CN101581690B - Special electrode for in-vivo voltammetry analysis and preparation method thereof - Google Patents
Special electrode for in-vivo voltammetry analysis and preparation method thereof Download PDFInfo
- Publication number
- CN101581690B CN101581690B CN 200810111625 CN200810111625A CN101581690B CN 101581690 B CN101581690 B CN 101581690B CN 200810111625 CN200810111625 CN 200810111625 CN 200810111625 A CN200810111625 A CN 200810111625A CN 101581690 B CN101581690 B CN 101581690B
- Authority
- CN
- China
- Prior art keywords
- carbon fiber
- electrode
- solution
- carbon
- pipette tips
- 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.)
- Expired - Fee Related
Links
Images
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a special electrode for in-vivo voltammetry analysis and a preparation method thereof. The preparation method of the special electrode comprises the following steps: 1) preparing carbon fiber coated with a carbon nanomaterial on surface; 2) preparing a carbon fiber microelectrode; 3) soaking the carbon fiber electrode prepared by the step 2) in solution for ultrasonic washing; and 4) subjecting the carbon fiber electrode prepared by the step 3) to electrochemical pretreatment to obtain the special electrode. Meanwhile, an electrochemical detection device for in vitro correction or in vivo real-time physiological activator monitoring is prepared by using the special electrode. The electrochemical detection device comprises the special electrode for physiological activator monitoring of the invention, a reference electrode and an auxiliary electrode. The electrochemical detection device prepared by using the special electrode of the invention can meet the requirements for the in-vivo voltammetry analysis of physiological activators and has a promising application prospect in researches in fields of neurophysiology, clinical medicine and the like.
Description
Technical field
The present invention relates to a kind of electrode special that can satisfy the physiological activator vivo voltammetry analysis and preparation method thereof.
Background technology
In the last few years, the research of chemical substance Changing Pattern in physiology, pathologic process had become the advanced problems of people's extensive concern, and this mainly is because the information of chemical substance live body real-time change can directly reflect the chemical nature in physiology and the pathologic process.For example, the variation of glucose and lactic acid can directly reflect brain self-energy metabolic process in the brain; Neurotransmitter dopamine exists level and Changing Pattern thereof directly related with important physiological phenomenons such as somatic movement and cerebrations in brain; The oxidative damage that has level and interior free yl and the synthetic of neuropeptide of ascorbic acid are closely related in the brain.Therefore, foundation can be applicable to Organism and learns the real-time monitoring method of live body of material and have very important physiology and pathology sense.
Microelectrode vivo voltammetry method has the advantages such as very high time and spatial resolution because employed electrode has micron or nano-grade size and damages less characteristics and method itself for biosome, is particularly suitable for the live body Real-Time Monitoring of physiological activator.At present, miniature electrochemical is to utilize carbon fiber microelectrodes with micro pipette tips, carbon paste microelectrode, metal microelectrode and some modified electrode to set up and develop the detection method of physiological activator basically.Although the method for having set up can satisfy the live body Real-Time Monitoring of part physiological activator, but still there is very large challenge in the research of microelectrode vivo voltammetry analysis method, is mainly reflected in the aspects such as the reappearance of preparation, method of the electrode that can satisfy the vivo voltammetry analysis purpose and stability.
Summary of the invention
The purpose of this invention is to provide a kind of electrode special of using for physiological activator live body Real-Time Monitoring and preparation method thereof.
Electrode special provided by the present invention prepares according to the method that may further comprise the steps:
1) carbon fiber of the surperficial coated carbon nano material of preparation;
2) with step 1) carbon fiber prepare carbon fiber microelectrodes with micro pipette tips;
3) with step 2) carbon fiber microelectrodes with micro pipette tips of preparation immerses in the solution and carries out ultrasonic cleaning;
4) with step 3) carbon fiber microelectrodes with micro pipette tips carry out electrochemical pre-treatment, namely obtain electrode special of the present invention.
The carbon fiber of surface coverage carbon nanomaterial wherein, described step 1) is prepared as follows:
At first, with carbon fiber and SiCl
4At high temperature reaction obtains SiO
2The carbon fiber that covers, the Pintsch process by iron-phthalocyanine again is at SiO
2The uniform and stable carbon nanomaterial of carbon fiber surface growth that covers.(list of references: Small 2006,2,1052-1059 and The Journal of Physical Chemistry B 1999,103,4223-4227)
The carbon fiber microelectrodes with micro pipette tips of described surface coverage carbon nanomaterial can be prepared as follows:
With described step 1) resulting carbon fiber attaches on the tinsel of conduction with conducting resinl, and penetrate in the glass capillary of the both ends open that has drawn, the glass tube front end exposes the carbon fiber of certain-length.Then the glass tube rear and front end is sealed with insulating gel, and prepared electrode is placed 100 ℃ of lower baking 1h, can obtain step 2) carbon fiber microelectrodes with micro pipette tips of described surface coverage carbon nanomaterial.The tinsel of described conduction specifically can be copper wire or iron wire.
Described step 3) ultrasonic cleaning in is successively at acetone, ethanol, 1.0～3.0M HNO
3Carry out in solution, 1.0～2.0M KOH solution and the intermediate water.
Described step 4) electrochemical pre-treatment can be carried out in acidic aqueous solution or alkaline aqueous solution; Described acidic aqueous solution specifically can be sulfuric acid solution or the 0.5M salpeter solution of 0.5M; Described alkaline aqueous solution specifically can be the NaOH solution of 0.5～1.0M, KOH solution or the 0.5～1.0M Ba (OH) of 0.5～1.0M
2Solution.
Described step 4) electrochemical pre-treatment in can adopt cyclic voltammetry, potential step method or chronoamperometry.
The method of electrochemical pre-treatment described step 4) specifically can according to following a) or b) carry out:
A) with step 3) the carbon fiber microelectrodes with micro pipette tips of surface coverage carbon nanomaterial immerse in the sulfuric acid solution or 0.5M salpeter solution of 0.5M, apply first+potential polarization 30～50s of 2.0V, then apply-potential polarization 10～30s of 1.0V, again with 0.05～0.2Vs
-1Sweep velocity in the potential range of 0.0-1.0V scan round till obtain stable cyclic voltammogram;
B) with step 3) the carbon fiber microelectrodes with micro pipette tips of surface coverage carbon nanomaterial immerse the NaOH solution of 1.0M, KOH solution or the 0.5～1.0M Ba (OH) of 1.0M
2In the solution, apply+potential polarization 50～180s of 1.0～1.5V.
Utilize electrode special of the present invention, can also prepare a kind of electrochemical detection device for live body Real-Time Monitoring physiological activator, comprising: the present invention is used for electrode special, contrast electrode and the auxiliary electrode of physiological activator monitoring.
Described electrode special and electrochemical detection device can be used for external correction and live body Real-Time Monitoring physiological activator; The physiological activator of described external correction is adrenaline, and the physiological activator of described live body Real-Time Monitoring is ascorbic acid.
Carbon nanomaterial causes people's broad interest owing to have unique physics and chemistry character in a lot of scientific researches and industrial circle.Carbon nanomaterial and have very important using value by the nano-complex that the whole bag of tricks obtains in the research of Electroanalytical Chemistry is becoming the focus of people's extensive concern based on the Electroanalytical Chemistry research of carbon nanomaterial and nano-complex thereof.
The present invention utilize surface coverage the carbon fiber of uniform and stable carbon nanomaterial prepare microelectrode, by it is carried out easy pre-service, can obtain the electrode special that physiological activator is had good electrocatalytic effect and satisfies the real-time volt-ampere analysis of physiological activator live body.This electrode special has been avoided manually modified on the fine little surface of carbon of carbon nanomaterial, thereby has an advantage that is easy to reappear.In addition, this electrode special has very high selectivity, lower detectability and stability preferably, can satisfy the vivo voltammetry analysis of physiological activator.This is invented described electrode special and is with a wide range of applications in the researchs such as neuro-physiology and clinical medicine.
Description of drawings
Fig. 1 is the synoptic diagram of the electrode special of embodiment 3 and embodiment 4; Wherein, 1 is copper wire, and 2 is glass capillary, and 3 is conducting resinl, and 4 is the carbon fiber of the surface coverage carbon nanomaterial of embodiment 1.
Fig. 2 is that the electrochemical detection device of embodiment 5 is to adrenergic voltammogram in the artificial cerebrospinal fluid.
Fig. 3 is that the electrochemical detection device of embodiment 6 is to the vivo voltammetry figure of ascorbic acid in the rat brain.
Embodiment
The preparation of the carbon fiber of embodiment 1, surface coverage carbon nanomaterial
Carbon fiber (T650-35, diameter are 7 μ m) (Fabric Development Inc.).Carbon fiber inserted in 1100 ℃ the high temperature furnace, and with SiCl
4The mixed airflow 20min that passes into 300mL/min argon gas and 40mL/min hydrogen injects the high temperature furnace that contains atmospheric oxygen, by utilizing SiCl
4With the reaction of carbon fiber, at the fine little Surface Creation SiO of carbon
2Thin layer.With prepared carbon fiber and 0.1～0.3g iron-phthalocyanine (FeC
32N
8H
16) place respectively same quartz glass tube, at Ar/H
2(volume ratio is 1: 1～1: 2, and flow velocity is 20～40cm
3Under/min) the atmosphere, carry out different heat treated for carbon is fine little with iron-phthalocyanine.Fine little thermal treatment is to be 800～1100 ℃ of lower heating 2～15min in temperature for carbon, is to be 500～600 ℃ of lower heating 2～15min in temperature for the thermal treatment of iron-phthalocyanine.The temperature of controlling subsequently both is 800～1100 ℃ of heating 20～30min, can obtain the carbon fiber of surface coverage carbon nanomaterial.The diameter of used carbon fiber has no significant effect this electrochemical catalysis performance of inventing described electrode special.(list of references: Small 2006,2,1052-1059 and The Journal of Physical Chemistry B1999,103,4223-4227)
The preparation of the carbon fiber microelectrodes with micro pipette tips of embodiment 2, surface coverage carbon nanomaterial
Attach on 5～10cm copper wire the carbon fiber of the surface coverage carbon nanomaterial of the embodiment 1 of 1～2cm is little with conducting resinl, and it is penetrated (internal diameter is 1.5mm in the glass capillary of the both ends open that has drawn, length is 10cm), taper end opening internal diameter is 30～50 μ m, and the fine little length of the carbon that this end exposes is about 1mm.The butt end of glass tube exposes copper wire.After the both ends open of glass tube sealed with insulating gel, prepared electrode placed 100 ℃ of lower baking 1h, namely got the carbon fiber microelectrodes with micro pipette tips of surface coverage carbon nanomaterial.
The carbon fiber electrode of the surface coverage carbon nanomaterial that 1) embodiment 2 is prepared is successively at acetone, ethanol, 1.0～3.0M HNO
3, ultrasonic in 1.0～2.0M KOH solution and the intermediate water.Ultrasound intensity is 20W/cm
2, ultrasonic frequency is 50kHz, and the mode of ultrasonication is the ultrasonic work 20s of every interval 15s, and the ultrasonic time is 2～5min;
2) with step 1) carbon fiber electrode carries out electrochemical activation in the sulfuric acid solution of 0.5M, namely at first apply at electrode+potential polarization 30～50s of 2.0V, then apply-potential polarization 10～30s of 1.0V.Resulting electrode passes through with 0.05～0.2Vs again
-1The scan round of sweep velocity in the potential range of 0.0-1.0V arrive, until obtain till the stable cyclic voltammogram.The prepared synoptic diagram that is used for physiological activator vivo voltammetry analysis electrode special as shown in Figure 1.
The carbon fiber electrode of the surface coverage carbon nanomaterial that 1) embodiment 2 is prepared is successively at acetone, ethanol, 1.0～3.0M HNO
3, ultrasonic in 1.0～2.0M KOH solution and the intermediate water.Ultrasound intensity is 20W/cm
2, ultrasonic frequency is 50kHz, and the mode of ultrasonication is the ultrasonic work 20s of every interval 15s, and the ultrasonic time is 2～5min;
2) with step 1) carbon fiber electrode carries out electrochemical activation in 0.5～1.0M NaOH solution, namely apply at electrode+1.0～+ current potential of 1.5V, polarization 50～180s.The prepared synoptic diagram that is used for physiological activator vivo voltammetry analysis electrode special as shown in Figure 1.
The external Electrochemical Detection of embodiment 5, physiological activator
The external electrochemical detection device of physiological activator comprises: the electrode special of embodiment 3 is working electrode, and homemade Ag/AgCl (internal-filling liquid is artificial cerebrospinal fluid) is contrast electrode, and platinum filament is auxiliary electrode.Document Analytical Chemistry 2007,79,6559-6565 are seen in the preparation of contrast electrode.This three electrode is inserted in the standard solution of certain density physiological activator and with electrochemical workstation and be connected the voltammogram of record physiological activator with data collector.This electrochemical workstation and data collector can adopt at present various equipment commonly used, such as electrochemical workstation BAS 100B/W be attached thereto the computer system that connects.
Fig. 2 is for utilizing above-mentioned electrochemical detection device to adrenergic external volt-ampere response diagram.The condition of cyclic voltammetric is: sweep limit is-0.1～+ 0.3V (vs.Ag/AgCl), sweep speed is 10mV/s, adrenergic concentration is 50 μ M.The result shows that prepared electrode special produces the current-responsive of stable state for adrenaline in artificial cerebrospinal fluid, and this current-responsive can be used for the external test of this material and proofread and correct adrenergic concentration in the animal body.
The vivo voltammetry of ascorbic acid monitoring in embodiment 6, the rat brain
The electrochemical detection device of physiological activator comprises: the electrode special of embodiment 4 is working electrode, and homemade Ag/AgCl (internal-filling liquid is artificial cerebrospinal fluid) is contrast electrode, and platinum filament is auxiliary electrode.Document Analytical Chemistry 2007,79,6559-6565 are seen in the preparation of contrast electrode.To be connected with data collector in the brain tissue of this three electrodes implantation rat and in electrochemical detection device.Galvanochemistry work detection device station and data collector can adopt at present various equipment commonly used, such as electrochemical workstation BAS 100B/W be attached thereto the computer system that connects.
Fig. 3 utilizes above-mentioned detection device to the vivo voltammetry response diagram of ascorbic acid in the rat brain.Adopting the condition of live body cyclic voltammetric to be: sweep limit is-0.25～+ 0.2V (vs.Ag/AgCl), sweep velocity is 10mV/s.The result shows that electrode special prepared among the present invention produces obvious current-responsive to the ascorbic acid in the rat brain, accordingly can the Real-Time Monitoring animal brain in the concentration of ascorbic acid.The species that have multiple electrochemical activity in rat brain, these species may be on electrode the generation current signal, and then disturb the mensuration of this method.Electrode special of the present invention has been realized its good electric catalysis and selective determination for ascorbic acid owing to the surface has carbon nanomaterial.The experiment by Micro-perfusion in Graft After ascorbic acid oxidase in brain has obtained further checking for the selectivity of ascorbic acid for prepared electrode special among the present invention.Wherein, (Analytical Chemistry 2007,79,6559-6565) carry out by the middle method of describing according to document for the experimental technique of the interior Micro-perfusion in Graft After ascorbic acid oxidase of brain.
Claims (10)
1. the preparation method of a microelectrode may further comprise the steps:
1) carbon fiber of the surperficial coated carbon nano material of preparation;
2) with step 1) carbon fiber prepare carbon fiber microelectrodes with micro pipette tips;
3) with step 2) carbon fiber microelectrodes with micro pipette tips of preparation immerses in the solution and carries out ultrasonic cleaning;
4) with step 3) carbon fiber microelectrodes with micro pipette tips carry out electrochemical pre-treatment, namely obtain described microelectrode;
The method of described electrochemical pre-treatment according to following a) or b) carry out:
A) with described step 3) the carbon fiber microelectrodes with micro pipette tips of surface coverage carbon nanomaterial immerse in the sulfuric acid solution or 0.5M salpeter solution of 0.5M, apply first+potential polarization 30～50s of 2.0V, then apply-potential polarization 10～30s of 1.0V, again with 0.05～0.2Vs
-1Sweep velocity in the potential range of 0.0-1.0V scan round till obtain stable cyclic voltammogram;
B) with described step 3) the carbon fiber microelectrodes with micro pipette tips of surface coverage carbon nanomaterial immerse the NaOH solution of 1.0M, KOH solution or the 0.5～1.0M Ba (OH) of 1.0M
2In the solution, apply+potential polarization 50～180s of 1.0～1.5V.
2. method according to claim 1, it is characterized in that: the carbon fiber of the surface coverage carbon nanomaterial described step 1) is prepared as follows: at first with carbon fiber and SiCl
4At high temperature reaction obtains SiO
2The carbon fiber that covers, the Pintsch process by iron-phthalocyanine again is at SiO
2The uniform and stable carbon nanomaterial of carbon fiber surface growth that covers.
3. method according to claim 1, it is characterized in that: the carbon fiber microelectrodes with micro pipette tips described step 2) is prepared as follows: with described step 1) resulting carbon fiber attaches on the tinsel of conduction with conducting resinl, and penetrate in the glass capillary of the both ends open that has drawn, then the glass tube rear and front end is sealed with insulating gel, and prepared electrode placed 100 ℃ of lower baking 1h, namely obtain carbon fiber microelectrodes with micro pipette tips.
4. method according to claim 1, it is characterized in that: described ultrasonic cleaning is successively at acetone, ethanol, 1.0～3.0M HNO
3Carry out in solution, 1.0～2.0M KOH solution and the intermediate water.
5. the microelectrode for preparing according to arbitrary described method among the claim 1-4.
6. electrochemical detection device, comprising: microelectrode claimed in claim 5, contrast electrode and auxiliary electrode.
7. the application of microelectrode claimed in claim 5 in external correction physiological activator.
8. application according to claim 7 is characterized in that: the physiological activator of described external correction is adrenaline.
9. the application of electrochemical detection device claimed in claim 6 in external correction physiological activator.
10. application according to claim 9 is characterized in that: the physiological activator of described external correction is adrenaline.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810111625 CN101581690B (en) | 2008-05-15 | 2008-05-15 | Special electrode for in-vivo voltammetry analysis and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810111625 CN101581690B (en) | 2008-05-15 | 2008-05-15 | Special electrode for in-vivo voltammetry analysis and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101581690A CN101581690A (en) | 2009-11-18 |
| CN101581690B true CN101581690B (en) | 2013-01-23 |
Family
ID=41363931
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200810111625 Expired - Fee Related CN101581690B (en) | 2008-05-15 | 2008-05-15 | Special electrode for in-vivo voltammetry analysis and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101581690B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102759554A (en) * | 2011-04-26 | 2012-10-31 | 电子科技大学 | Manufacturing method of L-glutamic-acid-modified carbon fiber microelectrode, and application thereof in detecting neurotransmitters |
| CN106501331B (en) * | 2016-09-19 | 2019-10-11 | 中国科学院化学研究所 | PH sensor, preparation method and purposes |
| CN107865637B (en) * | 2016-09-28 | 2019-12-20 | 中国科学院化学研究所 | Living body assay H2S electrode, preparation method and in vivo detection H2S device |
| CN107917948B (en) * | 2016-10-09 | 2020-03-10 | 中国科学院化学研究所 | In vivo detection electrode correction method and application thereof |
| CN107271510A (en) * | 2017-06-14 | 2017-10-20 | 浙江理工大学 | Carbon fibres deposit metal phthalocyanine prepares electrochemical sensor |
| CN110057897B (en) * | 2018-01-19 | 2020-10-09 | 中国科学院化学研究所 | Carbon fiber electrode modified by electrophoretic deposition carbon nano tube and application thereof in detection of living ascorbic acid |
| CN110031524B (en) * | 2019-02-21 | 2021-04-06 | 中国科学院化学研究所 | Method for measuring dopamine |
| CN110389384B (en) * | 2019-06-18 | 2020-12-22 | 杭州电子科技大学 | Carbon fiber electrode for low-frequency ocean electric field detection and preparation method thereof |
| CN111537576A (en) * | 2020-04-16 | 2020-08-14 | 中国科学院化学研究所 | Method for detecting neurochemical substance in brain |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1282870A (en) * | 1999-07-30 | 2001-02-07 | 武汉大学 | Process for preparing low-noise non-class carbon fibre electrode |
-
2008
- 2008-05-15 CN CN 200810111625 patent/CN101581690B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1282870A (en) * | 1999-07-30 | 2001-02-07 | 武汉大学 | Process for preparing low-noise non-class carbon fibre electrode |
Non-Patent Citations (3)
| Title |
|---|
| Liangti Qu 等.Carbon Microfibers Sheathed with Aligned Carbon Nanotubes: Towards Multidimensional,Multicomponent, and Multifunctional Nanomaterials.《small》.2006,(第2期),1052-1056. * |
| ZHI Lin-jie 等.Novel carbon nanostructures prepared by solid-state pyrolysis of iron phthalocyanine.《新型碳材料》.2006,第21卷(第2期),109-113. * |
| 陈荣生 等.单壁碳纳米管修饰的高灵敏纳米碳纤维电极.《高等学校化学学报》.2003,第24卷(第5期),808-810. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101581690A (en) | 2009-11-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101581690B (en) | Special electrode for in-vivo voltammetry analysis and preparation method thereof | |
| CN103462615B (en) | Micrometer-scale glucose sensor microelectrode | |
| Zhu et al. | Design of carbon nanotube fiber microelectrode for glucose biosensing | |
| CN108828043A (en) | A kind of flexibility perspiration sensor and its preparation method and application | |
| CN104777203A (en) | Preparation method of Pt-Ni alloy nano tube array electrode and application for enzyme-free glucose sensor | |
| CN105675693A (en) | Preparation method of Pt nanometer particle-modified Cu nanowire array electrode and use of Pt nanometer particle-modified Cu nanowire array electrode in enzyme-free glucose sensor | |
| CN105758909A (en) | Gold nanotube based flexible stretchable electrode and preparation method and application thereof | |
| KR20070044023A (en) | Fuel cell, fuel cell use method, fuel cell cathode electrode, electronic device, electrode reaction use device, and electrode reaction use device electrode | |
| CN106324059B (en) | A kind of preparation method of glucose sensor electrode without enzyme material | |
| CN102156156A (en) | Three-dimensional copper oxide nanometer flower-based chip enzyme-free glucose sensor electrode as well as preparation method and application thereof | |
| CN106404863A (en) | Microelectrode biosensor used for in-vivo online detection of plant zeatin, and application of microelectrode biosensor | |
| Aydin et al. | A facile method for fabricating carbon fiber-based gold ultramicroelectrodes with different shapes using flame etching and electrochemical deposition | |
| CN107436316A (en) | The preparation of glucose sensor based on graphene and graphene oxide composite material | |
| CN102636536A (en) | Preparation and application of Pt-Cu alloy hollow nanoparticle enzyme-free glucose sensor electrode | |
| CN109507273A (en) | A kind of preparation method of the flexible NiCoLDH@CS electrode for glucose sensor | |
| CN106112007A (en) | A kind of preparation method of silver nanoparticle dendrite | |
| CN103983675A (en) | Platinum and polyaniline compounded three-dimensional nanofiber functional structure glucose sensor with stainless steel needle as base and preparation method of sensor | |
| CN114235924B (en) | Enzyme-free blood glucose sensor microelectrode of Pt/Au nano-alloy modified acupuncture needle with cabbage structure and preparation method thereof | |
| CN106872537B (en) | A kind of three-dimensional flower-shaped cobalt nanometer sheet electrochemical glucose sensor and preparation method thereof | |
| CN110057897A (en) | The carbon nano tube modified carbon fiber electrode of electrophoretic deposition and its application in the detection of living body ascorbic acid | |
| CN108414599A (en) | Preparation method of the copper nano particles without enzyme electrochemical glucose sensor | |
| CN105806907B (en) | A kind of method for preparing microelectrode | |
| CN105911128A (en) | Enzyme-free glucose electrochemical sensor and application thereof | |
| CN109298048A (en) | A kind of copper-based sensor chip and preparation method thereof and detection method | |
| Hatami et al. | Nanoscale Electrochemical Sensors for Intracellular Measurements at the Single Cell |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130123 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |