CN106770600A - A kind of preparation method of highly sensitive alprazolam molecular imprinting electrochemical sensor - Google Patents
A kind of preparation method of highly sensitive alprazolam molecular imprinting electrochemical sensor Download PDFInfo
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- CN106770600A CN106770600A CN201710014693.3A CN201710014693A CN106770600A CN 106770600 A CN106770600 A CN 106770600A CN 201710014693 A CN201710014693 A CN 201710014693A CN 106770600 A CN106770600 A CN 106770600A
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Abstract
The invention discloses a kind of preparation method of highly sensitive alprazolam molecular imprinting electrochemical sensor, with alprazolam as template molecule, resveratrol as function monomer, azodiisobutyronitrile as initiator, nickel cobalt bimetallic organic framework materials are as dopant, using Acetylshikonin as crosslinking agent, a kind of highly sensitive alprazolam 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 alprazolam molecular engram electricity
The preparation method of chemical sensor.
Background technology
Alprazolam (Alprazolam) indication：For treating anxiety disorder, depression, insomnia.Can be used as anti-HD.
Acute alcohol withrawal symptom can be alleviated.There is preferable therapeutic action to drug induccd intractable hiccup.But because long-term use is such
Medicine can cause central nervous system to be in holddown or acute poisoning, myasthenia gravis, acute angle-closure glaucoma etc..
Heavy dose of use can cause chronic obstructive lung lesion and kidney, liver function hepatic disorder.
The method for determining alprazolam 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, it is sensitive not high the shortcomings of.Therefore, study a kind of high sensibility, easy Ah
General azoles logical sequence 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 easy, a kind of highly sensitive A Pu
The preparation method of azoles logical sequence molecular imprinting electrochemical sensor.
In order to solve the above technical problems, the present invention is adopted the following technical scheme that：With alprazolam as template molecule, white black false hellebore
Alcohol is function monomer, azodiisobutyronitrile is initiator, nickel cobalt bimetallic organic framework materials are dopant, with Acetylshikonin
For prepared by crosslinking agent.
A kind of preparation method of above-mentioned highly sensitive alprazolam molecular imprinting electrochemical sensor, be with alprazolam
Template molecule, resveratrol be function monomer, azodiisobutyronitrile be initiator, with Acetylshikonin as crosslinking agent, azo two
Isobutyronitrile is initiator, nickel cobalt bimetallic organic framework materials are dopant, and a kind of hydridization nickel cobalt is formed in glassy carbon electrode surface
Bimetallic organic framework materials alprazolam molecular imprinting polymer membrane, template molecule elution is obtained final product.
A kind of preparation method of above-mentioned highly sensitive alprazolam 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 mixed aqueous solution of the 15ml nickel sulfates of system and cobaltous sulfate (II) is molten with the 40ml salicylic acids that 5 drops/sec of speed is added drop-wise to preparation
In liquid, it is stirred vigorously with 3000 revs/min of speed during dropwise addition, then to carry out reaction 11 in the hot water kettle of 100ml at 118 DEG C small
When, the precipitation of gained is collected by centrifugation after cooling, 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>In to 10.0mL etoh solvents, sequentially add 0.20mmol~0.90mmol template molecule alprazolam,
The function monomer resveratrol of 1.0mmol~6.0mmol, the crosslinking 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
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 alprazolam as template molecule, resveratrol as function monomer, azodiisobutyronitrile for trigger
Agent, nickel cobalt bimetallic organic framework materials are dopant, with the alprazolam molecular engram that Acetylshikonin is prepared as crosslinking agent
Electrochemical sensor, delicately can be used to determine the content of alprazolam very much.The electricity for determining alprazolam is set up using the present invention
Chemical analysis method, with especially outstanding sensitivity；The concentration of alprazolam is 1.0 × 10-8~2.0 × 10-4Mol/L models
The good linear relationship (linearly dependent coefficient is R=0.9997) of interior presentation is enclosed, detection limit (S/N=3) is 2.8 × 10-9mol/
L, therefore, the alprazolam molecular imprinting electrochemical sensor has sensitivity higher, more than current detection method；And
Equipment is simple, make easy.
Brief description of the drawings
Fig. 1 is a kind of preparation method of highly sensitive alprazolam molecular imprinting electrochemical sensor in embodiment 1
Working curve diagram.
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 alprazolam 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 mixed aqueous solution of the 15ml nickel sulfates of system and cobaltous sulfate (II) is molten with the 40ml salicylic acids that 5 drops/sec of speed is added drop-wise to preparation
In liquid, it is stirred vigorously with 3000 revs/min of speed during dropwise addition, then to carry out reaction 11 in the hot water kettle of 100ml at 118 DEG C small
When, the precipitation of gained is collected by centrifugation after cooling, 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>In to 10.0mL etoh solvents, 0.6mmol template molecules alprazolam, 3.0mmol resveratrols are sequentially added
Function monomer, the crosslinking agent Acetylshikonin of 2.0mmol, the initiator azodiisobutyronitrile and step of 0.30mmol<1>Nickel
Cobalt dual-metal organic framework materials 0.050g, 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 alprazolam molecular imprinting electrochemical sensor electrode response characteristic is carried out with differential pulse voltammetry, is determined
The range of linearity and detection limit.Alprazolam molecular engram electrode is cultivated 9 points in the alprazolam solution of various concentrations respectively
(bottom liquid is 5.0mmol/L K to clock3[Fe(CN)6] -0.5mol/L pH=7.5 PBS solution), then carry out
Differential pulse voltammetry is measured.Alprazolam solution concentration is 1.0 × 10-8~2.0 × 10-4Presented in the range of mol/L good
Linear relationship；Linear equation is Ip (μ A)=- 0.1214c (μm ol/L)+27.62, and linearly dependent coefficient is R=0.9997, inspection
Rising limit (S/N=3) is 2.8 × 10-9mol/L。
Therefore, the alprazolam molecular engram sensor has sensitivity higher.
Claims (1)
1. a kind of preparation method of highly sensitive alprazolam molecular imprinting electrochemical sensor, it is characterised in that the sensor
It is prepared by the following method：The alprazolam of concentration 0.020mmol/mL~0.090mmol/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 Acetylshikonin of concentration 0.20mmol/ml are crosslinking agent, the nickel cobalt of concentration 0.0010g/ml~0.0060g/ml is double
Metal-organic framework material is dopant, and a kind of hydridization nickel cobalt bimetallic organic framework materials A Pu is formed 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, eluent mol ratio 1: 2
Son is obtained final product；
Specifically carried 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 sulfates are added drop-wise in the 40ml salicylic acid solutions of preparation with the mixed aqueous solution of cobaltous sulfate (II) with 5 drops/sec of speed,
It is stirred vigorously with 3000 revs/min of speed during dropwise addition, then carries out reaction 11 hours in the hot water kettle of 100ml at 118 DEG C, it is 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>In to 10.0mL etoh solvents, sequentially add 0.20mmol~0.90mmol template molecule alprazolam,
The function monomer resveratrol of 1.0mmol~6.0mmol, the crosslinking 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
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, 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 (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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Application publication date: 20170531 |