CN105353012B - A kind of preparation method of the Epanolol molecular imprinting electrochemical sensor of highly sensitive nano zircite doping - Google Patents
A kind of preparation method of the Epanolol molecular imprinting electrochemical sensor of highly sensitive nano zircite doping Download PDFInfo
- Publication number
- CN105353012B CN105353012B CN201510956285.0A CN201510956285A CN105353012B CN 105353012 B CN105353012 B CN 105353012B CN 201510956285 A CN201510956285 A CN 201510956285A CN 105353012 B CN105353012 B CN 105353012B
- Authority
- CN
- China
- Prior art keywords
- epanolol
- nano zircite
- molecular imprinting
- vinyl
- fluoro
- 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
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
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)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
Abstract
The invention discloses a kind of preparation method of the Epanolol molecular imprinting electrochemical sensor of highly sensitive nano zircite doping,Using Epanolol as template molecule,(5s,8s) ketone of 3 (base of 4 ' chlorine, 3 ' fluorine, 4 vinyl biphenyl 3) 4 hydroxyl, 8 methoxyl group, 1 azaspiro 3 alkene of [4.5] last of the ten Heavenly stems 2 is function monomer,Azodiisobutyronitrile is initiator,Nano zircite is dopant,With 3 (2 chlorine 2 (4 chlorphenyl) vinyl) 2,2 dimethyl cyclopropane carboxylic acid α cyano group (Phenoxyphenyl of 4 fluorine 3) methyl ester is as crosslinking agent,The Epanolol molecular imprinting electrochemical sensor of highly sensitive nano zircite doping is prepared for accordingly,The analysis method is simple and practical,It is complicated to overcome conventional analysis method,Equipment is expensive,The shortcomings that sensitivity is low.
Description
Technical field
The present invention relates to molecular imprinting electrochemical sensor, especially a kind of highly sensitive nano zircite doping according to
Dissolve the preparation method of Luo Er molecular imprinting electrochemical sensors.
Background technology
Selecting property of Epanolol blocks β1receptor, and no inherent sympathomimetic activity, main function is to be used to treat high blood
Pressure, can also treat angina pectoris, but due to long-term or such medicine, which is excessively used, can cause thermophilic medicine problem or insomnia, nausea etc. are secondary to make
With, or even fatal risk can be produced when discontinuing medication suddenly, therefore controlled substance is classified as by most country in the world.
The method of measure Epanolol has Gradient Elution method, RPLC-diode battle array
Row method etc..But there is the shortcomings of cost is high, time-consuming, sensitivity is not high in these methods due to needing expensive instrument and equipment；
Therefore, study a kind of high sensibility, easy Epanolol assay method has very important significance.
Molecular imprinting technology is using target molecule to be measured as template molecule, will be led to functional monomer complementary in structure
Cross covalently or non-covalently key and combine to form monomer template molecular complex with template molecule, add crosslinking agent and be allowed to enter with monomer
Row polymerisation forms template molecule polymer, by either physically or chemically removing template molecule after the completion of reaction, is divided
Sub- imprinted polymer, complementary and with Multiple recognition site the sky with former microsphere space structure is formed in the polymer
Cave.Current method is because the function monomer of selection can not be properly matched with template molecule, and the rigidity being crosslinked is also poor,
Therefore sensitivity is not high.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of equipment it is simple, make a kind of easy highly sensitive nanometer
The preparation method of the Epanolol molecular imprinting electrochemical sensor of zirconium oxide doping.
In order to solve the above technical problems, the present invention adopts the following technical scheme that：Using Epanolol as template molecule, (5s,
8s) -3- (4 '-chloro- 3 '-fluoro- 4- vinyl biphenyls -3- bases) -4- hydroxyls -8- methoxyl group -1- azaspiros [4.5] decyl- 3- alkene -2-
Ketone is function monomer, azodiisobutyronitrile is initiator, nano zircite is dopant, with 3- (the chloro- 2- of 2- (4- chlorphenyls) second
Alkenyl) -2,2- dimethyl cyclopropane carboxylic acids-alpha-cyano-(the fluoro- 3- Phenoxyphenyls of 4-)-methyl ester be crosslinking agent prepare.
A kind of preparation of the Epanolol molecular imprinting electrochemical sensor of above-mentioned highly sensitive nano zircite doping
Method, using Epanolol as template molecule, (5s, 8s) -3- (4 '-chloro- 3 '-fluoro- 4- vinyl biphenyls -3- bases) -4- hydroxyls -8-
Methoxyl group -1- azaspiros [4.5] decyl- 3- alkene -2- ketone is function monomer, azodiisobutyronitrile is initiator, with 3- (the chloro- 2- of 2-
(4- chlorphenyls) vinyl) -2,2- dimethyl cyclopropane carboxylic acids-alpha-cyano-(the fluoro- 3- Phenoxyphenyls of 4-)-methyl ester for hand over
Connection agent, nano zircite are dopant, and a kind of hybridized nanometer zirconium oxide Epanolol is formed in diameter 2mm glassy carbon electrode surfaces
Molecular imprinting polymer membrane, then template molecule is washed using the acetic acid and phenmethylol mixed solvent of eluant, eluent mol ratio 2: 3
It is de-, produce.
A kind of preparation of the Epanolol molecular imprinting electrochemical sensor of above-mentioned highly sensitive nano zircite doping
Method, comprise the following steps：
The ＞ of ＜ 1 into 10.0mL etoh solvents, sequentially add 0.2mmol~0.8mmol template molecules Epanolol,
2.0mmol~6mmol function monomers (5s, 8s) -3- (4 '-chloro- 3 '-fluoro- 4- vinyl biphenyls -3- bases) -4- hydroxyl -8- methoxies
Base -1- azaspiros [4.5] decyl- 3- alkene -2- ketone, 3.8mmol crosslinking agents 3- (the chloro- 2- of 2- (4- chlorphenyls) vinyl) -2,2- bis-
Methylcyclopropanecarboxylic acid-alpha-cyano-(the fluoro- 3- Phenoxyphenyls of 4-)-methyl ester, 0.6mmol initiator azodiisobutyronitriles and
0.0200g~0.0400g nano zircite, often add a kind of chemical reagent ultrasonic wave and dissolve 12 minutes；
The ＞ of ＜ 2 take the ＞ of the step ＜ 1 μ L of mixture 6 to be applied to clean smooth a diameter of 2mm glassy carbon electrode surface, and it is small to place 6
Shi Hou, the electrode after modification is placed in thermal polymerization 1.5 hours in 85 DEG C of vacuum drying chamber, then use eluant, eluent mol ratio for
2: 3 acetic acid and phenmethylol mixed solvent produce template molecule elution.
Research finds, using Epanolol as template molecule, (5s, 8s) -3- (4 '-chloro- 3 '-fluoro- 4- vinyl biphenyls -3-
Base) -4- hydroxyls -8- methoxyl group -1- azaspiros [4.5] decyl- 3- alkene -2- ketone is function monomer, azodiisobutyronitrile be initiator,
Nano zircite is dopant, with 3- (the chloro- 2- of 2- (4- chlorphenyls) vinyl) -2,2- dimethyl cyclopropane carboxylic acid's-alpha-cyanos -
Epanolol molecular imprinting electrochemical sensor prepared by (the fluoro- 3- Phenoxyphenyls of 4-)-methyl ester, available for measure according to dissolving Lip river
Your content.The electrochemical analysis method for determining Epanolol is established using the present invention, there is very outstanding sensitivity；According to dissolving Lip river
Your concentration is 2.5 × 10-8~1.8 × 10-4Good linear relationship (linearly dependent coefficient R=is presented in the range of mol/L
0.9988), detection limit (S/N=3) is 1.5 × 10-9Mol/L, therefore, the Epanolol molecular engram electricity of nano zircite doping
Chemical sensor has higher sensitivity, more than current detection method；And equipment is simple, it is simple to make.
Brief description of the drawings
Fig. 1 is that a kind of Epanolol molecular imprinting electrochemical of highly sensitive nano zircite doping passes in embodiment 1
The working curve diagram of sensor.
Embodiment
Embodiment 1
First, the processing of glass-carbon electrode
Glass-carbon electrode is polished with 1.0 μm, 0.3 μm and 0.05 μm of alumina powder successively on polishing cloth, is then placed in
Ultrasonic 8min in the nitric acid that volume ratio is 1: 1, ultrasonic 8min in absolute ethyl alcohol is placed into, be finally cleaned by ultrasonic with pure water clean.
2nd, the preparation of Epanolol molecular imprinting electrochemical sensor
The ＞ of ＜ 1 sequentially add 0.5mmol template molecules Epanolol, 5.0mmol function monomers into 10.0mL etoh solvents
(5s, 8s) -3- (4 '-chloro- 3 '-fluoro- 4- vinyl biphenyls -3- bases) -4- hydroxyls -8- methoxyl group -1- azaspiros [4.5] decyl- 3-
Alkene -2- ketone, 3.8mmol crosslinking agents 3- (the chloro- 2- of 2- (4- chlorphenyls) vinyl) -2,2- dimethyl cyclopropane carboxylic acid's-alpha-cyanos -
The nano zircite of (the fluoro- 3- Phenoxyphenyls of 4-)-methyl ester, 0.6mmol initiator azodiisobutyronitriles and 0.0250g, often
A kind of chemical reagent ultrasonic wave is added to dissolve 12 minutes；
The ＞ of ＜ 2 take the ＞ of the step ＜ 1 μ L of mixture 6 to be applied in clean smooth a diameter of 2mm glassy carbon electrode surface, place 6
After hour, the electrode after modification is placed in thermal polymerization 1.5 hours in 85 DEG C of vacuum drying chamber, then using eluant, eluent mol ratio
2: 3 acetic acid and phenmethylol mixed solvent are by template molecule elution, by magnetic agitation eluted template molecule, until being examined in eluent
Template molecule is not detected, then the solvent of trace electrode surface is washed away with ultra-pure water, then trace electrode is stored in ultra-pure water
It is stand-by.
3rd, the measure of the drafting of working curve and detection limit
The reality of the Epanolol molecular engram electrode response characteristic of nano zircite doping is carried out with differential pulse voltammetry
Test, determine the range of linearity and detection limit.By the Epanolol molecular engram electrode of nano zircite doping respectively in various concentrations
Epanolol solution in cultivate 6 minutes (bottom liquid be 5.0mmol/L K3[Fe(CN)6] -0.5mol/L pH=7.5 phosphate
Cushioning liquid solution), then carry out differential pulse voltammetry measurement.Epanolol solution concentration is 2.5 × 10-8~1.8 × 10-4Good linear relationship is presented in the range of mol/L；Linear equation is Ip (μ A)=- 0.1134c (μm ol/L)+23.50, linearly
Coefficient correlation is R=0.9988, and detection limit (S/N=3) is 1.5 × 10-9mol/L。
Therefore, the Epanolol molecular engram electrode of nano zircite doping has high sensitivity.
Claims (1)
1. a kind of preparation method of the Epanolol molecular imprinting electrochemical sensor of highly sensitive nano zircite doping, its
It is characterised by using 0.02mmol/mL~0.08mmol/mL Epanolol as template molecule, 0.2mmol/mL~0.6mmol/mL
(5s, 8s) -3- (4 '-chloro- 3 '-fluoro- 4- vinyl biphenyls -3- bases) -4- hydroxyls -8- methoxyl group -1- azaspiros [4.5] decyl- 3-
Alkene -2- ketone is function monomer, 0.06mmol/mL azodiisobutyronitriles are initiator, with the 0.38mmol/mL 3- (chloro- 2- (4- of 2-
Chlorphenyl) vinyl) -2,2- dimethyl cyclopropane carboxylic acids-alpha-cyano-(the fluoro- 3- Phenoxyphenyls of 4-)-methyl ester for crosslinking
Agent, 0.0020g/mL~0.0040g/mL nano zircites are dopant, and a kind of hybridized nanometer is formed in glassy carbon electrode surface
Zirconium oxide Epanolol molecular imprinting polymer membrane, then using eluant, eluent acetic acid and phenmethylol mixed solvent eluted template point
Son produces；
Specifically carried out by following operation：
<1>Into 10.0mL etoh solvents, sequentially add 0.2mmol~0.8mmol template molecules Epanolol, 2.0mmol~
6mmol function monomers (5s, 8s) -3- (4 '-chloro- 3 '-fluoro- 4- vinyl biphenyls -3- bases) -4- hydroxyl -8- methoxyl group -1- azepines
Spiral shell [4.5] decyl- 3- alkene -2- ketone, 3.8mmol crosslinking agents 3- (the chloro- 2- of 2- (4- chlorphenyls) vinyl) -2,2- dimethylcyclopropanes
Carboxylic acid-alpha-cyano-(the fluoro- 3- Phenoxyphenyls of 4-)-methyl ester, 0.6mmol initiator azodiisobutyronitriles and 0.0200g~
0.0400g nano zircite, often add a kind of chemical reagent ultrasonic wave and dissolve 12 minutes；
<2>Take step<1>The μ L of mixture 6 be applied in clean smooth a diameter of 2mm glassy carbon electrode surface, place 6 hours
Afterwards, the electrode after modification is placed in thermal polymerization 1.5 hours in 85 DEG C of vacuum drying chamber, then uses eluant, eluent mol ratio as 2:
3 acetic acid and phenmethylol mixed solvent produce template molecule elution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510956285.0A CN105353012B (en) | 2015-12-21 | 2015-12-21 | A kind of preparation method of the Epanolol molecular imprinting electrochemical sensor of highly sensitive nano zircite doping |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510956285.0A CN105353012B (en) | 2015-12-21 | 2015-12-21 | A kind of preparation method of the Epanolol molecular imprinting electrochemical sensor of highly sensitive nano zircite doping |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105353012A CN105353012A (en) | 2016-02-24 |
| CN105353012B true CN105353012B (en) | 2017-12-01 |
Family
ID=55329018
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510956285.0A Expired - Fee Related CN105353012B (en) | 2015-12-21 | 2015-12-21 | A kind of preparation method of the Epanolol molecular imprinting electrochemical sensor of highly sensitive nano zircite doping |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105353012B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2337332B (en) * | 1998-05-13 | 2002-12-18 | Univ Cranfield | Disposable affinity sensor |
| CN201188095Y (en) * | 2008-05-07 | 2009-01-28 | 济南大学 | Molecular engram membrane electrode for detecting circumstance incretion interference object |
| CN101556258A (en) * | 2009-04-03 | 2009-10-14 | 江苏工业学院 | Timolol maleate potentiometric chemical sensor and preparation method thereof |
| CN102043005A (en) * | 2010-10-29 | 2011-05-04 | 济南大学 | Nanometer synergistic molecularly imprinted membrane electrode for detecting forbidden drugs in weight-reducing health care product |
| CN102116759A (en) * | 2009-12-30 | 2011-07-06 | 宁波大学 | Selective electrode of tetracycline drugs and preparation method thereof |
| CN103926286A (en) * | 2014-04-25 | 2014-07-16 | 广西民族大学 | High-sensitivity nanometer cobalt oxide-doped talampicillin molecular imprinting electrochemical sensor and preparation method thereof |
| CN103926288A (en) * | 2014-04-25 | 2014-07-16 | 广西民族大学 | High-sensitivity nanometer cobalt oxide-doped amobarbital molecular imprinting electrochemical sensor and preparation method thereof |
-
2015
- 2015-12-21 CN CN201510956285.0A patent/CN105353012B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2337332B (en) * | 1998-05-13 | 2002-12-18 | Univ Cranfield | Disposable affinity sensor |
| CN201188095Y (en) * | 2008-05-07 | 2009-01-28 | 济南大学 | Molecular engram membrane electrode for detecting circumstance incretion interference object |
| CN101556258A (en) * | 2009-04-03 | 2009-10-14 | 江苏工业学院 | Timolol maleate potentiometric chemical sensor and preparation method thereof |
| CN102116759A (en) * | 2009-12-30 | 2011-07-06 | 宁波大学 | Selective electrode of tetracycline drugs and preparation method thereof |
| CN102043005A (en) * | 2010-10-29 | 2011-05-04 | 济南大学 | Nanometer synergistic molecularly imprinted membrane electrode for detecting forbidden drugs in weight-reducing health care product |
| CN103926286A (en) * | 2014-04-25 | 2014-07-16 | 广西民族大学 | High-sensitivity nanometer cobalt oxide-doped talampicillin molecular imprinting electrochemical sensor and preparation method thereof |
| CN103926288A (en) * | 2014-04-25 | 2014-07-16 | 广西民族大学 | High-sensitivity nanometer cobalt oxide-doped amobarbital molecular imprinting electrochemical sensor and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105353012A (en) | 2016-02-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105548298B (en) | A kind of preparation method of the dezocine molecular imprinting electrochemical sensor of highly sensitive nano zircite doping | |
| CN105548310B (en) | A kind of preparation method of the pafenolol molecular imprinting electrochemical sensor of highly sensitive nano zircite doping | |
| CN105628777B (en) | A kind of preparation method of the phenprobamate molecular imprinting electrochemical sensor of highly sensitive functionalization golden nanometer particle doping | |
| CN105510415B (en) | A kind of preparation method of the Meprobamate molecular imprinting electrochemical sensor of highly sensitive functionalization golden nanometer particle doping | |
| CN103926286B (en) | A kind of talampicillin molecular imprinting electrochemical sensor of highly sensitive nano oxidized cobalt doped and preparation method thereof | |
| CN103926289B (en) | A kind of micronomicin molecular imprinting electrochemical sensor of highly sensitive nano oxidized cobalt doped and preparation method thereof | |
| CN103926288B (en) | A kind of amobarbital molecular imprinting electrochemical sensor of highly sensitive nano oxidized cobalt doped and preparation method thereof | |
| CN102901757A (en) | Sudan I molecular imprinting electrochemical sensor and preparation method thereof | |
| CN105628762B (en) | A kind of preparation method of the Aniracetam molecular imprinting electrochemical sensor of highly sensitive functionalization Nano silver grain doping | |
| CN105548311B (en) | A kind of preparation method of the bevantolol molecular imprinting electrochemical sensor of highly sensitive nano zircite doping | |
| CN105353012B (en) | A kind of preparation method of the Epanolol molecular imprinting electrochemical sensor of highly sensitive nano zircite doping | |
| CN108007987A (en) | A kind of preparation method of ethyldopa molecular imprinting electrochemical sensor | |
| CN105628775B (en) | A kind of preparation method of the Levetiracetam molecular imprinting electrochemical sensor of highly sensitive functionalization Nano silver grain doping | |
| CN107976479A (en) | A kind of preparation method of mysoline molecular imprinting electrochemical sensor | |
| CN104597092A (en) | Preparation method of dicyandiamide molecular imprinting polymer membrane electrode | |
| CN106706738A (en) | Preparation method of high-sensitivity oxazepam molecular imprinting electrochemical sensor | |
| CN105628776B (en) | A kind of preparation method of the Felbamate molecular imprinting electrochemical sensor of highly sensitive functionalization golden nanometer particle doping | |
| CN107991498A (en) | A kind of preparation method of phensuximide molecular imprinting electrochemical sensor | |
| CN107917946A (en) | A kind of preparation method of triperazine molecular imprinting electrochemical sensor | |
| CN106770557A (en) | A kind of preparation method of highly sensitive Bezafibrate molecular imprinting electrochemical sensor | |
| CN107941878A (en) | A kind of preparation method of depamide molecular imprinting electrochemical sensor | |
| CN106596680A (en) | Preparation method of high-sensitivity mirtazapine molecularly-imprinted electrochemical sensor | |
| CN107957438A (en) | A kind of preparation method of eszopiclone molecular imprinting electrochemical sensor | |
| CN107957444A (en) | A kind of preparation method of easypro thiazine molecular imprinting electrochemical sensor | |
| CN109342541A (en) | A kind of preparation method of chlorimipramine molecular imprinting electrochemical sensor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20171201 Termination date: 20191221 |