CN106501335A - A kind of preparation method of highly sensitive estazolam molecular imprinting electrochemical sensor - Google Patents
A kind of preparation method of highly sensitive estazolam molecular imprinting electrochemical sensor Download PDFInfo
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- CN106501335A CN106501335A CN201710014694.8A CN201710014694A CN106501335A CN 106501335 A CN106501335 A CN 106501335A CN 201710014694 A CN201710014694 A CN 201710014694A CN 106501335 A CN106501335 A CN 106501335A
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- estazolam
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- 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 kind of preparation method of highly sensitive estazolam molecular imprinting electrochemical sensor, with estazolam as template molecule, resveratrol as function monomer, azodiisobutyronitrile as initiator, nickel cobalt bimetallic organic framework materials are as dopant, using acetylshikonin as cross-linking agent, a kind of highly sensitive estazolam molecular imprinting electrochemical sensor is prepared for accordingly, the analysis method is simple and practical, overcomes the low shortcoming of conventional analysis method complexity, apparatus expensive, sensitivity.
Description
Technical field
The present invention relates to molecular imprinting electrochemical sensor, especially a kind of highly sensitive estazolam molecular engram electricity
The preparation method of chemical sensor.
Background technology
Estazolam (Estazolam) indication：Estazolam is the extraction medicine of benzodiazepine medicine.Have control burnt
The properties such as worry, epilepsy, calm, muscle relaxant.Generally as the insomnia prescription of short-term, it is that quick absorption and half-life are medium
The stable class hypnotic drug of Benzodiazepine.But as the such medicine of life-time service can cause central nervous system in suppression shape
State or acute poisoning, myasthenia graviss, acute angle closure glaucoma etc..Heavy dose of use can cause chronic obstructive lung pathological changes and
Kidney, liver function liver function injury.
The method for determining estazolam has high performance liquid chromatography, application of gas chromatorgraphy/mass method etc..But these methods are due to needing
Expensive instrument and equipment, exist high cost, time-consuming, sensitive not high the shortcomings of.Therefore, a kind of high sensibility, easy Chinese mugwort are studied
Department's azoles logical sequence detection method is significant.
Molecular imprinting is with target molecule to be measured as template molecule, will lead to complementary functional monomer in structure
Cross covalently or non-covalently key and monomer template molecular complex is combined to form with template molecule, add cross-linking agent and be allowed to enter with monomer
Row polyreaction forms template molecule polymer, by either physically or chemically removing template molecule after the completion of reaction, is divided
Sub- imprinted polymer, forms and sky with multiple action site complementary with former microsphere space structure in the polymer
Cave.Current method is incorrect as the function monomer of selection is mated with template molecule and cross-linking agent, and the rigidity being crosslinked
Poor, therefore sensitivity is not high.
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 easy, a kind of highly sensitive Chinese mugwort department
The preparation method of azoles logical sequence molecular imprinting electrochemical sensor.
For solving above-mentioned technical problem, the present invention is adopted the following technical scheme that：With estazolam as template molecule, white hellebore
Alcohol is function monomer, azodiisobutyronitrile is initiator, nickel cobalt bimetallic organic framework materials are dopant, with acetylshikonin
Prepare for cross-linking agent.
A kind of preparation method of above-mentioned highly sensitive estazolam molecular imprinting electrochemical sensor, with estazolam be
Template molecule, resveratrol be function monomer, azodiisobutyronitrile be initiator, with acetylshikonin as cross-linking agent, azo two
Isopropyl cyanide is initiator, nickel cobalt bimetallic organic framework materials are dopant, forms a kind of hydridization nickel cobalt in glassy carbon electrode surface
Bimetallic organic framework materials estazolam molecular imprinting polymer membrane, template molecule elution is obtained final product.
A kind of preparation method of above-mentioned highly sensitive estazolam molecular imprinting electrochemical sensor, including following step
Suddenly：
<1>The mixing water of the nickel sulfate and the cobaltous sulfate (II) of 0.2mol/L that are solvent compound concentration as 0.2mol/L with water
Solution 15ml, the salicylic acid solution 40ml for being solvent compound concentration as 0.05mol/L with DMF, then take and match somebody with somebody
The 15ml nickel sulfate of system is molten with the 40ml salicylic acid that 5 drops/sec of speed is added drop-wise to preparation with the mixed aqueous solution of cobaltous sulfate (II)
In liquid, be stirred vigorously with 3000 revs/min of speed during Deca, then 118 DEG C in the hot water kettle of 100ml at carry out reacting 11 little
When, the precipitation of gained is collected by centrifugation after cooling, and DMF and absolute ethanol washing 2 times is respectively adopted, centrifugation is received
Collection precipitation, being deposited at 45 DEG C for collection is vacuum dried, that is, obtaining the nickel cobalt bimetallic with outstanding sensing capabilities has
Machine frame frame material；
<2>To in 10.0mL etoh solvents, sequentially add 0.20mmol～1.00mmol template molecule estazolam,
The function monomer resveratrol of 1.0mmol～6.0mmol, the cross-linking agent acetylshikonin of 2.0mmol, the initiator of 0.30mmol
Azodiisobutyronitrile and step<1>The nickel cobalt bimetallic organic framework materials 0.010g～0.060g of preparation, often adds one kindization
Learn reagent ultrasound wave to dissolve 5 minutes；
<3>Take step<2>9 μ L of mixture be applied to totally smooth glassy carbon electrode surface, after placing 8 hours, will modification
Electrode afterwards is placed in thermal polymerization 2.0 hours in 70 DEG C of vacuum drying oven, then using the acetonitrile and acetic acid mixing of mol ratio 1: 2
Template molecule elution is obtained final product by solvent eluant.
Experiment find, with estazolam as template molecule, resveratrol as function monomer, azodiisobutyronitrile be cause
Agent, nickel cobalt bimetallic organic framework materials are dopant, with the estazolam molecular engram that acetylshikonin is prepared as cross-linking agent
Electrochemical sensor, can delicately be used for the content for determining estazolam very much.The application present invention sets up the electricity for determining estazolam
Chemical analysis method, with especially outstanding sensitivity；The concentration of estazolam is 2.0 × 10-8～2.5 × 10-4Mol/L models
The good linear relationship (linearly dependent coefficient is R=0.9995) of interior presentation is enclosed, detection limit (S/N=3) is 3.8 × 10-9mol/
L, therefore, the estazolam molecular imprinting electrochemical sensor has higher sensitivity, more than current detection method；And
Equipment is simple, it is easy to make.
Description of the drawings
Fig. 1 is a kind of preparation method of highly sensitive estazolam molecular imprinting electrochemical sensor in embodiment 1
Working curve diagram.
Specific embodiment
Embodiment 1
First, the process of glass-carbon electrode
Glass-carbon electrode is polished with 1.0 μm, 0.3 μm and 0.05 μm of alumina powder on polishing cloth successively, is then placed in
Volume ratio be 1: 1 nitric acid in ultrasound 6min, place into ultrasound 6min in dehydrated alcohol, be finally cleaned by ultrasonic with pure water clean.
2nd, the preparation of estazolam molecular imprinting electrochemical sensor
<1>The mixing water of the nickel sulfate and the cobaltous sulfate (II) of 0.2mol/L that are solvent compound concentration as 0.2mol/L with water
Solution 15ml, the salicylic acid solution 40ml for being solvent compound concentration as 0.05mol/L with DMF, then take and match somebody with somebody
The 15ml nickel sulfate of system is molten with the 40ml salicylic acid that 5 drops/sec of speed is added drop-wise to preparation with the mixed aqueous solution of cobaltous sulfate (II)
In liquid, be stirred vigorously with 3000 revs/min of speed during Deca, then 118 DEG C in the hot water kettle of 100ml at carry out reacting 11 little
When, the precipitation of gained is collected by centrifugation after cooling, and DMF and absolute ethanol washing 2 times is respectively adopted, centrifugation is received
Collection precipitation, being deposited at 45 DEG C for collection is vacuum dried, that is, obtaining the nickel cobalt bimetallic with outstanding sensing capabilities has
Machine frame frame material；
<2>To in 10.0mL etoh solvents, 0.5mmol template molecule estazolam, 3.0mmol resveratrols is sequentially added
Function monomer, the cross-linking agent acetylshikonin of 2.0mmol, the initiator azodiisobutyronitrile of 0.30mmol and step<1>Nickel
Cobalt dual-metal organic framework materials 0.020g, often adds a kind of chemical reagent ultrasound wave to dissolve 5 minutes；
<3>Take step<2>9 μ L of mixture be applied to totally smooth glassy carbon electrode surface, after placing 8 hours, will modification
Electrode afterwards is placed in thermal polymerization 2.0 hours in 70 DEG C of vacuum drying oven, then using 1: 2 acetonitrile and acetic acid mixtures of eluents
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 is removed in washing, is 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 estazolam molecular imprinting electrochemical sensor electrode response characteristic is carried out with differential pulse voltammetry, is determined
The range of linearity and detection limit.Estazolam molecular engram electrode is cultivated 9 points respectively in the estazolam solution of variable concentrations
(bottom liquid is 5.0mmol/L K to clock3[Fe(CN)6] -0.5mol/L pH=7.5 phosphate buffered solution solution), then carry out
Differential pulse voltammetry is measured.Estazolam solution concentration is 2.0 × 10-8～2.5 × 10-4Present in the range of mol/L good
Linear relationship；Linear equation is Ip (μ A)=- 0.0894c (μm ol/L)+23.51, and linearly dependent coefficient is R=0.9995, inspection
Rising limit (S/N=3) is 3.8 × 10-9mol/L.
Therefore, the estazolam molecular engram sensor has higher sensitivity.
Claims (1)
1. a kind of preparation method of highly sensitive estazolam molecular imprinting electrochemical sensor, it is characterised in that the sensor
It is prepared by the following method：The estazolam of concentration 0.020mmol/mL～0.100mmol/ml is template molecule, concentration
The resveratrol of 0.10mmol/ml～0.60mmol/ml is function monomer, the azodiisobutyronitrile of concentration 0.03mmol/ml is
Initiator, the nickel cobalt pair that the acetylshikonin of concentration 0.20mmol/ml is cross-linking agent, concentration 0.0010g/ml～0.0060g/ml
Metal-organic framework material is dopant, forms a kind of hydridization nickel cobalt bimetallic organic framework materials Chinese mugwort department in glassy carbon electrode surface
Azoles logical sequence molecular imprinting polymer membrane, then using the acetonitrile and acetic acid mixed solvent eluted template point of eluant mol ratio 1: 2
Son is obtained final product；
Specifically carry out by following operation：
<1>The mixed aqueous solution of the nickel sulfate and the cobaltous sulfate (II) of 0.2mol/L that are solvent compound concentration as 0.2mol/L with water
15ml, the salicylic acid solution 40ml for being solvent compound concentration as 0.05mol/L with DMF, then take preparation
15ml nickel sulfate is added drop-wise in the 40ml salicylic acid solutions of preparation with 5 drops/sec of speed with the mixed aqueous solution of cobaltous sulfate (II),
Be stirred vigorously with 3000 revs/min of speed during Deca, then 118 DEG C in the hot water kettle of 100ml at carry out reacting 11 hours, cold
But the precipitation of gained is collected by centrifugation afterwards, DMF and absolute ethanol washing 2 times is respectively adopted, it is heavy to be collected by centrifugation
Form sediment, being deposited at 45 DEG C for collection is vacuum dried, that is, obtaining the nickel cobalt bimetallic with outstanding sensing capabilities has machine frame
Frame material；
<2>To in 10.0mL etoh solvents, sequentially add 0.20mmol～1.00mmol template molecule estazolam,
The function monomer resveratrol of 1.0mmol～6.0mmol, the cross-linking agent acetylshikonin of 2.0mmol, the initiator of 0.30mmol
Azodiisobutyronitrile and step<1>The nickel cobalt bimetallic organic framework materials 0.010g～0.060g of preparation, often adds one kindization
Learn reagent ultrasound wave to dissolve 5 minutes；
<3>Take step<2>9 μ L of mixture be applied to totally smooth glassy carbon electrode surface, after placing 8 hours, by modification after
Electrode is placed in thermal polymerization 2.0 hours in 70 DEG C of vacuum drying oven, then using the acetonitrile and acetic acid mixed solvent of mol ratio 1: 2
Template molecule elution is obtained final product by eluant.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN109342542A (en) * | 2018-11-06 | 2019-02-15 | 广西民族大学 | A kind of preparation method of benzhexol molecular imprinting electrochemical sensor |
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| CN109342542A (en) * | 2018-11-06 | 2019-02-15 | 广西民族大学 | A kind of preparation method of benzhexol molecular imprinting electrochemical sensor |
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