CN106706730A - Preparing method of Tolcapone molecular imprinting electrochemical sensor with high sensitivity - Google Patents
Preparing method of Tolcapone molecular imprinting electrochemical sensor with high sensitivity Download PDFInfo
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- CN106706730A CN106706730A CN201710014692.9A CN201710014692A CN106706730A CN 106706730 A CN106706730 A CN 106706730A CN 201710014692 A CN201710014692 A CN 201710014692A CN 106706730 A CN106706730 A CN 106706730A
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- tolcapone
- concentration
- template molecule
- molecular imprinting
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- 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
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- 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
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- 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
Abstract
The invention discloses a preparing method of a Tolcapone molecular imprinting electrochemical sensor with high sensitivity. Tolcapone is adopted as a template molecule, forsythoside is adopted as a functional monomer, azodiisobutyronitrile is adopted as an initiator, a cobalt zinc double metal organic frame material is adopted as a dopant, acetylshikonin is adopted as a crosslinking agent, and thus the Tolcapone molecular imprinting electrochemical sensor with the high sensitivity is prepared. The analysis method is simple and practical, and overcomes the disadvantages of a previous method of being complex, expensive in equipment, and low in sensitivity.
Description
Technical field
The present invention relates to molecular imprinting electrochemical sensor, especially a kind of highly sensitive Tolcapone molecular engram electrification
Learn the preparation method of sensor.
Background technology
Tolcapone (Tolcapone) indication：It is a kind of selectivity and reversible catechol O-methyltransferase
(COMT) inhibitor.The auxiliary for being clinically used to receive the Primary ventricular hemorrhage that levodopa and carbidopa combinations are treated is controlled
Treat.But because the such medicine of long-term use can cause dyskinesia, nausea, sleep disordered, myodystony, dreaminess, apocleisis, flesh
Meat cramp, orthostatic are uncomfortable, drowsiness, diarrhoea, amentia, dizziness, headache, illusion, vomiting, constipation, fatigue, upper breathing
Road infection, collapse, hidrosis, urinary tract infection, dry, stomachache, urine discoloration etc..Heavy dose of use can cause kidney, liver function liver function to decline
Exhaust.
The method for determining Tolcapone has high performance liquid chromatography, application of gas chromatorgraphy/mass method etc..But these methods are high due to needing
Expensive instrument and equipment, exist high cost, time-consuming, it is sensitive not high the shortcomings of.Therefore, a kind of high sensibility, easy support card are studied
Friend's detection method is significant.
Molecular imprinting technology is, with target molecule to be measured as template molecule, will to lead 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, forms with the complementation of former microsphere space structure and with the sky in multiple action site in the polymer
Cave.Current method is incorrect because the function monomer for selecting is matched with template molecule and crosslinking agent, and the rigidity being crosslinked
It is poor, therefore sensitivity is not high.
The content of the invention
The technical problem to be solved in the present invention is to provide that a kind of equipment is simple, make easily, a kind of highly sensitive support card
The preparation method of friend's molecular imprinting electrochemical sensor.
In order to solve the above technical problems, the present invention is adopted the following technical scheme that：With Tolcapone as template molecule, capsule of weeping forsythia fat glycosides
For function monomer, azodiisobutyronitrile be initiator, cobalt zinc bimetallic organic framework materials be dopant, be with Acetylshikonin
It is prepared by crosslinking agent.
The preparation method of above-mentioned a kind of highly sensitive Tolcapone molecular imprinting electrochemical sensor, with Tolcapone as template
Molecule, capsule of weeping forsythia fat glycosides be function monomer, azodiisobutyronitrile be initiator, with Acetylshikonin as crosslinking agent, the isobutyl of azo two
Nitrile is initiator, cobalt zinc bimetallic organic framework materials are dopant, and a kind of double gold of hydridization cobalt zinc are formed in glassy carbon electrode surface
Category organic framework materials Tolcapone molecular imprinting polymer membrane, template molecule elution is obtained final product.
A kind of preparation method of above-mentioned highly sensitive Tolcapone molecular imprinting electrochemical sensor, comprises the following steps：
<1>The mixing water of the cobaltous sulfate (II) and the zinc sulfate of 0.2mol/L that are solvent compound concentration as 0.2mol/L with water
Solution 15ml, the Isosorbide-5-Nitrae-cyclohexyl dicarboxylic acid solution 40ml for being solvent compound concentration as 0.05mol/L with DMF,
The mixed aqueous solution of the 15ml cobaltous sulfates (II) and zinc sulfate that then take preparation is added drop-wise to the 40ml of preparation with 5 drops/sec of speed
In Isosorbide-5-Nitrae-cyclohexyl dicarboxylic acid solution, it is stirred vigorously with 3000 revs/min of speed during dropwise addition, then 115 in the hot water kettle of 100ml
Reaction 8 hours is carried out at DEG C, the precipitation of gained is collected by centrifugation after cooling, DMF and absolute ethyl alcohol is respectively adopted
Washing 2 times, is collected by centrifugation precipitation, and being deposited at 45 DEG C for collection is vacuum dried, that is, obtain with outstanding sensing capabilities
Cobalt zinc bimetallic organic framework materials；
<2>In to 10.0mL etoh solvents, sequentially add 0.50mmol~1.50mmol template molecule Tolcapone,
The function monomer capsule of weeping forsythia fat glycosides of 1.0mmol~6.0mmol, the crosslinking agent Acetylshikonin of 2.0mmol, the initiator of 0.30mmol
Azodiisobutyronitrile and step<1>The cobalt zinc bimetallic organic framework materials 0.010g~0.120g of preparation, often adds one kindization
Reagent ultrasonic wave is learned to dissolve 5 minutes；
<3>Take step<2>The μ L of mixture 9 be applied to clean smooth glassy carbon electrode surface, after placing 8 hours, will modify
Electrode afterwards is placed in thermal polymerization 2.0 hours in 70 DEG C of vacuum drying chamber, is then mixed using the acetonitrile and acetic acid of mol ratio 1: 2
Solvent eluant, eluent obtains final product template molecule elution.
Experiment find, with Tolcapone as template molecule, capsule of weeping forsythia fat glycosides as function monomer, azodiisobutyronitrile as initiator,
Cobalt zinc bimetallic organic framework materials are dopant, with the Tolcapone molecular imprinting electrochemical that Acetylshikonin is prepared as crosslinking agent
Sensor, delicately can be used to determine the content of Tolcapone very much.The electrochemical analysis side for determining Tolcapone is set up using the present invention
Method, with especially outstanding sensitivity；The concentration of Tolcapone is 1.5 × 10-8~2.6 × 10-4Presented in the range of mol/L good
Linear relationship (linearly dependent coefficient is R=0.9994), detection limit (S/N=3) be 4.2 × 10-9Mol/L, therefore, the support card
Friend's molecular imprinting electrochemical sensor has sensitivity higher, more than current detection method；And equipment is simple, make appearance
Easily.
Brief description of the drawings
Fig. 1 is a kind of work of the preparation method of highly sensitive Tolcapone molecular imprinting electrochemical sensor in embodiment 1
Make curve map.
Specific embodiment
Embodiment 1
First, the treatment 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
Volume ratio be 1: 1 nitric acid in ultrasound 6min, place into ultrasound 6min in absolute ethyl alcohol, be finally cleaned by ultrasonic with pure water clean.
2nd, the preparation of Tolcapone molecular imprinting electrochemical sensor
<1>The mixing water of the cobaltous sulfate (II) and the zinc sulfate of 0.2mol/L that are solvent compound concentration as 0.2mol/L with water
Solution 15ml, the Isosorbide-5-Nitrae-cyclohexyl dicarboxylic acid solution 40ml for being solvent compound concentration as 0.05mol/L with DMF,
The mixed aqueous solution of the 15ml cobaltous sulfates (II) and zinc sulfate that then take preparation is added drop-wise to the 40ml of preparation with 5 drops/sec of speed
In Isosorbide-5-Nitrae-cyclohexyl dicarboxylic acid solution, it is stirred vigorously with 3000 revs/min of speed during dropwise addition, then 115 in the hot water kettle of 100ml
Reaction 8 hours is carried out at DEG C, the precipitation of gained is collected by centrifugation after cooling, DMF and absolute ethyl alcohol is respectively adopted
Washing 2 times, is collected by centrifugation precipitation, and being deposited at 45 DEG C for collection is vacuum dried, that is, obtain with outstanding sensing capabilities
Cobalt zinc bimetallic organic framework materials；
<2>In to 10.0mL etoh solvents, 1.0mmol template molecules Tolcapone, 3.0mmol capsule of weeping forsythia fat glycosides work(are sequentially added
Can monomer, the crosslinking agent Acetylshikonin of 2.0mmol, the initiator azodiisobutyronitrile and step of 0.30mmol<1>Cobalt zinc
Bimetallic organic framework materials 0.030g, often adds a kind of chemical reagent ultrasonic wave to dissolve 5 minutes；
<3>Take step<2>The μ L of mixture 9 be applied to clean smooth glassy carbon electrode surface, after placing 8 hours, will modify
Electrode afterwards is placed in thermal polymerization 2.0 hours in 70 DEG C of vacuum drying chamber, then the acetonitrile and acetic acid mixtures of eluents using 1: 2
By template molecule elution, by magnetic agitation eluted template molecule, until can not detect template molecule in eluent, then with ultrapure
The solvent acetonitrile and acetic acid of trace electrode surface are removed in washing, are then stored in trace electrode stand-by in ultra-pure water.
3rd, the measure of the drafting of working curve and detection limit
The experiment of Tolcapone molecular imprinting electrochemical sensor electrode response characteristic is carried out with differential pulse voltammetry, line is determined
Property scope and detection limit.Tolcapone molecular engram electrode is cultivated into 9 minutes (bottom liquid in the Tolcapone solution of various concentrations respectively
It is 5.0mmol/L K3[Fe(CN)6] -0.5mol/L pH=7.5 PBS solution), then carry out differential pulse
Voltammetry is measured.Tolcapone solution concentration is 1.5 × 10-8~2.6 × 10-4Good linear relationship is presented in the range of mol/L；
Linear equation is Ip (μ A)=- 0.0876c (μm ol/L)+23.44, and linearly dependent coefficient is R=0.9994, detection limit (S/N=
3) it is 4.2 × 10-9mol/L。
Therefore, the Tolcapone molecular engram sensor has sensitivity higher.
Claims (1)
1. a kind of preparation method of highly sensitive Tolcapone molecular imprinting electrochemical sensor, it is characterised in that the sensor is
It is prepared by the following method：The Tolcapone of concentration 0.050mmol/mL~0.150mmol/ml is template molecule, concentration
The capsule of weeping forsythia fat glycosides of 0.10mmol/ml~0.60mmol/ml is function monomer, the azodiisobutyronitrile of concentration 0.03mmol/ml is
Initiator, the Acetylshikonin of concentration 0.20mmol/ml are crosslinking agent, the cobalt zinc of concentration 0.0010g/ml~0.0120g/ml is double
Metal-organic framework material is dopant, and a kind of hydridization cobalt zinc bimetallic organic framework materials support card is formed in glassy carbon electrode surface
Friend's molecular imprinting polymer membrane, then using the acetonitrile and acetic acid mixed solvent eluted template molecule of eluant, eluent mol ratio 1: 2
Obtain final product；
Specifically carried out by following operation：
<1>The mixed aqueous solution of the cobaltous sulfate (II) and the zinc sulfate of 0.2mol/L that are solvent compound concentration as 0.2mol/L with water
15ml, the Isosorbide-5-Nitrae-cyclohexyl dicarboxylic acid solution 40ml for being solvent compound concentration as 0.05mol/L with DMF, then
The mixed aqueous solution of the 15ml cobaltous sulfates (II) and zinc sulfate that take preparation is added drop-wise to the 40ml1,4- of preparation with 5 drops/sec of speed
In cyclohexyl dicarboxylic acid solution, it is stirred vigorously with 3000 revs/min of speed during dropwise addition, then in the hot water kettle of 100ml at 115 DEG C
Reaction 8 hours is carried out, the precipitation of gained is collected by centrifugation after cooling, DMF and absolute ethanol washing is respectively adopted
2 times, precipitation is collected by centrifugation, being deposited at 45 DEG C for collection is vacuum dried, that is, obtain the cobalt with outstanding sensing capabilities
Zinc bimetallic organic framework materials；
<2>In to 10.0mL etoh solvents, template molecule Tolcapone, the 1.0mmol of 0.50mmol~1.50mmol are sequentially added
The function monomer capsule of weeping forsythia fat glycosides of~6.0mmol, the crosslinking agent Acetylshikonin of 2.0mmol, the initiator azo two of 0.30mmol
Isobutyronitrile and step<1>The cobalt zinc bimetallic organic framework materials 0.010g~0.120g of preparation, often adds a kind of chemical reagent
Ultrasonic wave dissolves 5 minutes；
<3>Take step<2>The μ L of mixture 9 be applied to clean smooth glassy carbon electrode surface, after placing 8 hours, after modification
Electrode is placed in thermal polymerization 2.0 hours in 70 DEG C of vacuum drying chamber, then using the acetonitrile and acetic acid mixed solvent of mol ratio 1: 2
Eluant, eluent obtains final product template molecule elution.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109324104A (en) * | 2018-11-06 | 2019-02-12 | 广西民族大学 | A kind of preparation method of neostigmine molecular imprinting electrochemical sensor |
| CN110423358A (en) * | 2019-08-14 | 2019-11-08 | 合肥工业大学 | The preparation and application of the porous carbon nano-tube material of the preparation method and one-dimensional N doping of one-dimensional tubulose MOF material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103926289A (en) * | 2014-04-25 | 2014-07-16 | 广西民族大学 | Nanometer cobaltous oxide doped micronomicin molecular imprinting electrochemical sensor with high sensitivity and preparation method of sensor |
| CN105566654A (en) * | 2016-01-28 | 2016-05-11 | 浙江省肿瘤医院 | One-dimensional structure metal-organic framework compound and preparation method thereof |
| CN106111196A (en) * | 2016-06-07 | 2016-11-16 | 青岛大学 | A kind of preparation method and application of iron porphyrin chloride/methylene blue@metallic organic framework composite electrode |
| CN106198701A (en) * | 2016-08-18 | 2016-12-07 | 济南大学 | A kind of metal-organic framework material area load molecular imprinted polymer membrane is for the electrochemical detection method of orthene |
-
2017
- 2017-01-09 CN CN201710014692.9A patent/CN106706730A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103926289A (en) * | 2014-04-25 | 2014-07-16 | 广西民族大学 | Nanometer cobaltous oxide doped micronomicin molecular imprinting electrochemical sensor with high sensitivity and preparation method of sensor |
| CN105566654A (en) * | 2016-01-28 | 2016-05-11 | 浙江省肿瘤医院 | One-dimensional structure metal-organic framework compound and preparation method thereof |
| CN106111196A (en) * | 2016-06-07 | 2016-11-16 | 青岛大学 | A kind of preparation method and application of iron porphyrin chloride/methylene blue@metallic organic framework composite electrode |
| CN106198701A (en) * | 2016-08-18 | 2016-12-07 | 济南大学 | A kind of metal-organic framework material area load molecular imprinted polymer membrane is for the electrochemical detection method of orthene |
Non-Patent Citations (1)
| Title |
|---|
| ZHENZHONG GUO, ET AL.: "Molecularly Imprinted Polymer/Metal Organic Framework Based Chemical Sensors", 《COATINGS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109324104A (en) * | 2018-11-06 | 2019-02-12 | 广西民族大学 | A kind of preparation method of neostigmine molecular imprinting electrochemical sensor |
| CN110423358A (en) * | 2019-08-14 | 2019-11-08 | 合肥工业大学 | The preparation and application of the porous carbon nano-tube material of the preparation method and one-dimensional N doping of one-dimensional tubulose MOF material |
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Application publication date: 20170524 |