistry and prepare Graphene/graphite oxide microarray as working electrode, the catalytic oxidation effect to hydrogen peroxide is achieved under the condition of non-loaded any catalyzer, not only avoid that enzyme easy in inactivation is unstable, cost is high and the shortcoming such as the cytotoxicity of metallic ion, and substantially increase the sensitivity detecting hydrogen peroxide, the hydrogen peroxide in environment and in live body can be measured quick, sensitive, exactly.Electrode material cost used is low, have certain theory and practical value; Preparation method is simple, repeatability is high.
Accompanying drawing explanation
Fig. 1 is the structural representation of graphene/graphene oxide tiny array electrode of the present invention; In figure, 1 be ito glass 1,2 be graphene oxide, 3 be RGO array;
Fig. 2 is the structural representation of Lithographic template;
Fig. 3 is the shape appearance figure of 6 samples prepared by embodiment 1; Wherein can find out color darker be Graphene, peripheral region is graphene oxide.
Fig. 4 is infrared (IR) spectrogram of 3 samples prepared by embodiment 1.
Fig. 5 be the graphene/graphene oxide array of different recovery time at catalysis voltage 0.6V, catalytic current densogram in 10mM aqueous hydrogen peroxide solution;
Fig. 6 is graphene/graphene oxide tiny array electrode of the present invention with the Na of 0.1M
2hPO
4the NaH of solution and 0.1M
2pO
4solution is electrolytic solution according to the mixed solution that volume ratio 4:1 forms, and adds variable concentrations hydrogen peroxide solution successively under agitation, the electric current-time curve obtained;
Fig. 7 is the concentration of hydrogen peroxide and the linear relationship chart of current-responsive;
Fig. 8 is the fluorescent microscope picture of graphene/graphene oxide array inoculation neurocyte prepared by the present invention, comprises cell F-actin albumen and nucleus;
With the Na of 0.1M after Fig. 9 graphene/graphene oxide array of the present invention inoculating cell
2hPO
4the NaH of solution and 0.1M
2pO
4in the mixed solution that solution forms according to volume ratio 4:1, under three-electrode system, with medicine PMA irritation cell secretion hydrogen peroxide, the timing ampere curve obtained.Wherein a curve is control group, and medicine PMA stimulates the array electrode of non-inoculating cell; B curve is experimental group, and medicine PMA stimulates the array electrode of inoculating cell.
Embodiment
As shown in Figure 1, a kind of graphene/graphene oxide tiny array electrode, is made up of ito glass 1 and the graphene layer be deposited on ito glass, and described graphene layer is by graphene oxide 2 and be embedded in ordered arrangement RGO array 3 in graphene oxide 2 and form.Further illustrate technical solution of the present invention below in conjunction with specific embodiment, these embodiments can not be interpreted as it is restriction to technical solution.
Embodiment 1: the present embodiment prepares graphene/graphene oxide tiny array electrode, comprises the following steps:
(1) cleaning of ito glass: the ito glass of 6mm × 9mm is placed in beaker, use the ultrasonic 10min of acetone, absolute ethyl alcohol, deionized water successively respectively, then nitrogen dries up stand-by.
(2) design Lithographic template, be provided with the figure of ordered arrangement in template, these figures can be circular, as shown in Figure 2, also can be square, triangle, hexagon etc., adopt conventional circular pattern in the present embodiment, and this template be prepared by Microelectronics Institute of Beijing Chinese Academy of Sciences.
(3) photoetching technique is adopted to carve array pattern on ito glass: be specially: be spun on by positive photoresist on ito glass, gluing rotating speed is 5000rpm, spin-coating time 10s; After spin coating, ito glass is dried 90s at 100 DEG C, obtains lithography layer; Then the Lithographic template described in step 2 is placed on lithography layer, uv-exposure 60s; At 100 DEG C, 90s is dried after exposure; Finally develop 24s; Prepare 5 samples.
(4) spin coating 4mg/mL graphene oxide (GO) in 6 substrates after step 3 processes, rotating speed 3000 rpm, spin-coating time 30s, rotate three times, obtains 6 substrates (I-1, I-2, I-3, I-4, I-5, I-6).
(5) respectively with above-mentioned substrate working electrode, silver/silver chloride electrode is contrast electrode, and platinized platinum is to electrode, with the Na of 0.2M
2hPO
4the NaH of solution and 0.2M
2pO
4solution is electrolytic solution according to the mixed solution that volume ratio 4:1 forms, under-1.1V constant potential, electrochemical reduction 7s(I-1), 15s(I-2), 22s(I-3), 30s(I-4), 45s(I-5), 60s(I-6); After electrochemical reducting reaction terminates, substrate acetone is soaked 2h, remove photoresist, obtain graphene/graphene oxide tiny array electrode.
I-1, I-2, I-3, I-4, I-5, I-6 sample obtained by microscopic examination step 5, as shown in Figure 3, as seen from the figure, when the recovery time is 7s, graphene array is the disk of 20 μm, spacing 60 μm, and array sizes is homogeneous complete, along with the increase of recovery time, Graphene radius constantly increases.Fig. 4 is the infrared spectrum curve of II-1, II-4 sample that step 5 obtains, C=O (1731 cm on data display graphene oxide
-1), C-OH (1224 cm
-1) and C-O-C peak (1065 cm
-1) disappear after reduction 7s, illustrate that graphene oxide is reduced.Then along with the increase of recovery time, the change of group peak is not obvious, just can obtain Graphene when reduction 7s is described.
Embodiment 2: graphene/graphene oxide array electrode embodiment 1 prepared is used for the mensuration of hydrogen peroxide concentration.
Fig. 5 is graphene/graphene oxide array (as shown in Figure 3) catalytic current densimetric curve in 10mM hydrogen peroxide of different recovery time, as can be seen from the figure, the ability of the electro-catalysis decomposing hydrogen dioxide solution of the sample I-4 of reduction 30s is the strongest, and therefore the present embodiment adopts sample I-4 to measure the concentration of unknown hydrogen peroxide.
Using sample I-4 be working electrode, silver/silver chloride electrode as contrast electrode, platinum plate electrode as to electrode, composition three-electrode system; When measuring hydrogen peroxide concentration, three-electrode system is placed in and fills the Na that 30ml concentration is 0.1M
2hPO
4solution and concentration are the NaH of 0.1M
2pO
4in the beaker of the mixed solution that solution forms according to volume ratio 4:1, then 0.6V constant voltage is applied on the working electrode (s, record current-time curve, when background current reach stable after, in solution, 34 μ L hydrogen peroxide solutions (concentration as shown in Figure 6) are added every 50s, by measuring the response current of the hydrogen peroxide of variable concentrations, obtain electric current-time curve, as shown in Figure 6.According to the data of Fig. 6, the electric current-curve of solubility shown in Fig. 7 can be obtained further.As shown in Figure 7, response current and hydrogen peroxide concentration meet equation of linear regression J=1.5+26.7C, and variance is 0.990; Wherein J is responsive current density value, and unit is nAmm
-2, C is concentration, and unit is mM.It can thus be appreciated that, C=(J-1.5)/26.7.
Embodiment 3: graphene/graphene oxide tiny array electrode I-4 embodiment 1 prepared is used for the cultivation of neurocyte and the mensuration of emiocytosis hydrogen peroxide.
Inoculate neurocyte PC12 after going back sample I-4 sterilizing, inoculum density 3000/mL, in containing 10% hyclone, 1% dual anti-nutrient culture media, cultivate 24h.By the two actin of transfect cell of immunofluorescence and the growth conditions of nucleus observation of cell, wherein, adopt the F-actin albumen of Acti-Stain Phalloidin transfect cell, DAPI transfect cell core.When emiocytosis hydrogen peroxide detects, graphene/graphene oxide array inoculating cell to be cultivated after 24h as working electrode, silver/silver chloride electrode as contrast electrode, platinum plate electrode as to electrode, and composition three-electrode system is placed in and fills the Na that 30ml concentration is 0.2M
2hPO
4the NaH of solution and 0.2M
2pO
4in the beaker of the mixed solution that solution forms according to volume ratio 4:1, then 0.6V constant voltage is applied on the working electrode (s, when background current reach stable after, inject to working electrode 12-myristic acid-13-acetic acid phorbol (PMA) that 10 μ L concentration are 100nM, record current-time curve.The non-inoculating cell of control group, other operations are identical with experimental group.
According to the method described above, graphene/graphene oxide microarray is used for the cultivation of neurocyte and the mensuration of emiocytosis hydrogen peroxide.Fig. 8 is the fluorescent microscope picture of graphene/graphene oxide microarray inoculation neurocyte prepared by the present invention.Can find out that cell majority is distributed on graphene oxide, growth conditions is good, and cell feeler is fixed on the interface of Graphene and graphene oxide more, and the hydrogen peroxide being conducive to emiocytosis is diffused on Graphene.Because cell is seeded on array electrode, the direct catalyzed decomposition of hydrogen peroxide of emiocytosis, according to J=1.5+26.7C, directly can calculate the hydrogen peroxide concentration of emiocytosis, does not need further calculating.Fig. 9 is the Na at 0.1M after graphene/graphene oxide microarray of the present invention inoculation neurocyte PC12
2hPO
4the NaH of solution and 0.1M
2pO
4in the mixed solution that solution forms according to volume ratio 4:1, be the PMA irritation cell secretion hydrogen peroxide of 100nM by 10 μ L concentration, the timing ampere curve obtained.Wherein a curve is control group, and medicine PMA stimulates the array electrode of non-inoculating cell; B curve is experimental group, and medicine PMA stimulates the array electrode of inoculating cell.Find out in figure, during PMA stimulation test group, produce response current instantaneously, and very fast electric current recovers initial position very soon, the very fast catalyzed decomposition of hydrogen peroxide of secretion is described.The responsive current density that first time PMA stimulates is 3.9nAmm
-2, according to the equation of linear regression that embodiment 2 obtains, the concentration calculating the hydrogen peroxide of emiocytosis is 0.15mM.It can thus be appreciated that graphene/graphene oxide microarray preparation method prepared by the inventive method is simple, repeatability is high, cost is lower.Can stablize, detect accurately, rapidly and sensitively the concentration of hydrogen peroxide for hydrogen peroxide sensor, its detectability reaches ~ 200nM, and the hydrogen peroxide sensor of the noble metal catalyst reported with great majority is suitable.Especially in cell sensor, show good biologically active and higher sensitivity, there is very large Development volue.
Claims (6)
1. a graphene/graphene oxide tiny array electrode, it is characterized in that, be made up of ito glass (1) and the conductive layer be deposited on ito glass (1), described conductive layer is by graphene oxide (2) and be embedded in ordered arrangement RGO array (3) in graphene oxide (2) and form.
2. a preparation method for graphene/graphene oxide tiny array electrode according to claim 1, is characterized in that, comprise the following steps:
(1) adopt photoetching technique to build array pattern on ito glass, be specially: be spun on by positive photoresist on ito glass, gluing rotating speed is 5000rpm, spin-coating time 10s; After spin coating, ito glass is dried 90s at 100 DEG C, obtains lithography layer; Then Lithographic template is placed on lithography layer, uv-exposure 60s; At 100 DEG C, dry 90s after exposure, finally develop 24s; Described Lithographic template has the figure of ordered arrangement;
(2) be that the graphene oxide water solution of 4mg/mL is spun in substrate prepared by step 1 further by concentration, rotating speed 3000 rpm, spin-coating time 30s;
(3) substrate after processing using step 2 is as working electrode, and silver/silver chloride electrode is contrast electrode, and platinized platinum is to electrode, with the Na of 0.2M
2hPO
4the NaH of solution and 0.2M
2pO
4solution is electrolytic solution according to the mixed solution that volume ratio 4:1 forms, under-1.1V constant potential, and electrochemical reduction 7 ~ 60s; After electrochemical reducting reaction terminates, substrate acetone is soaked 2h, remove photoresist, obtain graphene/graphene oxide tiny array electrode.
3. an application for graphene/graphene oxide tiny array electrode according to claim 1, it is characterized in that, this is applied as: graphene/graphene oxide tiny array electrode is used for the concentration detecting hydrogen peroxide solution.
4. application according to claim 3, it is characterized in that: concentration graphene/graphene oxide tiny array electrode being used for detecting hydrogen peroxide solution, be specially: be that working electrode, silver/silver chloride electrode are as contrast electrode, platinum plate electrode as to electrode using graphene/graphene oxide microarray according to claim 1, composition three-electrode system, measure the current-responsive value J of hydrogen peroxide solution sample to be measured, C=(J-1.5)/26.7; Wherein, J is current density response, C concentration value.
5. an application for graphene/graphene oxide tiny array electrode according to claim 1, it is characterized in that, this is applied as: concentration graphene/graphene oxide tiny array electrode being used for the hydrogen peroxide detecting emiocytosis.
6. application according to claim 5, it is characterized in that: concentration graphene/graphene oxide tiny array electrode being used for detecting the hydrogen peroxide of emiocytosis, be specially: on the graphene/graphene oxide tiny array electrode that cell is inoculated in, using postvaccinal graphene/graphene oxide tiny array electrode be working electrode, silver/silver chloride electrode as contrast electrode, platinum plate electrode as to electrode, take PBS solution as electrolytic solution; Stimulate the cell on working electrode to produce secretion hydrogen peroxide with PMA, measure current-responsive value J; According to C=(J-1.5)/26.7, calculate the concentration of emiocytosis hydrogen peroxide; Wherein, J is current density response, C concentration value.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510080785.2A CN104655698B (en) | 2015-02-15 | 2015-02-15 | Graphene/graphene oxide tiny array electrode and preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510080785.2A CN104655698B (en) | 2015-02-15 | 2015-02-15 | Graphene/graphene oxide tiny array electrode and preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104655698A true CN104655698A (en) | 2015-05-27 |
| CN104655698B CN104655698B (en) | 2017-07-25 |
Family
ID=53247077
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510080785.2A Active CN104655698B (en) | 2015-02-15 | 2015-02-15 | Graphene/graphene oxide tiny array electrode and preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104655698B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105136860A (en) * | 2015-07-24 | 2015-12-09 | 浙江大学 | Humidity sensor based on graphene oxide/graphene/silicon and preparation method thereof |
| CN109468220A (en) * | 2018-11-15 | 2019-03-15 | 江南大学 | Graphene chip for microbial cell biological information real-time detection |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102181877A (en) * | 2011-04-25 | 2011-09-14 | 同济大学 | Graphene oxide for electrochemical reduction and preparation method of graphene |
| CN102653454A (en) * | 2011-08-12 | 2012-09-05 | 京东方科技集团股份有限公司 | Preparation method for patterned graphene membrane |
| CN102879442A (en) * | 2012-10-12 | 2013-01-16 | 上海交通大学 | Graphene quantum dot modified electrochemical sensor, and preparation method and application thereof |
| CN104039695A (en) * | 2011-09-19 | 2014-09-10 | 卧龙岗大学 | Reduced graphene oxide and method of producing same |
-
2015
- 2015-02-15 CN CN201510080785.2A patent/CN104655698B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102181877A (en) * | 2011-04-25 | 2011-09-14 | 同济大学 | Graphene oxide for electrochemical reduction and preparation method of graphene |
| CN102653454A (en) * | 2011-08-12 | 2012-09-05 | 京东方科技集团股份有限公司 | Preparation method for patterned graphene membrane |
| CN104039695A (en) * | 2011-09-19 | 2014-09-10 | 卧龙岗大学 | Reduced graphene oxide and method of producing same |
| CN102879442A (en) * | 2012-10-12 | 2013-01-16 | 上海交通大学 | Graphene quantum dot modified electrochemical sensor, and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 张美宁 等: "石墨烯微电极阵列的制备及应用", 《中国化学会第28届学术年会第9分会场摘要集》 * |
| 邵瑞强: "石墨烯氧化物的光还原以及其器件制备的基础研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105136860A (en) * | 2015-07-24 | 2015-12-09 | 浙江大学 | Humidity sensor based on graphene oxide/graphene/silicon and preparation method thereof |
| CN109468220A (en) * | 2018-11-15 | 2019-03-15 | 江南大学 | Graphene chip for microbial cell biological information real-time detection |
| CN109468220B (en) * | 2018-11-15 | 2020-05-01 | 江南大学 | Graphene chip for real-time detection of biological information of microbial cells |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104655698B (en) | 2017-07-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | A thin film polyethylene terephthalate (PET) electrochemical sensor for detection of glucose in sweat | |
| Wang et al. | Au-nanoclusters incorporated 3-amino-5-mercapto-1, 2, 4-triazole film modified electrode for the simultaneous determination of ascorbic acid, dopamine, uric acid and nitrite | |
| Niu et al. | Fabrication of graphene and gold nanoparticle modified acupuncture needle electrode and its application in rutin analysis | |
| Ramulu et al. | Nanowires array modified electrode for enhanced electrochemical detection of nucleic acid | |
| Ahmad et al. | High performance cholesterol sensor based on ZnO nanotubes grown on Si/Ag electrodes | |
| Pradhan et al. | High-performance, flexible enzymatic glucose biosensor based on ZnO nanowires supported on a gold-coated polyester substrate | |
| Liu et al. | Reagentless glucose biosensor based on direct electron transfer of glucose oxidase immobilized on colloidal gold modified carbon paste electrode | |
| Zhao et al. | Direct electrochemistry of horseradish peroxidase at carbon nanotube powder microelectrode | |
| Haghighi et al. | Direct electron transfer from glucose oxidase immobilized on an overoxidized polypyrrole film decorated with Au nanoparticles | |
| CN101975807B (en) | Three-dimensional Pt-Pb nano floricome type enzyme-free glucose sensor electrode as well as preparation and application thereof | |
| Du et al. | Nonenzymatic uric acid electrochemical sensor based on graphene-modified carbon fiber electrode | |
| Xiao et al. | An reagentless glucose biosensor based on direct electrochemistry of glucose oxidase immobilized on poly (methylene blue) doped silica nanocomposites | |
| Gokoglan et al. | Paper based glucose biosensor using graphene modified with a conducting polymer and gold nanoparticles | |
| Yang et al. | Direct electrochemical determination of morphine on a novel gold nanotube arrays electrode | |
| Wu et al. | Amperometric cholesterol biosensor based on zinc oxide films on a silver nanowire–graphene oxide modified electrode | |
| CN104977343B (en) | A kind of high performance biosensors based on graphene/mesoporous carbon nano-composite material and preparation method thereof | |
| Hatamie et al. | Fabrication and characterization of highly-ordered Zinc Oxide nanorods on gold/glass electrode, and its application as a voltammetric sensor | |
| US20170176414A1 (en) | Electrochemical method and device for detecting the effect of anticancer drugs | |
| CN102156156A (en) | Three-dimensional copper oxide nanometer flower-based chip enzyme-free glucose sensor electrode as well as preparation method and application thereof | |
| Chuang et al. | Multifunctional microelectrode array (mMEA) chip for neural-electrical and neural-chemical interfaces: characterization of comb interdigitated electrode towards dopamine detection | |
| CN103207224A (en) | Electrochemical biosensor electrode for detection of hydrogen peroxide and preparation method thereof | |
| Zhan et al. | A novel epinephrine biosensor based on gold nanoparticles coordinated polydopamine-functionalized acupuncture needle microelectrode | |
| CN107436316A (en) | The preparation of glucose sensor based on graphene and graphene oxide composite material | |
| CN105466980A (en) | Living plant ascorbic acid detection method based on microelectrode biosensor | |
| Li et al. | Simultaneous detection of lactate and glucose by integrated printed circuit board based array sensing chip |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200114 Address after: Room c105-1, Lianhua Zhigu Pioneer Park, No.128, Danxia Road, economic development zone, Hefei City, Anhui Province, 230000 Patentee after: Hefei Yupu Health Technology Co.,Ltd. Address before: 310018, No. 928, No. 2, Poplar Street, Hangzhou Economic Development Zone, Hangzhou, Zhejiang Patentee before: ZHEJIANG SCI-TECH University |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200429 Address after: Room 101, floor 6, office building 494, Huaguang Avenue (original Changzheng Road), Yuhui District, Bengbu City, Anhui Province Patentee after: Anhui Zhongke Dayu Technology Co.,Ltd. Address before: Room c105-1, Lianhua Zhigu Pioneer Park, No.128, Danxia Road, economic development zone, Hefei City, Anhui Province, 230000 Patentee before: Hefei Yupu Health Technology Co.,Ltd. |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Preparation and application of graphene/graphene oxide microarray electrode Effective date of registration: 20221227 Granted publication date: 20170725 Pledgee: Bengbu Longhu Sub branch of Huishang Bank Co.,Ltd. Pledgor: Anhui Zhongke Dayu Technology Co.,Ltd. Registration number: Y2022980029070 |