CN107941878A - A kind of preparation method of depamide molecular imprinting electrochemical sensor - Google Patents

Abstract

The invention discloses a kind of preparation method of depamide molecular imprinting electrochemical sensor, using depamide as template molecule, sprout be function monomer containing disconnected oxidation loganin, azodiisobutyronitrile is initiator, nanoclay is dopant, crosslinking agent is used as using the trans feruloyltyramines of N, the depamide molecular imprinting electrochemical sensor of highly sensitive nanoclay doping is prepared for accordingly, the analysis method is simple and practical, overcomes the shortcomings that conventional analysis method is complicated, equipment is expensive, sensitivity is low.

Description

A kind of preparation method of depamide molecular imprinting electrochemical sensor

Technical field

The present invention relates to molecular imprinting electrochemical sensor, especially a kind of depamide molecular imprinting electrochemical sensing The preparation method of device.

Background technology

Depamide (Valpromide), alias are Valpromide.It is a kind of wide spectrum, effect it is strong, quick New antiepileptic drugs, extensive anticonvulsant action, and without excitement has sedation, available for controlling for all kinds epilepsy Treat.Major defect is long-term or such medicine is excessively used can cause liver and kidney dysfunction, erythematosus lupus.

Measure depamide method have gas chromatography, gas phase-mass spectrography, Gradient Elution method and Solid Phase Extraction chromatography etc..But these methods are due to needing expensive instrument and equipment, there are it is of high cost, time-consuming, sensitivity The shortcomings of not high.Therefore, study a kind of high sensibility, easy depamide assay method has very important significance.

Molecular imprinting technology is using target molecule to be measured as template molecule, will be led to functional monomer complementary in structure Cross covalently or non-covalently key and template molecule and combine to form monomer template molecular complex, add crosslinking agent be allowed to monomer into 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 complementary and with Multiple recognition site the sky with former microsphere space structure in the polymer Cave.Current method is since the function monomer of selection cannot be properly matched with template molecule, and crosslinked rigidity is also poor, Therefore sensitivity is not high.

The content of the invention

The technical problem to be solved in the present invention is to provide a kind of equipment it is simple, make a kind of easy depamide molecule The preparation method of trace electrochemical sensor.

In order to solve the above technical problems, the present invention adopts the following technical scheme that：Using depamide as template molecule, sprout Containing disconnected oxidation loganin be function monomer, azodiisobutyronitrile is initiator, nanoclay is dopant, with the trans asafoetides of N- Acyl tyrasamine is prepared for crosslinking agent.

The preparation method of above-mentioned a kind of depamide molecular imprinting electrochemical sensor, using depamide as template point Son, sprout containing disconnected oxidation loganin are function monomer, azodiisobutyronitrile is initiator, using the trans feruloyltyramines of N- as friendship Connection agent, nanoclay are dopant, and a kind of hybridized nanometer clay depamide is formed in 2 mm glassy carbon electrode surfaces of diameter Molecular imprinting polymer membrane, then using eluant, eluent molar ratio 2:1 acetic acid and 2- amylalcohol mixed solvents washes template molecule It is de-, to obtain the final product.

A kind of preparation method of above-mentioned depamide molecular imprinting electrochemical sensor, comprises the following steps：

<1>Into 10.0 mL etoh solvents, the mmol template molecules depamide of 0.15 mmol~2.0,2.0 are sequentially added The mmol function monomers sprout of mmol~6.0 containing disconnected oxidation loganin, the trans feruloyltyramines of 4.0 mmol crosslinking agents N-, The nanoclay of the g of 0.11 mmol initiator azodiisobutyronitriles and 0.0100 g~0.0800, often adds a kind of chemical reagent Ultrasonic wave dissolves 8 minutes；

<2>Take step<1>8 μ L of mixture be applied in the glassy carbon electrode surface of clean smooth a diameter of 2 mm, it is small to place 6 Shi Hou, when the electrode after modification is placed in thermal polymerization 1.5 is small in 80 DEG C of vacuum drying chamber, then using eluant, eluent molar ratio For 2:1 acetic acid and 2- amylalcohols mixed solvent are by template molecule elution, to obtain the final product.

Research finds, is function monomer containing disconnected oxidation loganin using depamide as template molecule, sprout, azo two Isobutyronitrile is initiator, nanoclay is dopant, the depamide point prepared using the trans feruloyltyramines of N- as crosslinking agent Sub- trace electrochemical sensor, the content available for measure depamide.Established using the present invention and measure depamide Electrochemical analysis method, has very outstanding sensitivity；The concentration of depamide is 1.2 × 10^-8 ~ 2.2×10^-4 mol/ It is presented good linear relationship (linearly dependent coefficient is R=0.9995) in the range of L, detection limit (S/N=3) it is 3.6 × 10^-9 Mol/L, therefore, the depamide molecular imprinting electrochemical sensor of nanoclay doping have higher sensitivity, exceed Current detection method；And equipment is simple, it is simple to make.

Brief description of the drawings

Fig. 1 is a kind of working curve of the preparation method of depamide molecular imprinting electrochemical sensor in embodiment 1 Figure.

Embodiment

Embodiment 1

First, the processing 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 body Product is than being 1:8 min of ultrasound in 1 nitric acid, place into 8 min of ultrasound in absolute ethyl alcohol, are finally cleaned by ultrasonic with pure water clean.

2nd, the preparation of depamide molecular imprinting electrochemical sensor

<1>Into 10.0 mL etoh solvents, 1.0 mmol template molecules depamides, 4.0 mmol function lists are sequentially added Body sprout is containing disconnected oxidation loganin, the trans feruloyltyramines of 4.0 mmol crosslinking agents N-, 0.11 mmol initiators azo two The nanoclay of isobutyronitrile and 0.0500 g, often adds a kind of chemical reagent ultrasonic wave and dissolves 8 minutes；

<2>Take step<1>8 μ L of mixture be applied in the glassy carbon electrode surface of clean smooth a diameter of 2 mm, it is small to place 6 Shi Hou, when the electrode after modification is placed in thermal polymerization 1.5 is small in 80 DEG C of vacuum drying chamber, then using eluant, eluent molar ratio For 2:1 acetic acid and 2- amylalcohols mixed solvent are by template molecule elution, by magnetic agitation eluted template molecule, until eluent In can't detect template molecule, then the solvent of trace electrode surface is washed away with ultra-pure water, is then stored in trace electrode ultrapure It is stand-by in water.

3rd, the measure of the drafting of working curve and detection limit

The experiment of the depamide molecular engram electrode response characteristic of nanoclay doping is carried out with differential pulse voltammetry, is surveyed Constant linear scope and detection limit.By the depamide molecular engram electrode of nanoclay doping respectively in the third figured silk fabrics of various concentrations Cultivated 6 minutes in oxalyl amine aqueous solution（Bottom liquid is 5.0 mmol/L K₃[Fe(CN)₆] -0.5 mol/L pH=7.5 phosphate Buffer solution solution）, then carry out differential pulse voltammetry measurement.Depamide solution concentration is 1.2 × 10^-8 ~ 2.2× 10^-4Good linear relationship is presented in the range of mol/L；Linear equation isIp(μA) = -0.1039 с (μmol/L) + 23.17, linearly dependent coefficient is R=0.9995, detection limit (S/N=3) it is 3.6 × 10^-9 mol/L。

Therefore, the molecular engram electrode of nanoclay doping depamide has high sensitivity.

Claims (1)

1. a kind of preparation method of depamide molecular imprinting electrochemical sensor, it is characterised in that with 0.015 mmol/mL The depamide of~0.20 mmol/mL is template molecule, the sprout of the mmol/mL of 0.20 mmol/mL~0.60 is containing disconnected oxidation Loganin is function monomer, the azodiisobutyronitrile of 0.011 mmol/mL is initiator, trans with the N- of 0.40 mmol/mL Feruloyltyramine is crosslinking agent, the nanoclay of the g/mL of 0.0010 g/mL~0.0080 is dopant, in glassy carbon electrode surface It is upper to form a kind of hybridized nanometer clay depamide molecular imprinting polymer membrane, then using eluant, eluent acetic acid and 2- amylalcohols Mixed solvent eluted template molecule to obtain the final product；

Specifically carried out by following operation：

<1>Into 10.0 mL etoh solvents, the mmol template molecules depamide of 0.15 mmol~2.0,2.0 are sequentially added The mmol function monomers sprout of mmol~6.0 containing disconnected oxidation loganin, the trans feruloyltyramines of 4.0 mmol crosslinking agents N-, The nanoclay of the g of 0.11 mmol initiator azodiisobutyronitriles and 0.0100 g~0.0800, often adds a kind of chemical reagent Ultrasonic wave dissolves 8 minutes；

<2>Take step<1>8 μ L of mixture be applied in the glassy carbon electrode surface of clean smooth a diameter of 2 mm, it is small to place 6 Shi Hou, when the electrode after modification is placed in thermal polymerization 1.5 is small in 80 DEG C of vacuum drying chamber, then using eluant, eluent molar ratio For 2:1 acetic acid and 2- amylalcohols mixed solvent are by template molecule elution, to obtain the final product.