CN107957444A - A kind of preparation method of easypro thiazine molecular imprinting electrochemical sensor - Google Patents

Abstract

The invention discloses a kind of preparation method of easypro thiazine molecular imprinting electrochemical sensor; to relax thiazine as template molecule, Oridonin be function monomer, azodiisobutyronitrile is initiator, nanoclay is dopant; crosslinking agent is used as to coumaric acyl tyrasamine so that N is trans; the easypro thiazine 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 easypro thiazine molecular imprinting electrochemical sensor

Technical field

The present invention relates to molecular imprinting electrochemical sensor, especially a kind of easypro thiazine molecular imprinting electrochemical sensor Preparation method.

Background technology

Relax thiazine (Sultiame) also known as sulthiam, and clinic is mainly used for the breaking-out of epilepsy limitation or the control to break out greatly, If it is more preferable to share effect with other antiepileptics.It is but long-term or such medicine is excessively used can cause weight loss and spirit aspect Change, occasionally have abdominal pain, in addition also have because Liver and kidney function damage.

The method of the easypro thiazine of measure has gas phase-mass spectrography, Gradient Elution method and RP-HPLC color Spectrum-diode array 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 easypro thiazine 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 easypro thiazine molecular engram The preparation method of electrochemical sensor.

In order to solve the above technical problems, the present invention adopts the following technical scheme that：Using the thiazine that relaxes as template molecule, Rabdosia rubescens first Element is function monomer, azodiisobutyronitrile is initiator, nanoclay is dopant, using N- it is trans-to coumaric acyl tyrasamine as It is prepared by crosslinking agent.

A kind of preparation method of above-mentioned easypro thiazine molecular imprinting electrochemical sensor, to relax, thiazine is insulted as template molecule, winter Careless A prime is function monomer, azodiisobutyronitrile be initiator, using N- it is trans-coumaric acyl tyrasamine is glued as crosslinking agent, nanometer Soil is dopant, and it is thin that a kind of hybridized nanometer clay thiazine molecularly imprinted polymer that relaxes is formed in 2 mm glassy carbon electrode surfaces of diameter Film, then using eluant, eluent molar ratio 1:1 acetic acid and propanol solvent mixture are by template molecule elution, to obtain the final product.

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

<1>Into 10.0 mL etoh solvents, sequentially add the mmol template molecules of 0.2 mmol~1.0 and relax thiazine, 1.0 mmol ~8.0 mmol function monomers Oridonins, 4.5 mmol crosslinking agents N- are trans-to coumaric acyl tyrasamine, 0.12 The nanoclay of the g of mmol initiator azodiisobutyronitriles and 0.0100 g~0.0800, often adds a kind of chemical reagent ultrasonic wave Dissolving 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 85 DEG C of vacuum drying chamber, then using eluant, eluent molar ratio For 1:1 acetic acid and propanol solvent mixture are by template molecule elution, to obtain the final product.

Research finds, be function monomer to relax thiazine as template molecule, Oridonin, azodiisobutyronitrile be initiation Agent, nanoclay are dopant, using N- it is trans-the easypro thiazine molecular imprinting electrochemical that is prepared to coumaric acyl tyrasamine as crosslinking agent Sensor, the content for the thiazine that relaxes available for measure.The electrochemical analysis method of the easypro thiazine of measure is established using the present invention, is had very Outstanding sensitivity；The concentration of easypro thiazine is 1.5 × 10^-8 ~ 5.5×10^-4Good linear relationship is presented in the range of mol/L (linearly dependent coefficient is R=0.9998), detection limit (S/N=3) it is 4.5 × 10^-9Mol/L, therefore, nanoclay doping Easypro thiazine molecular imprinting electrochemical sensor there is higher sensitivity, more than current detection method；And equipment is simple, Make simple.

Brief description of the drawings

Fig. 1 is a kind of working curve diagram of the preparation method of easypro thiazine molecular imprinting electrochemical sensor in embodiment 1.

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 easypro thiazine molecular imprinting electrochemical sensor

<1>Into 10.0 mL etoh solvents, sequentially add 0.25 mmol template molecules and relax thiazine, 4.5 mmol function monomer winters Insult careless A prime, 4.5 mmol crosslinking agents N- it is trans-to coumaric acyl tyrasamine, 0.12 mmol initiator azodiisobutyronitriles and The nanoclay of 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 85 DEG C of vacuum drying chamber, then using eluant, eluent molar ratio 1:1 acetic acid and propanol solvent mixture are by template molecule elution, by magnetic agitation eluted template molecule, until being detected in eluent Less than template molecule, then the solvent of trace electrode surface is washed away with ultra-pure water, then trace electrode is stored in ultra-pure water and is treated With.

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

The experiment of the easypro thiazine molecular engram electrode response characteristic of nanoclay doping is carried out with differential pulse voltammetry, measures line Property scope and detection limit.By the easypro thiazine molecular engram electrode of nanoclay doping respectively in the easypro thiazine solution of various concentrations Cultivate 6 minutes（Bottom liquid is 5.0 mmol/L K₃[Fe(CN)₆] -0.5 mol/L pH=7.5 phosphate buffer solution it is molten Liquid）, then carry out differential pulse voltammetry measurement.Thiazine solution concentration of relaxing is 1.5 × 10^-8 ~ 5.5×10^-4Mol/L scopes It is interior that good linear relationship is presented；Linear equation isIP (μ A)=8.1628 с (μm ol/L)+1.282, linearly dependent coefficient For R=0.9998, detection limit (S/N=3) it is 4.5 × 10^-9 mol/L。

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

Claims (1)

1. a kind of preparation method of easypro thiazine molecular imprinting electrochemical sensor, it is characterised in that with 0.02 mmol/mL~0.10 The easypro thiazine of mmol/mL is template molecule, the Oridonin of the mmol/mL of 0.10 mmol/mL~0.80 be function monomer, The azodiisobutyronitrile of 0.012 mmol/mL be initiator, using the N- of 0.45 mmol/mL it is trans-to coumaric acyl tyrasamine as friendship Join agent, the g/mL nanoclays of 0.0010 g/mL~0.0080 are dopant, a kind of hydridization is formed in glassy carbon electrode surface and is received Rice clay relaxes thiazine molecular imprinting polymer membrane, is then using eluant, eluent acetic acid and propanol solvent mixture eluted template molecule ；

Specifically carried out by following operation：

<1>Into 10.0 mL etoh solvents, sequentially add the mmol template molecules of 0.2 mmol~1.0 and relax thiazine, 1.0 mmol ~8.0 mmol function monomers Oridonins, 4.5 mmol crosslinking agents N- are trans-to coumaric acyl tyrasamine, 0.12 The nanoclay of the g of mmol initiator azodiisobutyronitriles and 0.0100 g~0.0800, often adds a kind of chemical reagent ultrasonic wave Dissolving 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 85 DEG C of vacuum drying chamber, then using eluant, eluent molar ratio For 1:1 acetic acid and propanol solvent mixture are by template molecule elution, to obtain the final product.