CN105548298A - Method for preparing high-sensitivity nano-zirconia-doped dezocine molecular imprinting electrochemical sensor - Google Patents
Method for preparing high-sensitivity nano-zirconia-doped dezocine molecular imprinting electrochemical sensor Download PDFInfo
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- CN105548298A CN105548298A CN201510956437.7A CN201510956437A CN105548298A CN 105548298 A CN105548298 A CN 105548298A CN 201510956437 A CN201510956437 A CN 201510956437A CN 105548298 A CN105548298 A CN 105548298A
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- dezocine
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Abstract
The present invention discloses a method for preparing a high-sensitivity nano-zirconia-doped dezocine molecular imprinting electrochemical sensor, the high-sensitivity nano-zirconia-doped dezocine molecular imprinting electrochemical sensor is prepared by use of dezocine as a template molecule, (5s, 8s)-3-(4'-chloro-3'-fluoro-4-propenyl-biphenyl-3-yl)-4-hydroxy-8-methoxy-1-aza-spiro [4.5] dec-3-ene-2-one as a single function monomer, azobisisobutyronitrile as an initiator, nano-zirconia as a dopant and maleic rosin ethylene glycol acrylate as a crosslinking agent, wherein the maleic rosin ethylene glycol acrylate is prepared from rosin as a raw material, and the method is simple and practical, and overcomes the shortcomings that a conventional analysis method is complicated, expensive in equipment, and low in sensitivity.
Description
Technical field
The present invention relates to molecular imprinting electrochemical sensor, especially a kind of preparation method of dezocine molecular imprinting electrochemical sensor of highly sensitive nano zircite doping.
Background technology
The main function of dezocine is for analgesia, be mainly used in Post operation intramuscular injection pain relieving, but because this type of medicine of excessive use can cause the spinoff such as disorientation, illusion, perspiration, tachycardia, fatal risk can be produced to Coronary Heart Disease Patients time excessive, be therefore classified as controlled substance by most country in the world.
The method measuring dezocine has ultraviolet spectroscopy, Gradient Elution method, reversed-phase high-performance liquid chromatography-diode array etc.But these methods are owing to needing expensive instrument and equipment, the shortcoming such as there is high, the consuming time length of cost or sensitivity is not high; Therefore, that study a kind of high sensibility, easy dezocine assay method has very important significance.
Molecular imprinting is for template molecule with target molecule to be measured, to be combined with template molecule by covalently or non-covalently key to form monomer template molecular complex by having in structure complementary functional monomer, add crosslinking chemical again to make it to carry out polyreaction with monomer and form template molecule polymkeric substance, template molecule is removed by physics or chemical method after having reacted, obtain molecularly imprinted polymer, formed complementary with former microsphere space structure in the polymer and there is the hole in Multiple recognition site.Current method can not be mated with template molecule rightly due to the function monomer chosen, and crosslinked rigidity is also poor, and therefore sensitivity is not high.
Summary of the invention
The technical problem to be solved in the present invention is to provide the preparation method that a kind of equipment is simple, make the dezocine molecular imprinting electrochemical sensor of easy a kind of highly sensitive nano zircite doping.
For solving the problems of the technologies described above, the present invention adopts following technical scheme: take dezocine as template molecule, (5s, 8s)-4-hydroxyl-8-methoxyl-1-azaspiro [4.5]-3-in last of the ten Heavenly stems alkene-2-ketone is function monomer to-3-(4 '-chloro-3 '-fluoro-4-propenyl biphenyl-3-base), azoisobutyronitrile is initiating agent, nano zircite is adulterant, with maleic rosin acrylic acid glycol ester for prepared by crosslinking chemical.
The preparation method of the dezocine molecular imprinting electrochemical sensor of above-mentioned a kind of highly sensitive nano zircite doping, take dezocine as template molecule, (5s, 8s)-3-(4 '-chloro-3 '-fluoro-4-propenyl biphenyl-3-base)-4-hydroxyl-8-methoxyl-1-azaspiro [4.5]-3-in last of the ten Heavenly stems alkene-2-ketone is function monomer, azoisobutyronitrile is initiating agent, with maleic rosin acrylic acid glycol ester for crosslinking chemical, nano zircite is adulterant, diameter 2mm glassy carbon electrode surface is formed a kind of hybridized nanometer zirconia dezocine molecular imprinting polymer membrane, then adopt the acetic acid of eluant, eluent mol ratio 1: 2 and isopropyl alcohol mixed solvent by template molecule elution, obtain.
The preparation method of the dezocine molecular imprinting electrochemical sensor of above-mentioned a kind of highly sensitive nano zircite doping, comprises the following steps:
<1> is in 10.0mL etoh solvent, add 0.3mmol ~ 0.6mmol template molecule dezocine, 1.0mmol ~ 5.0mmol function monomer (5s successively, 8s) nano zircite of-3-(4 '-chloro-3 '-fluoro-4-propenyl biphenyl-3-base)-4-hydroxyl-8-methoxyl-1-azaspiro [4.5]-3-in last of the ten Heavenly stems alkene-2-ketone, 5mmol crosslinking chemical maleic rosin acrylic acid glycol ester, 0.25mmol initiating agent azoisobutyronitrile and 0.0250g ~ 0.0450g, often adds a kind of chemical reagent ultrasound wave and dissolves 9 minutes;
The potpourri 8 μ L that <2> gets step <1> is applied in the glassy carbon electrode surface that totally smooth diameter is 2mm, place after 5 hours, thermal polymerization 3.5 hours in the vacuum drying chamber that electrode after modifying is placed in 75 DEG C, then adopt eluant, eluent mol ratio be 1: 2 acetic acid and isopropyl alcohol mixed solvent by template molecule elution, to obtain final product.
Research finds, take dezocine as template molecule, (5s, 8s)-4-hydroxyl-8-methoxyl-1-azaspiro [4.5]-3-in last of the ten Heavenly stems alkene-2-ketone is function monomer to-3-(4 '-chloro-3 '-fluoro-4-propenyl biphenyl-3-base), azoisobutyronitrile is initiating agent, nano zircite is adulterant, with the dezocine molecular imprinting electrochemical sensor that maleic rosin acrylic acid glycol ester is prepared for crosslinking chemical, can be used for the content measuring dezocine.Application the present invention sets up the electrochemical analysis method measuring dezocine, has very outstanding sensitivity; The concentration of dezocine is 1.0 × 10
-8~ 2.0 × 10
-4present good linear relationship (linearly dependent coefficient is R=0.9992) within the scope of mol/L, detection limit (S/N=3) is 1.2 × 10
-9mol/L, therefore, the dezocine molecular imprinting electrochemical sensor of nano zircite doping has higher sensitivity, exceedes current detection method, and equipment simple, make simple and easy.
Accompanying drawing explanation
Fig. 1 is the working curve diagram of the preparation method of the dezocine molecular imprinting electrochemical sensor of a kind of highly sensitive nano zircite doping in embodiment 1.
Embodiment
Embodiment 1
One, the process of glass-carbon electrode
Glass-carbon electrode is used on polishing cloth the alumina powder polishing of 1.0 μm, 0.3 μm and 0.05 μm successively, then put into the ultrasonic 8min of nitric acid that volume ratio is 1: 1, then put into the ultrasonic 8min of absolute ethyl alcohol, finally use pure water ultrasonic cleaning clean.
Two, the preparation of dezocine molecular imprinting electrochemical sensor
<1> is in 10.0mL etoh solvent, add 0.4mmol template molecule dezocine, 2.0mmol function monomer (5s successively, 8s) nano zircite of-3-(4 '-chloro-3 '-fluoro-4-propenyl biphenyl-3-base)-4-hydroxyl-8-methoxyl-1-azaspiro [4.5]-3-in last of the ten Heavenly stems alkene-2-ketone, 5mmol crosslinking chemical maleic rosin acrylic acid glycol ester, 0.25mmol initiating agent azoisobutyronitrile and 0.0350g, often adds a kind of chemical reagent ultrasound wave and dissolves 9 minutes;
The potpourri 8 μ L that <2> gets step <1> is applied in the glassy carbon electrode surface that totally smooth diameter is 2mm, place after 5 hours, thermal polymerization 3.5 hours in the vacuum drying chamber that electrode after modifying is placed in 75 DEG C, then adopt eluant, eluent mol ratio 1: 2 acetic acid and isopropyl alcohol mixed solvent by template molecule elution, by magnetic agitation eluted template molecule, until can't detect template molecule in eluent, the solvent of trace electrode surface is washed away again with ultrapure water, then trace electrode is stored in ultrapure water stand-by.
Three, the drafting of working curve and the mensuration of detection limit
Carry out the experiment of the dezocine molecular engram electrode response characteristic of nano zircite doping with differential pulse voltammetry, measure the range of linearity and detection limit.By nano zircite adulterate dezocine molecular engram electrode respectively in the dezocine solution of variable concentrations cultivate within 7 minutes, (end liquid is 5.0mmol/LK
3[Fe (CN)
6] the phosphate buffered solution solution of-0.5mol/LpH=7.5), then carry out differential pulse voltammetry measurement.Dezocine solution concentration is 1.0 × 10
-8~ 2.0 × 10
-4good linear relationship is presented within the scope of mol/L; Linear equation is Ip (μ A)=-0.096c (μm ol/L)+23.09, and linearly dependent coefficient is R=0.9992, and detection limit (S/N=3) is 1.2 × 10
-9mol/L.
Therefore, the dezocine molecular engram electrode of this nano zircite doping has high sensitivity.
Claims (1)
1. the preparation method of the dezocine molecular imprinting electrochemical sensor of a highly sensitive nano zircite doping, it is characterized in that with the dezocine of 0.03mmol/mL ~ 0.06mmol/ml for template molecule, (the 5s of 0.1mmol/ml ~ 0.5mmol/ml, 8s)-3-(4 '-chloro-3 '-fluoro-4-propenyl biphenyl-3-base)-4-hydroxyl-8-methoxyl-1-azaspiro [4.5]-3-in last of the ten Heavenly stems alkene-2-ketone is function monomer, 0.025mmol/ml azoisobutyronitrile is initiating agent, 0.5mmol/ml maleic rosin acrylic acid glycol ester is crosslinking chemical, 0.0025g/ml ~ 0.0045g/ml nano zircite is adulterant, glassy carbon electrode surface is formed a kind of hybridized nanometer zirconia dezocine molecular imprinting polymer membrane, then adopt eluant, eluent acetic acid and isopropyl alcohol mixed solvent eluted template molecule and get final product,
Specifically undertaken by following operation:
<1> is in 10.0mL etoh solvent, add 0.3mmol ~ 0.6mmol template molecule dezocine, 1.0mmol ~ 5.0mmol function monomer (5s successively, 8s) nano zircite of-3-(4 '-chloro-3 '-fluoro-4-propenyl biphenyl-3-base)-4-hydroxyl-8-methoxyl-1-azaspiro [4.5]-3-in last of the ten Heavenly stems alkene-2-ketone, 5mmol crosslinking chemical maleic rosin acrylic acid glycol ester, 0.25mmol initiating agent azoisobutyronitrile and 0.0250g ~ 0.0450g, often adds a kind of chemical reagent ultrasound wave and dissolves 9 minutes;
The potpourri 8 μ L that <2> gets step <1> is applied in the glassy carbon electrode surface that totally smooth diameter is 2mm, place after 5 hours, thermal polymerization 3.5 hours in the vacuum drying chamber that electrode after modifying is placed in 75 DEG C, then adopt eluant, eluent mol ratio be 1: 2 acetic acid and isopropyl alcohol mixed solvent by template molecule elution, to obtain final product.
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102735729A (en) * | 2012-07-18 | 2012-10-17 | 广西民族大学 | Electrochemical paracetamol molecular imprinting transducer and manufacturing method thereof |
CN102759560A (en) * | 2012-07-20 | 2012-10-31 | 广西民族大学 | Aspirin molecule imprint electrochemical sensor and preparation method thereof |
CN102901756A (en) * | 2012-10-13 | 2013-01-30 | 广西民族大学 | Tripolycyanamide molecular imprinting electrochemical sensor and preparation method thereof |
CN102901757A (en) * | 2012-10-13 | 2013-01-30 | 广西民族大学 | Sudan I molecular imprinting electrochemical sensor and preparation method thereof |
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 |
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 CN201510956437.7A patent/CN105548298B/en not_active Expired - Fee Related
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102735729A (en) * | 2012-07-18 | 2012-10-17 | 广西民族大学 | Electrochemical paracetamol molecular imprinting transducer and manufacturing method thereof |
CN102759560A (en) * | 2012-07-20 | 2012-10-31 | 广西民族大学 | Aspirin molecule imprint electrochemical sensor and preparation method thereof |
CN102901756A (en) * | 2012-10-13 | 2013-01-30 | 广西民族大学 | Tripolycyanamide molecular imprinting electrochemical sensor and preparation method thereof |
CN102901757A (en) * | 2012-10-13 | 2013-01-30 | 广西民族大学 | Sudan I molecular imprinting electrochemical sensor and preparation method thereof |
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 |
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 |
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CN106770558A (en) * | 2017-01-09 | 2017-05-31 | 广西民族大学 | A kind of preparation method of highly sensitive pemoline molecular imprinting electrochemical sensor |
CN107917945A (en) * | 2017-12-02 | 2018-04-17 | 广西民族大学 | A kind of preparation method of Timiperone molecular imprinting electrochemical sensor |
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CN107957443A (en) * | 2017-12-02 | 2018-04-24 | 广西民族大学 | A kind of preparation method of ethymal molecular imprinting electrochemical sensor |
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