CN110514725A - Dopamine electrochemical sensing electrode and its preparation based on Fe-PANI - Google Patents
Dopamine electrochemical sensing electrode and its preparation based on Fe-PANI Download PDFInfo
- Publication number
- CN110514725A CN110514725A CN201910687668.0A CN201910687668A CN110514725A CN 110514725 A CN110514725 A CN 110514725A CN 201910687668 A CN201910687668 A CN 201910687668A CN 110514725 A CN110514725 A CN 110514725A
- Authority
- CN
- China
- Prior art keywords
- solution
- added
- pani
- electrode
- hydrochloric acid
- 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
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 56
- 229960003638 dopamine Drugs 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 78
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 39
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000725 suspension Substances 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000005498 polishing Methods 0.000 claims abstract description 14
- 239000012265 solid product Substances 0.000 claims abstract description 14
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 239000012074 organic phase Substances 0.000 claims abstract description 11
- 229920000557 Nafion® Polymers 0.000 claims abstract description 10
- 229960000935 dehydrated alcohol Drugs 0.000 claims abstract description 10
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 238000013019 agitation Methods 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 239000000178 monomer Substances 0.000 claims abstract description 6
- 239000002086 nanomaterial Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 5
- 238000005374 membrane filtration Methods 0.000 claims abstract description 4
- 239000008363 phosphate buffer Substances 0.000 claims description 14
- 238000012360 testing method Methods 0.000 claims description 14
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 8
- 230000008020 evaporation Effects 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- 235000009508 confectionery Nutrition 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 4
- 229960004756 ethanol Drugs 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 2
- -1 DOPA Amine Chemical class 0.000 claims 1
- WTDRDQBEARUVNC-UHFFFAOYSA-N L-Dopa Natural products OC(=O)C(N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-UHFFFAOYSA-N 0.000 claims 1
- ADHFGLVXSIGCIG-UHFFFAOYSA-N diazanium sulfate hydrochloride Chemical compound [NH4+].[NH4+].Cl.[O-]S([O-])(=O)=O ADHFGLVXSIGCIG-UHFFFAOYSA-N 0.000 claims 1
- 239000006185 dispersion Substances 0.000 claims 1
- 150000002576 ketones Chemical class 0.000 claims 1
- 229960004502 levodopa Drugs 0.000 claims 1
- 239000012071 phase Substances 0.000 claims 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 abstract description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 40
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 27
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 description 27
- 229940116269 uric acid Drugs 0.000 description 27
- 229960005070 ascorbic acid Drugs 0.000 description 20
- 235000010323 ascorbic acid Nutrition 0.000 description 20
- 239000011668 ascorbic acid Substances 0.000 description 20
- 238000001514 detection method Methods 0.000 description 15
- 230000001590 oxidative effect Effects 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 4
- 201000010099 disease Diseases 0.000 description 4
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 2
- 230000006399 behavior Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000002858 neurotransmitter agent Substances 0.000 description 2
- 238000000083 pulse voltammetry Methods 0.000 description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 206010019280 Heart failures Diseases 0.000 description 1
- 208000001647 Renal Insufficiency Diseases 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 206010040047 Sepsis Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 238000005251 capillar electrophoresis Methods 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000000835 electrochemical detection Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 210000000750 endocrine system Anatomy 0.000 description 1
- 239000002158 endotoxin Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 201000006370 kidney failure Diseases 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000036403 neuro physiology Effects 0.000 description 1
- 208000018360 neuromuscular disease Diseases 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 201000000980 schizophrenia Diseases 0.000 description 1
- 208000013223 septicemia Diseases 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The present invention provides a kind of dopamine electrochemical sensing electrodes and preparation method thereof for being based on Fe2O3 doping polyaniline (Fe-PANI) nano material, comprising: aniline monomer is added in dichloromethane solution and is ultrasonically formed organic phase solution by S1；S2, is successively slowly added to N-Methyl pyrrolidone aqueous solution and ferric chloride solution into the organic phase solution under agitation, stands after being protected from light stirring a period of time at room temperature；Ammonium persulfate-hydrochloric acid solution is slowly added in step S2 in reaction solution by S3, is stood and is obtained solid product with organic system membrane filtration after reacting；Solid product cleaning, filtering, naturally dry are obtained Fe-PANI powder by S4；S5, will be spare after glass-carbon electrode grinding and polishing；S6 takes Fe-PANI powder ultrasonic disperse in dehydrated alcohol, and Nafion solution ultrasonic disperse is added and forms suspension；S7 takes hanging drop to be added to the glass-carbon electrode after step S5 polishing, obtains Fe-PANI modified electrode.
Description
Technical field
The present invention relates to a kind of based on the dopamine electrochemical sensing electrode of Fe2O3 doping polyaniline and its preparation.
Background technique
Dopamine (DA) is a kind of to suffer from important function in nervous centralis, angiocarpy, kidney and endocrine system
Neurotransmitter, and in human body can the behaviors such as thinking, work, movement to people have an impact.Dopamine is in human body just
Chang Hanliang is 0.2-0.4g/ml, can be caused when the content of dopamine in human body is too low such as schizophrenia, heart failure, pa
The diseases such as the gloomy disease of gold, neuromuscular disorders.Otherwise DA content is excessive, people can be allowed to feel excited, happy, be easy addicted.In addition exist
In terms of medicine, dopamine is also commonly used for treating the diseases such as depression, renal failure and endotoxin septicemia.Therefore, have
Selectively, in high sensitivity detect neurotransmitter dopamine concentration, to diagnose on a molecular scale these diseases have it is important
Application value, the quality of research and related drugs for neuro-physiology controls important in inhibiting.
At present the common detection method of dopamine have fluorescent spectrometry, colleges and universities' liquid phase method, capillary electrophoresis, colorimetric method,
Electrochemical analysis detection method etc..Wherein electrochemical detection method has easy to operate, highly sensitive, good selective, becomes
The common method of dopamine detection.So in brain and body fluid, other than dopamine, also contain uric acid (UA) and ascorbic acid
(AA), and the oxidizing potential of three is very close, and the presence of uric acid and ascorbic acid produces the measurement of dopamine in detection architecture
Raw interference.Therefore, how effectively to exclude the interference that uric acid and ascorbic acid detect dopamine is current dopamine electrochemistry
The important research content of sensing.
Summary of the invention
The present invention provides a kind of dopamine electrochemical sensing electrode based on Fe2O3 doping polyaniline, can effectively solve
State problem.
The present invention is implemented as follows:
The present invention provides a kind of preparation side of dopamine electrochemical sensing electrode based on Fe2O3 doping polyaniline nano material
Method, comprising the following steps:
S1, ultrasound in 50mL dichloromethane solution, which is added, in 0.5mL aniline monomer keeps its evenly dispersed formation transparent uniform
Organic phase solution；
S2 is successively slowly added to the N- methyl pyrrole of the 0.2mol/L of 50mL into the organic phase solution under agitation
The ferric chloride solution of the 0.5mol/L of pyrrolidone aqueous solution and 0.05mL are stood after being protected from light stirring a period of time at room temperature；
0.3g ammonium persulfate is added in the hydrochloric acid solution of the 2mol/L of 8.6mL and forms ammonium persulfate-hydrochloric acid solution by S3,
Ammonium persulfate-hydrochloric acid solution is slowly added in step S2 in reaction solution, uses organic system filter membrane after standing reaction a period of time
Solid product is obtained by filtration；
Solid product cleaning, filtering, naturally dry are obtained Fe-PANI powder by S4；
S5, by the glass-carbon electrode successively use 3 μm, 1 μm, 0.3 μm, after the alumina powder grinding and polishing of 50nm it is spare；
S6 takes the Fe-PANI powder ultrasonic disperse of 1~3mg in 0.5mL dehydrated alcohol, and the Nafion of 5~15 μ L is added
Solution ultrasonic disperse forms it into uniform suspension；
S7, the glassy carbon electrode surface for taking the suspension of 10-40 μ L to be added drop-wise to after step S5 polishing with 10-20 μ L/ times, stands
Continue that suspension is added dropwise after solution evaporation, operation finally obtains Fe-PANI modified electrode repeatedly.
The present invention also provides a kind of dopamine electricity based on Fe2O3 doping polyaniline nano material obtained based on the above method
Chemical sensitisation electrode；It tests environment are as follows: by working electrode, graphite electrode or platinum electrode of Fe-PANI modified electrode is to electricity
Pole, the sweet common-battery of saturation extremely reference electrode carry out DPV test, wherein potential range -0.1V-0.9V (vs.SCE), scan amplitude
For 50mV, pulse width 50ms, entire environment of testing carries out in the phosphate buffer of pH=6.6-7.2.
The beneficial effects of the present invention are: Fe-PANI modified electrode has preferable anti-interference ability to UA for detecting DA,
And it is not interfered by AA under the conditions of AA concentration is lower than 1mM；0.005 μM is limited to DA detection, 0.5 μM is limited to UA detection.Therefore
Fe-PANI modified electrode under by AA disturbed condition, can simultaneously not detect UA when detecting DA.
Detailed description of the invention
It, below will be to use required in embodiment in order to illustrate more clearly of the technical solution of embodiment of the present invention
Attached drawing be briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not to be seen as
It is the restriction to range, it for those of ordinary skill in the art, without creative efforts, can be with root
Other relevant attached drawings are obtained according to these attached drawings.
Fig. 1 is in 0.1M, the phosphate buffer that pH is 6.8, and the AA of UA, 2mM of 1mM, 200 μM of DA are repaired in polyaniline
Adorn the DPV figure on electrode.
It is 0.1M that Fig. 2, which is in concentration, and AA, 200 μM of the DA of UA, 2mM of 1mM are in Fe- in the phosphate buffer that pH is 6.8
DPV figure on PANI modified electrode.
It is 0.1M that Fig. 3, which is in concentration, and pH is in 6.8 phosphate buffer, a series of concentration DA is in Fe-PANI modified electrode
On DPV figure.
Fig. 4 is the linear relationship curve graph of DA concentration and peak current.
It is 0.1M that Fig. 5, which is in concentration, and pH is in 6.8 phosphate buffer, a series of concentration UA is in Fe-PANI modified electrode
On DPV figure.
Fig. 6 is the linear relationship curve graph of UA concentration and peak current.
Specific embodiment
To keep the purposes, technical schemes and advantages of embodiment of the present invention clearer, implement below in conjunction with the present invention
The technical solution in embodiment of the present invention is clearly and completely described in attached drawing in mode, it is clear that described reality
The mode of applying is some embodiments of the invention, rather than whole embodiments.Based on the embodiment in the present invention, ability
Domain those of ordinary skill every other embodiment obtained without creative efforts, belongs to the present invention
The range of protection.Therefore, the detailed description of the embodiments of the present invention provided in the accompanying drawings is not intended to limit below and is wanted
The scope of the present invention of protection is sought, but is merely representative of selected embodiment of the invention.Based on the embodiment in the present invention,
Every other embodiment obtained by those of ordinary skill in the art without making creative efforts belongs to this
Invent the range of protection.
In the description of the present invention, term " first ", " second " are used for description purposes only, and should not be understood as instruction or dark
Show relative importance or implicitly indicates the quantity of indicated technical characteristic.The feature of " first ", " second " is defined as a result,
It can explicitly or implicitly include one or more of the features.In the description of the present invention, the meaning of " plurality " is two
It is a or more than two, unless otherwise specifically defined.
The embodiment of the present invention provides a kind of dopamine electrochemical sensing electrode based on Fe2O3 doping polyaniline nano material
Preparation method, comprising the following steps:
S1, ultrasound in 50mL dichloromethane solution, which is added, in 0.5mL aniline monomer keeps its evenly dispersed formation transparent uniform
Organic phase solution；
S2 is successively slowly added to the N- methyl pyrrole of the 0.2mol/L of 50mL into the organic phase solution under agitation
The ferric chloride solution of the 0.5mol/L of pyrrolidone aqueous solution and 0.05mL are stood after being protected from light stirring a period of time at room temperature；
0.3g ammonium persulfate is added in the hydrochloric acid solution of the 2mol/L of 8.6mL and forms ammonium persulfate-hydrochloric acid solution by S3,
Ammonium persulfate-hydrochloric acid solution is slowly added in step S2 in reaction solution, uses organic system filter membrane after standing reaction a period of time
Solid product is obtained by filtration；
Solid product cleaning, filtering, naturally dry are obtained Fe-PANI powder by S4；
S5, by the glass-carbon electrode successively use 3 μm, 1 μm, 0.3 μm, after the alumina powder grinding and polishing of 50nm it is spare；
S6 takes the Fe-PANI powder ultrasonic disperse of 1~3mg in 0.5mL dehydrated alcohol, and the Nafion of 5~15 μ L is added
Solution ultrasonic disperse forms it into uniform suspension；
S7, the glassy carbon electrode surface for taking the suspension of 10-40 μ L to be added drop-wise to after step S5 polishing with 10-20 μ L/ times, stands
Continue that suspension is added dropwise after solution evaporation, operation finally obtains Fe-PANI modified electrode repeatedly.
The test environment of the Fe-PANI modified electrode are as follows: using Fe-PANI modified electrode as working electrode, graphite electrode
Or platinum electrode is to carry out DPV test to electrode, the sweet common-battery of saturation extremely reference electrode, wherein potential range -0.1V-0.9V
(vs.SCE), scan amplitude 50mV, pulse width 50ms, entire environment of testing is in pH=6.6-7.2 hair phosphate buffer
It carries out.As further improved, in addition, the pH value of environment also has larger impact to test in entire test, work as pH=
When 6.6-7.2 is more than this range, the proton doping level of polyaniline changes, to influence to detect the anti-interference of substance
Property, sensitivity and stability, it is therefore preferred that entirely test environment carries out in the phosphate buffer of pH=6.8-7.2.
As further improved, in step s 2, it is 10-50h that mixed solution, which is protected from light the time,.
As further improved, in step s3, being added after ammonium persulfate-hydrochloric acid solution and standing the reaction time is 15-
35min。
As further improved, in step s 4, the step of solid product is cleaned, includes:
The solid product is successively cleaned filtration product, hydrochloric acid solution with distilled water, hydrochloric acid solution, ethanol washing by S41
Concentration range be 0.1-2mol/L.In step in S41, hydrochloric acid solution clean so that polyaniline keep certain electric conductivity and
Dispersibility.The hydrochloric acid cleaning solution of right excessively high solubility will influence the cleaning of product simultaneously so that polyaniline is easily dispersed into homogeneous solution
Destroy filtering film layer.Therefore it is furthermore preferred that the concentration range of the hydrochloric acid solution is 0.1-1.2mol/L.
As further improved, in step s 6, the Fe-PANI powder ultrasonic disperse for taking 1~3mg is in 0.5mL
In dehydrated alcohol, Nafion solution ultrasonic disperse the step of forming it into uniform suspension that 5~15 μ L are added, includes:
S61 takes the Fe-PANI powder ultrasonic disperse of 2mg in 0.5mL dehydrated alcohol, and the Nafion solution of 10 μ L is added
Ultrasonic disperse forms it into uniform suspension.
As further improved, in the step s 7, the suspension for taking 10-40 μ L is added drop-wise to step with 10-20 μ L/ times
Glassy carbon electrode surface after rapid S5 polishing, standing continue that suspension is added dropwise after solution evaporation, and operation finally obtains Fe- repeatedly
The step of PANI modified electrode includes:
S71 takes the suspension of 20 μ L to be directly added drop-wise to the glassy carbon electrode surface after step S5 polishing, stands to solution evaporation
After obtain Fe-PANI modified electrode.
Embodiment 1:
50mL methylene chloride is added in round-bottomed flask, then 0.5mL aniline monomer is added in dichloromethane solution and is surpassed
Sound makes its evenly dispersed transparent uniform organic phase solution of formation.By obtained organic phase solution put with magnetic stirring apparatus on,
The N-Methyl pyrrolidone aqueous solution and 0.05mL of 50mL0.2mol/L are successively slowly added into solution under agitation
The ferric chloride solution of 0.5mol/L is stood after being protected from light stirring 20h at room temperature.It weighs 0.3g ammonium persulfate and is dissolved in 8.6mL 2mol/L
Hydrochloric acid solution in, ammonium persulfate-hydrochloric acid solution is obtained after being completely dissolved.Ammonium persulfate-hydrochloric acid mixed solution is burnt along round bottom
Bottle bottle wall is slowly added in the dichloromethane-N-methylmo pyrrolidones reaction solution under static conditions, stands reaction after twenty minutes
Solid product is obtained with the organic system membrane filtration in 0.22 μm of aperture, successively uses distilled water, 1mol/L hydrochloric acid solution, ethanol washing
Filtration product is cleaned, naturally dry obtains Fe-PANI powder.The glass-carbon electrode that diameter is 5mm is successively used into 3 μm, 1 μm, 0.3 μ
M, spare after the alumina powder grinding and polishing of 50nm.Take 2mg Fe-PANI powder ultrasonic disperse in 0.5mL dehydrated alcohol,
The Nafion solution ultrasonic disperse 30min that 10 μ L are added forms it into uniform suspension.The hanging drop of 20 μ L is taken to be added to dry
Net glassy carbon electrode surface, it is stand-by that standing obtains Fe-PANI modified electrode after solution evaporation.It is with Fe-PANI modified electrode
Working electrode, graphite electrode are to carry out Pulse Voltammetry (DPV) test to electrode, the sweet common-battery of saturation extremely reference electrode.It is wherein electric
Position range -0.1V-0.9V (vs.SCE), scan amplitude 50mV, pulse width 50ms.Entire experiment is in phosphate buffer
It is carried out in the environment of (0.1M PBS solution, pH=6.8).
Comparative example:
50mL methylene chloride is added in round-bottomed flask, then 0.5mL aniline monomer is added in dichloromethane solution and is surpassed
Sound makes its evenly dispersed transparent uniform organic phase solution of formation.By obtained organic phase solution put with magnetic stirring apparatus on,
The N-Methyl pyrrolidone aqueous solution of 50mL0.2mol/L is successively slowly added into solution under agitation, is protected from light at room temperature
It is stood after stirring 20h.It weighs 0.3g ammonium persulfate to be dissolved in the hydrochloric acid solution of 8.6mL 2mol/L, obtains over cure after being completely dissolved
Sour ammonium-hydrochloric acid solution.Dichloromethane ammonium persulfate-hydrochloric acid mixed solution being slowly added to along round-bottomed flask bottle wall under static conditions
In alkane-N-Methyl pyrrolidone reaction solution, stands reaction and obtained after twenty minutes with the organic system membrane filtration in 0.22 μm of aperture
Solid product, successively cleans filtration product with distilled water, 1mol/L hydrochloric acid solution, ethanol washing, and naturally dry obtains PANI powder
Body.By the glass-carbon electrode that diameter is 5mm successively use 3 μm, 1 μm, 0.3 μm, after the alumina powder grinding and polishing of 50nm it is spare.It takes
For 2mg PANI powder ultrasonic disperse in 0.5mL dehydrated alcohol, the Nafion solution ultrasonic disperse 30min that 10 μ L are added makes its shape
At uniform suspension.The hanging drop of 20 μ L is taken to be added to clean glassy carbon electrode surface, standing obtains after solution evaporation
PANI electrode is stand-by.It is to be carried out to electrode, the sweet common-battery of saturation extremely reference electrode using PANI electrode as working electrode, graphite electrode
Pulse Voltammetry (DPV) test.Wherein potential range -0.1V-0.9V (vs.SCE), scan amplitude 50mV, pulse width 50ms.
Entire experiment carries out in the environment of phosphate buffer (0.1M PBS solution, pH=6.8).
Test case:
Fig. 1 is in 0.1M, the phosphate buffer that pH is 6.8, and the AA of UA, 2mM of 1mM, 200 μM of DA are repaired in polyaniline
Adorn the DPV figure on electrode.From figure 1 it appears that between 0.2V-0.7V, spike potential is the oxidizing potential of DA in figure
0.27V；The oxidizing potential of UA is between 0.3V-0.7V, spike potential 0.4V.Therefore the electrochemical response signal of DA and UA is deposited
Overlapping in part, i.e., the presence of UA can generate interference to the detection of DA to a certain extent.And AA is in current potential in the system
There are two oxidation peaks by 0.1V-0.3V and 0.7V-0.85V, wherein the oxidation signal between 0.1V-0.3V is to a certain extent
The detection of DA is had an impact.Therefore polyaniline modified electrode will receive to a certain extent in the detection process to DA UA and
The interference of AA.
It is 0.1M that Fig. 2, which is in concentration, and AA, 200 μM of the DA of UA, 2mM of 1mM are in Fe- in the phosphate buffer that pH is 6.8
DPV figure on PANI modified electrode.From figure 2 it can be seen that the oxidizing potential of DA is located on Fe-PANI modified electrode in figure
Between 0.15V-0.4V, spike potential 0.25V；The oxidizing potential of UA is between 0.3V-0.7V, spike potential 0.38V；AA's
Spike potential is 0.14V, and peak current is smaller.Since the DPV oxidizing potential section overlapping degree of UA and DA is smaller, in detection DA signal
When, UA interferes it smaller.Under the conditions of the AA of high concentration, the spike potential of AA and UA still have certain signal and overlap, AA
To UA detection there are certain interference.Fe-PANI modified electrode is limited to 1mM to the detection of AA, when AA concentration is lower than 1mM,
AA, without apparent electrochemical response behavior, is not present the detection of DA and significantly interferes on Fe-PANI modified electrode.
It is 0.1M that Fig. 3, which is in concentration, and pH is in 6.8 phosphate buffer, a series of concentration DA is in Fe-PANI modified electrode
On DPV figure, the oxidizing potential range of DA is between 0.15V-0.45V in figure, spike potential 0.25V.With the increasing of DA concentration
Greatly, the response current on electrode is limited to 0.005 μM also with increase, detection.
Fig. 4 is the linear relationship curve graph of DA concentration and peak current.It can be seen from the figure that the concentration model detected in the text
0.005 μM -200 μM are enclosed, bilinear relation is presented between DA concentration and peak current.In high concentration (10 μM -200 μM) linearity curve
For y1=0.06993x+2.57355, coefficient R2=0.983.It is y in low concentration (0.005 μM -10 μM) linearity curve2
=0.27676x+0.48846, coefficient R2=0.94948.
It is 0.1M that Fig. 5, which is in concentration, and pH is in 6.8 phosphate buffer, a series of concentration UA is in Fe-PANI modified electrode
On DPV figure, it can be seen that the potential range of the oxidation signal of UA is 0.25V-0.55V in figure, peak position current potential is 0.38V.With
The increase of UA concentration, for the response current on electrode also with increase, detection is limited to 0.5 μM.
Fig. 6 is the linear relationship curve graph of UA concentration and peak current.It can be seen from the figure that the concentration model detected in the text
0.1 μM of -1mM is enclosed, bilinear relation is presented between UA concentration and peak current.It is y in high concentration (50 μM of -1mM) linearity curve1=
0.0099x+0.97386, coefficient R2=0.99995.It is y in low concentration (0.1 μM -50 μM) linearity curve2=
0.02777x+0.09553, coefficient R2=0.98998.
The foregoing is merely the preferred embodiment of the present invention, are not intended to restrict the invention, for this field
For technical staff, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any
Modification, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (7)
1. a kind of preparation method of the dopamine electrochemical sensing electrode based on Fe2O3 doping polyaniline nano material, feature exist
In, comprising the following steps:
S1, ultrasound in 50mL dichloromethane solution, which is added, in 0.5mL aniline monomer its evenly dispersed formed transparent uniform
Machine phase solution；
S2 is successively slowly added to the N- crassitude of the 0.2mol/L of 50mL into the organic phase solution under agitation
The ferric chloride solution of the 0.5mol/L of ketone aqueous solution and 0.05mL are stood after being protected from light stirring a period of time at room temperature；
0.3g ammonium persulfate is added in the hydrochloric acid solution of the 2mol/L of 8.6mL and forms ammonium persulfate-hydrochloric acid solution by S3, incited somebody to action
Ammonium sulfate-hydrochloric acid solution is slowly added in step S2 in reaction solution, uses organic system membrane filtration after standing reaction a period of time
Obtain solid product；
Solid product cleaning, filtering, naturally dry are obtained Fe-PANI powder by S4；
S5, by the glass-carbon electrode successively use 3 μm, 1 μm, 0.3 μm, after the alumina powder grinding and polishing of 50nm it is spare；
S6 takes the Fe-PANI powder ultrasonic disperse of 1~3mg in 0.5mL dehydrated alcohol, and the Nafion solution of 5~15 μ L is added
Ultrasonic disperse forms it into uniform suspension；
S7, the glassy carbon electrode surface for taking the suspension of 10-40 μ L to be added drop-wise to after step S5 polishing with 10-20 μ L/ times, stands to molten
Continue that suspension is added dropwise after liquid volatilization, operation finally obtains Fe-PANI modified electrode repeatedly.
2. preparation method as described in claim 1, which is characterized in that in step s 2, mixed solution is protected from light the time and is
10-50h。
3. preparation method as described in claim 1, which is characterized in that in step s3, after ammonium persulfate-hydrochloric acid solution is added
The standing reaction time is 15-35min.
4. preparation method as described in claim 1, which is characterized in that in step s 4, the step of solid product is cleaned packet
It includes:
The solid product is successively cleaned filtration product with distilled water, hydrochloric acid solution, ethanol washing by S41, hydrochloric acid solution it is dense
Degree range is 0.1-2mol/L.
5. preparation method as described in claim 1, which is characterized in that in step s 6, the Fe-PANI powder for taking 1~3mg
For body ultrasonic disperse in 0.5mL dehydrated alcohol, the Nafion solution ultrasonic disperse that 5~15 μ L are added forms it into uniform suspension
The step of liquid includes:
S61 takes the Fe-PANI powder ultrasonic disperse of 2mg in 0.5mL dehydrated alcohol, and the Nafion solution ultrasound of 10 μ L is added
Dispersion forms it into uniform suspension.
6. preparation method as described in claim 1, which is characterized in that in the step s 7, the suspension for taking 10-40 μ L with
The 10-20 μ L/ times glassy carbon electrode surface being added drop-wise to after step S5 polishing, standing continue that suspension is added dropwise after solution evaporation, instead
Operating the step of finally obtaining Fe-PANI modified electrode again includes:
S71 takes the suspension of 20 μ L to be directly added drop-wise to the glassy carbon electrode surface after step S5 polishing, stands and obtain after solution evaporation
To Fe-PANI modified electrode.
7. a kind of dopamine electrochemical sensing electrode based on Fe2O3 doping polyaniline nano material, which is characterized in that the DOPA
Amine electrochemical sensing electrode is to be prepared by the method for any one of claim 1-6；It tests environment are as follows: with Fe-PANI
Modified electrode is that working electrode, graphite electrode or platinum electrode are to carry out DPV survey to electrode, the sweet common-battery of saturation extremely reference electrode
Examination, wherein potential range -0.1V-0.9 V (vs.SCE), scan amplitude 50mV, pulse width 50ms entirely test environment
It is carried out in the phosphate buffer of pH=6.6-7.2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910687668.0A CN110514725B (en) | 2019-07-29 | 2019-07-29 | Fe-PANI-based dopamine electrochemical sensing electrode and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910687668.0A CN110514725B (en) | 2019-07-29 | 2019-07-29 | Fe-PANI-based dopamine electrochemical sensing electrode and preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110514725A true CN110514725A (en) | 2019-11-29 |
| CN110514725B CN110514725B (en) | 2020-12-11 |
Family
ID=68624250
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910687668.0A Expired - Fee Related CN110514725B (en) | 2019-07-29 | 2019-07-29 | Fe-PANI-based dopamine electrochemical sensing electrode and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110514725B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113804737A (en) * | 2021-08-26 | 2021-12-17 | 宁德师范学院 | Preparation method of polyaniline-loaded silver/cuprous oxide multi-element nano composite material and modified electrode |
| CN113884560A (en) * | 2021-09-30 | 2022-01-04 | 宁德师范学院 | Graphene-based Pt-Pd bimetallic nano composite material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103316706A (en) * | 2013-06-15 | 2013-09-25 | 湖南科技大学 | Metal-doped polyaniline and polypyrrole compound carbonization electric catalyst and preparation method thereof |
| CN104950027A (en) * | 2015-06-20 | 2015-09-30 | 常州大学 | Synthesis of graphene/polyaniline/gold nanoparticle composite material and application thereof to dopamine detection |
| CN106832271A (en) * | 2017-02-14 | 2017-06-13 | 黑龙江大学 | A kind of CNT/phthalocyanine/polyaniline trielement composite material and its preparation method and application |
-
2019
- 2019-07-29 CN CN201910687668.0A patent/CN110514725B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103316706A (en) * | 2013-06-15 | 2013-09-25 | 湖南科技大学 | Metal-doped polyaniline and polypyrrole compound carbonization electric catalyst and preparation method thereof |
| CN104950027A (en) * | 2015-06-20 | 2015-09-30 | 常州大学 | Synthesis of graphene/polyaniline/gold nanoparticle composite material and application thereof to dopamine detection |
| CN106832271A (en) * | 2017-02-14 | 2017-06-13 | 黑龙江大学 | A kind of CNT/phthalocyanine/polyaniline trielement composite material and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| M.U. ANU PRATHAP ET.AL: "Tailoring properties of polyaniline for simultaneous determination of a quaternary mixture of ascorbic acid, dopamine, uric acid, and tryptophan", 《SENSORS AND ACTUATORS B: CHEMICAL》 * |
| 樊荣 等: "铁掺杂聚苯胺/功能化石墨烯制备高效Fe-N-C型氧还原催化剂研究", 《化工新型材料》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113804737A (en) * | 2021-08-26 | 2021-12-17 | 宁德师范学院 | Preparation method of polyaniline-loaded silver/cuprous oxide multi-element nano composite material and modified electrode |
| CN113804737B (en) * | 2021-08-26 | 2024-02-13 | 宁德师范学院 | Polyaniline loaded silver/cuprous oxide multi-element nanocomposite and preparation method of modified electrode |
| CN113884560A (en) * | 2021-09-30 | 2022-01-04 | 宁德师范学院 | Graphene-based Pt-Pd bimetallic nano composite material and preparation method thereof |
| CN113884560B (en) * | 2021-09-30 | 2023-04-28 | 宁德师范学院 | Graphene-based Pt-Pd bimetallic nanocomposite and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110514725B (en) | 2020-12-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110514728B (en) | High-sensitivity Fe-PANI/Pt @ Au dopamine electrochemical detection electrode and preparation thereof | |
| Özel et al. | Chitosan coated carbon fiber microelectrode for selective in vivo detection of neurotransmitters in live zebrafish embryos | |
| Michael et al. | Peer reviewed: color images for fast-scan CV measurements in biological systems | |
| Wen et al. | One-step fabrication of poly (o-aminophenol)/multi-walled carbon nanotubes composite film modified electrode and its application for levofloxacin determination in pharmaceuticals | |
| Yang et al. | The nano-Au self-assembled glassy carbon electrode for selective determination of epinephrine in the presence of ascorbic acid | |
| Li et al. | A sensitive and selective sensor for dopamine determination based on a molecularly imprinted electropolymer of o-aminophenol | |
| Dai Lam et al. | Electrochemically selective determination of dopamine in the presence of ascorbic and uric acids on the surface of the modified Nafion/single wall carbon nanotube/poly (3-methylthiophene) glassy carbon electrodes | |
| Liu et al. | Development and characterization of an amperometric sensor for triclosan detection based on electropolymerized molecularly imprinted polymer | |
| Patel | Electrochemistry for bioanalysis | |
| US20150090601A1 (en) | Cathodized gold nanoparticle graphite pencil electrode and method for glucose detection | |
| CN110514725A (en) | Dopamine electrochemical sensing electrode and its preparation based on Fe-PANI | |
| Babaei et al. | A sensor for simultaneous determination of dopamine and morphine in biological samples using a multi-walled carbon nanotube/chitosan composite modified glassy carbon electrode | |
| CN107179348B (en) | A kind of double-template trace electrochemical sensor and its preparation method and application | |
| CN103675076A (en) | Preparation method and application of electrochemical aptamer sensor for detecting dopamine (DA) | |
| CN107037109A (en) | The chloramphenicol detection biology sensor and method of Magneto separate signal amplification integration | |
| Hu et al. | Selective response of dopamine in the presence of ascorbic acid on l-cysteine self-assembled gold electrode | |
| CN106404863A (en) | Microelectrode biosensor used for in-vivo online detection of plant zeatin, and application of microelectrode biosensor | |
| Smith et al. | Quantitative comparison of enzyme immobilization strategies for glucose biosensing in real‐time using fast‐scan cyclic voltammetry coupled with carbon‐fiber microelectrodes | |
| Lavanya et al. | Detection of catecholamine neurotransmitters by nanostructured SnO2-based electrochemical sensors: a review of recent progress | |
| CN110514726B (en) | Fe-PANI/Au modified electrode for sensitive detection of dopamine and uric acid and preparation thereof | |
| CN106501338A (en) | A kind of electrochemical method for detecting p-nitrophenol based on C60 composites | |
| CN109211989A (en) | A kind of electrochemical aptamer sensor and its preparation and detection method for detecting Atrazine | |
| CN110514727A (en) | Based on Fe2O3 doping polyaniline/platinum dopamine selective electrochemical detecting electrode and its preparation | |
| Mirani et al. | Effect and investigating of oxygen/nitrogen on modified glassy carbon electrode chitosan/carbon nanotube and best detection of nicotine using Cyclic voltammetry measurement technique | |
| Zhang et al. | Poly (O-aminobenzoic acid) modified glassy carbon electrode for electrochemical detection of dopamine in the presence of ascorbic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20201211 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |