CN106770525A - A kind of preparation method of highly sensitive pizotifen molecular imprinting electrochemical sensor - Google Patents
A kind of preparation method of highly sensitive pizotifen molecular imprinting electrochemical sensor Download PDFInfo
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- CN106770525A CN106770525A CN201710014695.2A CN201710014695A CN106770525A CN 106770525 A CN106770525 A CN 106770525A CN 201710014695 A CN201710014695 A CN 201710014695A CN 106770525 A CN106770525 A CN 106770525A
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- 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
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Abstract
The invention discloses a kind of preparation method of highly sensitive pizotifen molecular imprinting electrochemical sensor, with pizotifen as template molecule, gentiamarin as function monomer, azodiisobutyronitrile as initiator, copper base metal organic framework materials are as dopant, using evodin as crosslinking agent, a kind of highly sensitive pizotifen 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 pizotifen molecular imprinting electrochemical
The preparation method of sensor.
Background technology
Pizotifen (Pizotifen) indication：Pizotifen is mainly used in typical and atypical antimigraine, can mitigate symptom
And attack times, it is evident in efficacy, but to acute migraine attack without mitigation at once.Also can try to control erythromelalgia, blood
Pipe nervous edema, chronic urticaria and room and VPB etc..But because long-term use or excessive such medicine can go out
Existing drowsiness, weak, increased weight, occasionally there is nausea, and dizzy, dry is flushing, and the phenomenon such as courbature, severe patient can cause glaucoma, preceding
Row gland hypertrophy and kidney, dyshepatia.
The method for determining pizotifen 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 benzene thiophene are studied
Pyridine 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 benzene thiophene
The preparation method of pyridine molecular imprinting electrochemical sensor.
In order to solve the above technical problems, the present invention is adopted the following technical scheme that：With pizotifen as template molecule, gentiamarin
For function monomer, azodiisobutyronitrile be initiator, copper base metal organic framework materials be dopant, with evodin for friendship
It is prepared by connection agent.
The preparation method of above-mentioned a kind of highly sensitive pizotifen molecular imprinting electrochemical sensor, with pizotifen as template
Molecule, gentiamarin be function monomer, azodiisobutyronitrile be initiator, with evodin as crosslinking agent, the isobutyl of azo two
Nitrile is initiator, copper base metal organic framework materials are dopant, and forming a kind of hydridization copper base metal in glassy carbon electrode surface has
Machine frame frame material pizotifen molecular imprinting polymer membrane, template molecule elution is obtained final product.
A kind of preparation method of above-mentioned highly sensitive pizotifen molecular imprinting electrochemical sensor, comprises the following steps：
<1>With water be solvent compound concentration as 0.5mol/L copper sulfate solution 10ml, with DMF
For solvent compound concentration is the trimesic acid solution 50ml of 0.05mol/L, the 10ml copper sulfate solutions of preparation are then taken with 5
Drop/sec speed be added drop-wise in the 50ml benzenetricarboxylic acid solution of preparation, be stirred vigorously with 3000 revs/min of speed during dropwise addition,
Carry out reaction 11 hours in the hot water kettle of 100ml at 118 DEG C again, the precipitation of gained be collected by centrifugation after cooling, N is respectively adopted,
Dinethylformamide and absolute ethanol washing 2 times, are collected by centrifugation precipitation, by collect be deposited in 45 DEG C at carry out vacuum and do
It is dry, that is, obtain the copper base metal organic framework materials with outstanding sensing capabilities；
<2>In to 10.0mL etoh solvents, sequentially add 0.20mmol~0.90mmol template molecule pizotifen,
The function monomer gentiamarin of 2.0mmol~9.0mmol, the crosslinking agent evodin of 3.0mmol, the initiator of 0.20mmol
Azodiisobutyronitrile and step<1>The copper base metal organic framework materials 0.010g~0.060g of preparation, often adds a kind of chemistry
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, 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 pizotifen as template molecule, gentiamarin as function monomer, azodiisobutyronitrile as initiator,
Copper base metal organic framework materials are dopant, are passed with the pizotifen molecular imprinting electrochemical that evodin is prepared as crosslinking agent
Sensor, delicately can be used to determine the content of pizotifen very much.The electrochemical analysis method for determining pizotifen is set up using the present invention,
With especially outstanding sensitivity；The concentration of pizotifen is 1.5 × 10-8~2.0 × 10-4In the range of good linear pass is presented
System's (linearly dependent coefficient is R=0.9996), detection limit (S/N=3) is 4.5 × 10-9Mol/L, therefore, copper base metal has machine frame
The pizotifen molecular imprinting electrochemical sensor of frame material doping has sensitivity higher, more than current detection method；And
And equipment is simple, make easy.
Brief description of the drawings
Fig. 1 is a kind of work of the preparation method of highly sensitive pizotifen 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 pizotifen molecular imprinting electrochemical sensor
<1>With water be solvent compound concentration as 0.5mol/L copper sulfate solution 10ml, with DMF
For solvent compound concentration is the trimesic acid solution 50ml of 0.05mol/L, the 10ml copper sulfate solutions of preparation are then taken with 5
Drop/sec speed be added drop-wise in the 50ml benzenetricarboxylic acid solution of preparation, be stirred vigorously with 3000 revs/min of speed during dropwise addition,
Carry out reaction 11 hours in the hot water kettle of 100ml at 118 DEG C again, the precipitation of gained be collected by centrifugation after cooling, N is respectively adopted,
Dinethylformamide and absolute ethanol washing 2 times, are collected by centrifugation precipitation, by collect be deposited in 45 DEG C at carry out vacuum and do
It is dry, that is, obtain the copper base metal organic framework materials with outstanding sensing capabilities；
<2>In to 10.0mL etoh solvents, 0.5mmol template molecules pizotifen, 3.0mmol gentiamarin work(are sequentially added
Can monomer, the crosslinking agent evodin of 3.0mmol, the initiator azodiisobutyronitrile and step of 0.20mmol<1>It is copper-based
Metal-organic framework material 0.020g, 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 pizotifen molecular imprinting electrochemical sensor electrode response characteristic is carried out with differential pulse voltammetry, line is determined
Property scope and detection limit.Pizotifen molecular engram electrode is cultivated into 9 minutes (bottom liquid in the pizotifen 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.Pizotifen solution concentration is 1.5 × 10-8~2.0 × 10-4Good linear relationship is presented in the range of mol/L；
Linear equation is Ip (μ A)=- 0.0981c (μ .mol/L)+23.12, and linearly dependent coefficient is R=0.9996, detection limit (S/N
=3) it is 4.5 × 10-9mol/L。
Therefore, the pizotifen molecular engram sensor has sensitivity higher.
Claims (1)
1. a kind of preparation method of highly sensitive pizotifen molecular imprinting electrochemical sensor, it is characterised in that the sensor is
It is prepared by the following method：The pizotifen of concentration 0.020mmol/mL~0.090mmol/ml is template molecule, concentration
The gentiamarin of 0.20mmol/ml~0.90mmol/ml is function monomer, the azodiisobutyronitrile of concentration 0.02mmol/ml is
Initiator, the evodin of concentration 0.30mmol/ml are crosslinking agent, the copper-based gold of concentration 0.0010g/ml~0.0060g/ml
Category organic framework materials are dopant, and a kind of hydridization copper base metal organic framework materials pizotifen point is formed in glassy carbon electrode surface
Sub- imprinted polymer films, are then obtained final product using the acetonitrile and acetic acid mixed solvent eluted template molecule of eluant, eluent mol ratio 1: 2；
Specifically carried out by following operation：
<1>With water be solvent compound concentration as 0.5mol/L copper sulfate solution 10ml, with DMF as molten
Agent compound concentration for 0.05mol/L trimesic acid solution 50ml, then take the 10ml copper sulfate solutions of preparation with 5 drop/
The speed of second is added drop-wise in the 50ml benzenetricarboxylic acid solution of preparation, is stirred vigorously with 3000 revs/min of speed during dropwise addition, then
Reaction 11 hours is carried out in the hot water kettle of 100ml at 118 DEG C, the precipitation of gained is collected by centrifugation after cooling, N, N- bis- is respectively adopted
NMF and absolute ethanol washing 2 times, are collected by centrifugation precipitation, being deposited at 45 DEG C of collecting are vacuum dried, i.e.,
Obtain the copper base metal organic framework materials with outstanding sensing capabilities；
<2>In to 10.0mL etoh solvents, template molecule pizotifen, the 2.0mmol of 0.20mmol~0.90mmol are sequentially added
The function monomer gentiamarin of~9.0mmol, the crosslinking agent evodin of 3.0mmol, the initiator azo two of 0.20mmol
Isobutyronitrile and step<1>The copper base metal organic framework materials 0.010g~0.060g of preparation, often adds a kind of chemical reagent to surpass
Sound 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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Citations (4)
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|---|---|---|---|---|
| CN102735729A (en) * | 2012-07-18 | 2012-10-17 | 广西民族大学 | Electrochemical paracetamol molecular imprinting transducer and manufacturing method thereof |
| EP2674759A1 (en) * | 2011-02-04 | 2013-12-18 | Council of Scientific & Industrial Research | Molecularly imprinted conducting polymer film based aqueous amino acid sensors |
| CN105973958A (en) * | 2016-05-05 | 2016-09-28 | 济南大学 | Preparation method of fluorouracil molecularly imprinted electrochemical sensor |
| 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 CN201710014695.2A patent/CN106770525A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2674759A1 (en) * | 2011-02-04 | 2013-12-18 | Council of Scientific & Industrial Research | Molecularly imprinted conducting polymer film based aqueous amino acid sensors |
| CN102735729A (en) * | 2012-07-18 | 2012-10-17 | 广西民族大学 | Electrochemical paracetamol molecular imprinting transducer and manufacturing method thereof |
| CN105973958A (en) * | 2016-05-05 | 2016-09-28 | 济南大学 | Preparation method of fluorouracil molecularly imprinted electrochemical sensor |
| 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 |
|---|
| 者为 等.: "均苯三甲酸合铜选择性降低卷烟主流烟气中的HCN", 《烟草化学》 * |
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