CN102507683A - Modified electrode based on functionalized multi-walled carbon nanotube, electrochemical system and application thereof - Google Patents
Modified electrode based on functionalized multi-walled carbon nanotube, electrochemical system and application thereof Download PDFInfo
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- CN102507683A CN102507683A CN2011103318008A CN201110331800A CN102507683A CN 102507683 A CN102507683 A CN 102507683A CN 2011103318008 A CN2011103318008 A CN 2011103318008A CN 201110331800 A CN201110331800 A CN 201110331800A CN 102507683 A CN102507683 A CN 102507683A
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Abstract
The invention provides a modified electrode based on a functionalized multi-walled carbon nanotube, an electrochemical system and application thereof. In the presence of AA (ascorbic acid) and UA (uric acid), a glassy carbon electrode volt-ampere sensor modified by the f-MWCNT (functionalized multi-walled carbon nanotube) made from SDS (sodium dodecyl sulfate) can be used for sensitively detecting DA (dopi amine). The f-MWCNT-glassy carbon electrode sensor not only has high oxidative and catalytic activity for the DA and the UA, but also can completely eliminate interference of the AA with the DA and simultaneously well distinguish the DA from the UA, thereby detecting the DA. A detection line for the DA by means of square wave voltammetry is 2.0X10-8, and the sensor has fine sensitivity, selectivity and stability.
Description
Technical field
The present invention relates to a kind of electrochemical system that detects dopamine and preparation method thereof.
Background technology
Dopamine (DA) is a neurotransmitter important in the mammalian central nervous system, and its change in concentration and cerebration in body has direct relation, and is significant to the research of its assay method.Because DA has better electrochemical activation, its content of available electrochemical method determining.Yet ascorbic acid (AA) and uric acid (UA) a large amount of in the biosome coexist with DA; Had a strong impact on the mensuration of DA. therefore having made up the number of chemical modified electrode comes optionally to measure DA; As on the nanotube of titania, modifying Pd, the nano particle of Pt and Au, electrode of the modified oxide of polymkeric substance, metal or the like; The formation more complicated of these methods, cost are also than higher.Therefore, development has that preparation is simple, response is fast, the method for reappearance, good stability, detection DA that antijamming capability is strong is extremely important.
Summary of the invention
Technical matters to be solved by this invention provide a kind of simple, sensitive, detect detecting electrode, its preparation method of dopamine molecule fast, and the electrochemical system of using and uses thereof.
A kind of modified electrode, it is used to detect dopamine, and said electrode comprises basal electrode and the carbon nano-tube film that is coated on said basal electrode surface, and said carbon nano-tube film is meant the multi-walled carbon nano-tubes through sodium dodecylsulphonate (SDS) functionalization.
Said basal electrode is a glass-carbon electrode; And/or said carbon nano-tube film be selected from multi-walled carbon nano-tubes (
f-MWCNT).
The preparation method of above-mentioned modified electrode comprises the steps:
(1) CNT is dispersed in the sodium dodecyl sulfate solution, the ultrasonic and/or dispersed with stirring with this solution is filtered at last, and with the unnecessary sodium dodecylsulphonate of second distillation water washing, is drying to obtain required CNT again;
(2) with in the step (1) through functionalized carbon nanotube be dispersed in the redistilled water solution, this solution is coated on the CNT, be drying to obtain said modified electrode.
Preferably, in the step (1), the multi-walled carbon nano-tubes of per 100 mg is dispersed in the sodium dodecyl sulfate solution of 0.25 M.
Above-mentioned modified electrode is used to detect the content of dopamine.
A kind of detection dopamine is used electrochemical system, contains the above-mentioned working electrode through modifying, and also can contain saturated calomel reference electrode and platinum to electrode.
A kind of method that detects dopamine comprises the steps,
(1) with glass-carbon electrode insert fill 5 mL contain the 5mM potassium ferricyanide, probe molecule concentration is in the potassium chloride electrolyte solution of 0.1 M; Employing is working electrode, platinum with the glass-carbon electrode for being the three-electrode system of contrast electrode to electrode, saturated calomel electrode; Cyclic voltammetry scan characterizes naked glass-carbon electrode;
(2) dopamine sample to be measured is joined in the described electrochemical system of claim 6, carry out cyclic voltammetry scan, obtain cyclic voltammogram.
The present invention with the multi-wall carbon nano-tube modified glassy carbon of SDS functionalization (
f-MWCNT-GCE) under the interference of AA and UA, detect DA; Because the multi-walled carbon nano-tubes of SDS functionalization is compared with the method for traditional CNT with acid functionalization, both there has not been the structure of destroying carbon nanometer tube also to make CNT electronegative, because AA is electronegative; So can get rid of the interference of AA to DA; Simultaneously again can catalytic oxidation DA and UA, can clearly from UA, distinguish DA, thereby reach detection DA.At length, from cyclic voltammogram, can find out the redox peak of dopamine, go out the peak position about 0.2V, and ascorbic acid not go out the peak on modified electrode, so can avoid the interference of ascorbic acid dopamine; This modified electrode to uric acid detect go out the peak position about 0.33V and the spike potential that goes out of dopamine differ 130mV, so can avoid the interference of ascorbic acid, also can from uric acid, distinguish dopamine, thereby reach the anti-interference detection of dopamine.
Advantage of the present invention is:
1 and other the method for detection DA compare, the process of modified electrode is fairly simple, cost is low.
2, the multi-walled carbon nano-tubes with the SDS functionalization has negative charge; And do not damage the structure of multi-walled carbon nano-tubes, because AA is electronegative, so can get rid of the interference of AA to DA; Simultaneously again can catalytic oxidation DA and UA; Can clearly from UA, distinguish DA, thereby reach detection DA, relatively sensitiveer to the detection of DA.Using square wave voltammetry is 2.0 * 10 to the detection line of DA
-8
Description of drawings
Do further detailed explanation below in conjunction with the accompanying drawing specific embodiments of the invention.
Fig. 1 be naked glass-carbon electrode (solid line) and f-MWCNT modified glassy carbon (dotted line) to 1 mM ascorbic acid (a), 0.05 mM uric acid (b) and the cyclic voltammogram of 0.05 mM dopamine (c) in the phosphate buffer (pH=7) of 0.05 M; Sweep speed: 50 mV s
-1
Fig. 2 be naked glass-carbon electrode (a) and f-MWCNT modified glassy carbon (b) in the PBS of 0.05M (pH=7) respectively to 0.6 mM AA, the comparison diagram of the cyclic voltammogram that the mixed solution of 0.025 mM UA and 0.05 mM DA detects; Sweep speed: 50 mV s
-1
Fig. 3 is for to contain 100 mM AA, and in the PBS of the 0.05M of 1.5 mM UA (pH=7) solution, the f-MWCNT modified glassy carbon is to the square wave voltammogram of the change in concentration (0.2～35 mM) of DA;
Fig. 4 is the DA concentration and the electric current linear relationship chart of the test result of Fig. 3.
Embodiment
The water that uses in the experimentation is redistilled water, test used reagent be analyze pure.
(1) this tests employed instrument and reagent
Instrument: CHI660 electrochemical workstation (CH instrument company, the U.S.) is used for cyclic voltammetry and square wave voltammetry experiment; The automatic dual pure water distiller of quartz ampoule heated type (1810B, Asian-Pacific Glass-Tech. Co., Shanghai City) is used to steam redistilled water; Electronic balance (Beijing Sai Duolisi Instr Ltd.) is used for the weighing medicine; Ultrasonic cleaner (Kunshan Ultrasonic Instruments Co., Ltd.); Alundum (Al polishing powder (0.30 mm, 0.05 mm, Shanghai occasion China instrument reagent company) is used to handle glass-carbon electrode; Saturated mercurous chloride electrode (CHI III, U.S. CH instrument company) is a contrast electrode; Platinum is to electrode.
Reagent: ascorbic acid, dopamine, uric acid, sodium dodecylsulphonate (Beijing is through Bioisystech Co., Ltd of HTC of section) multi-walled carbon nano-tubes (Nanoport company limited, China Shenzhen).
(2) a kind of DA sensor based on f-MWCNT-GCE, its preparation and detection dopamine may further comprise the steps:
A. the multi-walled carbon nano-tubes of 100mg is dispersed in the solution of sodium dodecylsulphonate (SDS) of 400 mL 0.25M; This solution placed 1000 mL beakers ultrasonic one hour; Being placed on the magnetic stirring apparatus stirring at normal temperature then filtered this solution after 24 hours on sintered filter funnel; And clean three times with secondary water and wash unnecessary SDS off; The filter cake of the multi-walled carbon nano-tubes that obtains is placed in the surface plate in vacuum drying chamber 80 degrees centigrade of following vacuum drying 12 hours, is dispersed in the multi-walled carbon nano-tubes of SDS functionalization in the redistilled water then and makes multi-walled carbon nano-tubes be uniformly dispersed subsequent use (0.5mg/mL) in ultrasonic 15 minutes.
B. glass-carbon electrode is polished to minute surface with the alundum (Al suspension of 0.3 μ m, 0.05 μ m successively, more successively after volume fraction is the ethanol, redistilled water ultrasonic cleaning of 95 %, the glass-carbon electrode after obtaining handling; It is in the 0.1 M potassium chloride electrolyte solution that insertion fills the volumetric molar concentration that 5 mL contain 5 mM potassium ferricyanide probe molecules; And to adopt with the glass-carbon electrode be working electrode, with platinum for being that the three-electrode system of contrast electrode carries out cyclic voltammetry scan to electrode, with saturated mercurous chloride electrode; Glass-carbon electrode is characterized, obtain the cyclic voltammogram (CV) of naked glass-carbon electrode.
C. the f-MWCNT that drips last 5 μ L after said glass-carbon electrode taking-up being dried up with redistilled water flushing, ear washing bulb places under the infrared lamp and dries, and makes the f-MWCNT modified glassy carbon.
D. to adopt naked glass-carbon electrode and described f-MWCNT modified glassy carbon be working electrode, with platinum for being that the three-electrode system of contrast electrode contains 0.6 mM AA at 5mL respectively to electrode, with saturated mercurous chloride electrode; 0.05 (PBS in the phosphate buffer of mM DA and 0.025 mM UA; PH=7) carry out cyclic voltammetry scan, obtain AA respectively, UA; The cyclic voltammetric comparison diagram of DA, shown in Figure 1;
Can find out from Fig. 1 (a); F-MWCNT-GCE is to AA oxidation peak current little than naked GCE; That is because f-MWCNT-GCE has negative charge AA to be had the effect of repulsion, (b) of Fig. 1, (c) f-MWCNT-GCE to the oxidation peak current of UA and DA all than naked GCE greatly.
E. to adopt naked glass-carbon electrode and described f-MWCNT modified glassy carbon be working electrode, with platinum for being that the three-electrode system of contrast electrode contains 0.6 mM AA at 5mL to electrode, with saturated mercurous chloride electrode; 0.025 the mixed solution of the phosphate buffer of mM UA and 0.05 mM DA (0.5 mM PBS; PH=7) carry out cyclic voltammetry scan in; Obtain the cyclic voltammetric comparison diagram of naked glass carbon and f-MWCNT modified glassy carbon respectively, shown in Figure 2;
Can find out that from Fig. 2 (a) naked GCE is at AA, the oxidation peak in the mixed solution of UA and DA is superimposed, and f-MWCNT-GCE can get rid of the interference of AA in Fig. 2 (b), can from UA, distinguish DA again.
F. to adopt naked glass-carbon electrode and described f-MWCNT modified glassy carbon be working electrode, with platinum for being that the three-electrode system of contrast electrode contains 0.6 mM AA at 5mL to electrode, with saturated mercurous chloride electrode; 0.025 the mixed solution of the phosphate buffer of mM UA (0.5 mM PBS; PH=7) concentration of DA is carried out the scanning of square wave volt-ampere, the square wave voltammogram of f-MWCNT modified glassy carbon from 0.2 to 35mM in;
From Fig. 3, Fig. 4, can find out UA and the AA not influence of detection to DA, along with the variation of DA concentration, it is linear that the electric current of the oxidation peak of DA and the variation of concentration are.
What should explain at last is: the above is merely the preferred embodiments of the present invention; Be not limited to the present invention; Although the present invention has been carried out detailed explanation with reference to previous embodiment; For a person skilled in the art, it still can be made amendment to the technical scheme that aforementioned each embodiment put down in writing, and perhaps part technical characterictic wherein is equal to replacement.All within spirit of the present invention and principle, any modification of being done, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (8)
1. modified electrode, it is used to detect dopamine, and said electrode comprises basal electrode and the carbon nano-tube film that is coated on said basal electrode surface, it is characterized in that said carbon nano-tube film is meant the multi-walled carbon nano-tubes through the sodium dodecylsulphonate functionalization.
2. modified electrode according to claim 1 is characterized in that said basal electrode is a glass-carbon electrode; And/or said carbon nano-tube film is selected from multi-walled carbon nano-tubes.
3. the preparation method of claim 1 or 2 described modified electrodes is characterized in that, comprises the steps:
(1) CNT is dispersed in the sodium dodecyl sulfate solution, the ultrasonic and/or dispersed with stirring with this solution is filtered at last, and with the unnecessary sodium dodecylsulphonate of second distillation water washing, is drying to obtain required CNT again;
(2) with in the step (1) through functionalized carbon nanotube be dispersed in the redistilled water solution, this solution is coated on the CNT, be drying to obtain said modified electrode.
4. the preparation method of modified electrode according to claim 3 is characterized in that, in the step (1), the multi-walled carbon nano-tubes of per 100 mg is dispersed in the sodium dodecyl sulfate solution of 0.25 M.
5. the purposes of the described modified electrode of claim 1 is characterized in that, is used to detect the content of dopamine.
6. a detection dopamine is used electrochemical system, it is characterized in that contain working electrode in the described electrochemical system, described working electrode is the described modified electrode of claim 1.
7. electrochemical system according to claim 6 is characterized in that, also contains saturated calomel reference electrode and platinum in the described electrochemical system to electrode.
8. method that detects dopamine is characterized in that: comprises the steps,
(1) with glass-carbon electrode insert fill 5 mL contain the 5mM potassium ferricyanide, probe molecule concentration is in the potassium chloride electrolyte solution of 0.1 M; Employing is working electrode, platinum with the glass-carbon electrode for being the three-electrode system of contrast electrode to electrode, saturated calomel electrode; Cyclic voltammetry scan characterizes naked glass-carbon electrode;
(2) dopamine sample to be measured is joined in the described electrochemical system of claim 6, carry out cyclic voltammetry scan, obtain cyclic voltammogram.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102980927A (en) * | 2012-11-21 | 2013-03-20 | 西安建筑科技大学 | Preparation method and application of carbon nanometer pipe/poly-nicotinic acid composite ornament electrode |
| CN103151129A (en) * | 2013-03-26 | 2013-06-12 | 哈尔滨工业大学 | Preparation method of multiwalled carbon nanotube (MWCNT)/ ferroferric oxide (Fe3O4)/zinc oxide (ZnO) ternary heterogeneous nanocomposite |
| CN104034790A (en) * | 2014-06-12 | 2014-09-10 | 中国科学院理化技术研究所 | Perfluorinated sulfonic acid resin modified SnO2-coated ZnO nanotube array electrode used for detecting dopamine and application of nanotube array electrode |
| CN104090010A (en) * | 2014-07-29 | 2014-10-08 | 无锡百灵传感技术有限公司 | Method for preparing electrochemical sensor for detecting almotriptan |
| CN104165911A (en) * | 2014-08-07 | 2014-11-26 | 江南大学 | Preparation of carbon nanotube composite material electrochemical sensor capable of detecting dopamine and paracetamol simultaneously |
| CN104831277A (en) * | 2015-04-13 | 2015-08-12 | 济南大学 | Preparation method and application of poly-sulfosalicylic acid / titanium dioxide / carbon nanotube nanocomposite with electrode as substrate |
| CN106841344A (en) * | 2017-04-07 | 2017-06-13 | 西北师范大学 | The preparation and application of a kind of poroid SWCN and its modified electrode |
| CN107422014A (en) * | 2017-07-13 | 2017-12-01 | 云南大学 | Modified electrode and preparation method and detection method for detection of alkaline phosphatase |
| CN107941875A (en) * | 2017-11-25 | 2018-04-20 | 于世金 | The detection method and detecting electrode material of a kind of electrochemistry of uric acid in urine |
| CN111474220A (en) * | 2020-01-13 | 2020-07-31 | 湖南科技大学 | Method for detecting dopamine by using acidified grapyne nanotube/short multi-walled carbon nanotube modified electrode |
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2011
- 2011-10-27 CN CN2011103318008A patent/CN102507683A/en active Pending
Non-Patent Citations (1)
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| XU YANG ,ET AL.: "Selective Detection of Dopamine in the Presence of High-Concentration Ascorbic Acid Using Multi-wall Carbon Nanotubes-Sodium Dodecyl Sulfate Modif ied Glassy Carbon Electrode", 《西南大学学报(自然科学版)》 * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102980927A (en) * | 2012-11-21 | 2013-03-20 | 西安建筑科技大学 | Preparation method and application of carbon nanometer pipe/poly-nicotinic acid composite ornament electrode |
| CN103151129A (en) * | 2013-03-26 | 2013-06-12 | 哈尔滨工业大学 | Preparation method of multiwalled carbon nanotube (MWCNT)/ ferroferric oxide (Fe3O4)/zinc oxide (ZnO) ternary heterogeneous nanocomposite |
| CN103151129B (en) * | 2013-03-26 | 2015-05-27 | 哈尔滨工业大学 | Preparation method of multiwalled carbon nanotube (MWCNT)/ ferroferric oxide (Fe3O4)/zinc oxide (ZnO) ternary heterogeneous nanocomposite |
| CN104034790A (en) * | 2014-06-12 | 2014-09-10 | 中国科学院理化技术研究所 | Perfluorinated sulfonic acid resin modified SnO2-coated ZnO nanotube array electrode used for detecting dopamine and application of nanotube array electrode |
| CN104090010A (en) * | 2014-07-29 | 2014-10-08 | 无锡百灵传感技术有限公司 | Method for preparing electrochemical sensor for detecting almotriptan |
| CN104165911A (en) * | 2014-08-07 | 2014-11-26 | 江南大学 | Preparation of carbon nanotube composite material electrochemical sensor capable of detecting dopamine and paracetamol simultaneously |
| CN104831277A (en) * | 2015-04-13 | 2015-08-12 | 济南大学 | Preparation method and application of poly-sulfosalicylic acid / titanium dioxide / carbon nanotube nanocomposite with electrode as substrate |
| CN106841344A (en) * | 2017-04-07 | 2017-06-13 | 西北师范大学 | The preparation and application of a kind of poroid SWCN and its modified electrode |
| CN106841344B (en) * | 2017-04-07 | 2018-12-11 | 西北师范大学 | The preparation and application of a kind of poroid single-walled carbon nanotube and its modified electrode |
| CN107422014A (en) * | 2017-07-13 | 2017-12-01 | 云南大学 | Modified electrode and preparation method and detection method for detection of alkaline phosphatase |
| CN107422014B (en) * | 2017-07-13 | 2019-07-12 | 云南大学 | Modified electrode and preparation method and detection method for detection of alkaline phosphatase |
| CN107941875A (en) * | 2017-11-25 | 2018-04-20 | 于世金 | The detection method and detecting electrode material of a kind of electrochemistry of uric acid in urine |
| CN111474220A (en) * | 2020-01-13 | 2020-07-31 | 湖南科技大学 | Method for detecting dopamine by using acidified grapyne nanotube/short multi-walled carbon nanotube modified electrode |
| CN111474220B (en) * | 2020-01-13 | 2022-05-27 | 湖南科技大学 | Method for detecting dopamine by using acidified grapyne nanotube/short multi-walled carbon nanotube modified electrode |
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Application publication date: 20120620 |