CN109342541A - A kind of preparation method of chlorimipramine molecular imprinting electrochemical sensor - Google Patents

Abstract

The invention discloses a kind of preparation methods of chlorimipramine molecular imprinting electrochemical sensor, using chlorimipramine as template molecule, abscisic acid is function monomer, azodiisobutyronitrile is initiator, cobalt nickel layer shape powder composite material is dopant, it is sensing film modifier with 4- propoxyl group -4'- cyanobiphenyl, using isoliquiritigenin as crosslinking agent, it is prepared for high sensitivity accordingly, the chlorimipramine molecular imprinting electrochemical sensor of the cobalt nickel layer shape powder composite material doping of resistance to falling property, the analysis method is simple and practical, it is complicated to overcome previous analysis method, equipment is expensive, the low disadvantage of sensitivity.

Description

A kind of preparation method of chlorimipramine molecular imprinting electrochemical sensor

Technical field

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

Background technique

Chlorimipramine (Clomipramine) is a kind of antidepressants, and main function is that central nervous system is blocked to go The reuptake of methylepinephrine and serotonin, it is stronger to the blocking effect of the reuptake of serotonin, and play antidepression and Angst resistance effect also has calm and anticholinergic effect.But such drug is excessively used and will cause has to caused by medicaments insensitive Dry, eye-blurred, dysuria, the side effects such as bone marrow suppression, renal function, liver function impairment, therefore by big portion in the world Point country is classified as controlled substance.

The method of measurement chlorimipramine has high performance liquid chromatography, application of gas chromatorgraphy/mass method etc..However these methods are due to needing The disadvantages of expensive instrument and equipment, there are at high cost, time-consuming, sensitivity is not high.Therefore, study a kind of high sensibility, it is easy Chlorimipramine measuring method have very important significance.

Molecular imprinting technology will be led to functional monomer complementary in structure using object to be measured molecule as template molecule Cross covalently or non-covalently key and form monomer template molecular complex in conjunction with template molecule, add crosslinking agent be allowed to and monomer into Row polymerization reaction forms template molecule polymer, after the reaction was completed by either physically or chemically removing template molecule, is divided Sub- imprinted polymer forms sky complementary and with Multiple recognition site with former microsphere space structure in the polymer Cave.Current method is crosslinked film toughness and rigidity since the function monomer of selection cannot be properly matched with template molecule Also poor, therefore sensitivity is not high and resistance to falling property is bad.

Summary of the invention

The purpose of the present invention is prepare a kind of chlorimipramine molecular imprinting electrochemical sensing of highly sensitive and high crash resistance Device.

In order to reach the purpose of the present invention, simple, production letter that the technical problem to be solved in the present invention is to provide a kind of equipment Easily, the large specific surface area of sensing membrane, electron transmission speed is fast and the chlorimipramine molecular imprinting electrochemical sensor of high-flexibility Preparation method.

In order to solve the above technical problems, the present invention adopts the following technical scheme: using chlorimipramine as template molecule, abscisic acid It is initiator for function monomer, azodiisobutyronitrile, cobalt nickel layer shape powder composite material is dopant, 4- propoxyl group -4'- cyano Biphenyl is sensing film modifier, is prepared by crosslinking agent of isoliquiritigenin.

A kind of preparation method of above-mentioned chlorimipramine molecular imprinting electrochemical sensor, using chlorimipramine as template molecule, Abscisic acid is function monomer, azodiisobutyronitrile is initiator, using isoliquiritigenin as crosslinking agent, cobalt nickel layer shape powder composite material It is sensing film modifier for dopant, 4- propoxyl group -4'- cyanobiphenyl, forms one kind in 2 mm glassy carbon electrode surface of diameter Hydridization cobalt nickel layer shape powder composite material chlorimipramine molecular imprinting polymer membrane, then using eluant, eluent molar ratio 3:1's Acetic acid and isobutanol mixed solvent by template molecule elution to get.

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

<1>taking water as a solvent and preparing 20 mL concentration is that the cobaltous sulfate of 0.25 mol/L, 0.25 mol/L nickel sulfate and concentration are The ascorbic mixed aqueous solution of 0.5 mol/L is that 0.05 mol/L pentaerythrite two is sub- by solvent compound concentration of benzyl alcohol 5 mL of di(2-ethylhexyl)phosphate stearyl, then by 5 mL pentaerythrite diphosphorous acid distearyl ester solutions of preparation with 5 drops/sec of speed Degree be added drop-wise in 20 mL cobaltous sulfates, nickel sulfate and the vitamin C mixed solution of above-mentioned preparation, during dropwise addition with 2500 turns/ Component velocity is vigorously stirred, then carries out reaction 2 hours at 130 DEG C in the hot water kettle of 50 mL, is collected by centrifugation after cooling resulting Precipitating, using dehydrated alcohol wash 3 times, precipitating is collected by centrifugation, by collection be deposited at 50 DEG C be dried in vacuo to get To cobalt nickel layer shape powder composite material；

<2>into 10.0 mL etoh solvents, the mmol template molecule of 1.5 mmol~2.5 chlorimipramine, 3.0 are sequentially added The mmol function monomer of mmol~7.5 abscisic acid, 4.5 mmol crosslinking agent isoliquiritigenins, 0.15 mmol initiator azo two are different The cobalt nickel layer shape powder composite material of the g of 0.0100 g~0.0350 prepared by butyronitrile, step<1>and the third oxygen of 4- of 0.010 g Base -4'- cyanobiphenyl senses film modifier, every to be added a kind of the dissolution of chemical reagent ultrasonic wave 8 minutes；

<3>taking the 8 μ L of mixture of step<2>to be applied to clean smooth diameter is that it is small to place 6 in the glassy carbon electrode surface of 2 mm Electrode after modification is placed in 85 DEG C of vacuum oven thermal polymerization 1.5 hours, then uses eluant, eluent molar ratio by Shi Hou For 3:1 acetic acid and isobutanol mixed solvent by template molecule elution to get.

The study found that be function monomer using chlorimipramine as template molecule, abscisic acid, azodiisobutyronitrile is initiator, Cobalt nickel layer shape powder composite material is dopant, 4- propoxyl group -4'- cyanobiphenyl is sensing film modifier, is with isoliquiritigenin The chlorimipramine molecular imprinting electrochemical sensor of crosslinking agent preparation, can be used for measuring the content of chlorimipramine.Using the present invention The electrochemical analysis method of measurement chlorimipramine is established, there is very outstanding sensitivity；The concentration of chlorimipramine is 1.5 × 10^-8 ~ 1.9×10^-4It is presented within the scope of mol/L good linear relationship (linearly dependent coefficient is R=0.9996), detection limit (S/ NIt=3) is 3.2 × 10^-9Mol/L, therefore, cobalt nickel layer shape powder composite material adulterates and 4- propoxyl group -4'- cyanobiphenyl Modified chlorimipramine molecular imprinting electrochemical sensor sensitivity with higher, more than current detection method；In addition, falling Implement and issue after examination and approval the existing sensor still there is preferable repeatability during measure chlorimipramine, because the sensors a bit with compared with Good crash resistance；And equipment is simple, production is simple.

Detailed description of the invention

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

Specific embodiment

Embodiment 1

One, the processing of glass-carbon electrode

Glass-carbon electrode is successively polished with 1.0 μm, 0.3 μm and 0.05 μm of alumina powder on polishing cloth, is then placed in body Product ratio is 8 min of ultrasound in the nitric acid of 1:1, places into 8 min of ultrasound in dehydrated alcohol, is finally cleaned by ultrasonic with pure water clean.

Two, the preparation of chlorimipramine molecular imprinting electrochemical sensor

<1>taking water as a solvent and preparing 20 mL concentration is that the cobaltous sulfate of 0.25 mol/L, 0.25 mol/L nickel sulfate and concentration are The ascorbic mixed aqueous solution of 0.5 mol/L is that 0.05 mol/L pentaerythrite two is sub- by solvent compound concentration of benzyl alcohol 5 mL of di(2-ethylhexyl)phosphate stearyl, then by 5 mL pentaerythrite diphosphorous acid distearyl ester solutions of preparation with 5 drops/sec of speed Degree be added drop-wise in 20 mL cobaltous sulfates, nickel sulfate and the vitamin C mixed solution of above-mentioned preparation, during dropwise addition with 2500 turns/ Component velocity is vigorously stirred, then carries out reaction 2 hours at 130 DEG C in the hot water kettle of 50 mL, is collected by centrifugation after cooling resulting Precipitating, using dehydrated alcohol wash 3 times, precipitating is collected by centrifugation, by collection be deposited at 50 DEG C be dried in vacuo to get To cobalt nickel layer shape powder composite material；

<2>into 10.0 mL etoh solvents, the mmol template molecule of 1.5 mmol~2.5 chlorimipramine, 3.0 are sequentially added The mmol function monomer of mmol~7.5 abscisic acid, 4.5 mmol crosslinking agent isoliquiritigenins, 0.15 mmol initiator azo two are different The cobalt nickel layer shape powder composite material of the g of 0.0100 g~0.0350 prepared by butyronitrile, step<1>and the third oxygen of 4- of 0.010 g Base -4'- cyanobiphenyl senses film modifier, every to be added a kind of the dissolution of chemical reagent ultrasonic wave 8 minutes；

<3>taking the 8 μ L of mixture of step<2>to be applied to clean smooth diameter is that it is small to place 6 in the glassy carbon electrode surface of 2 mm Electrode after modification is placed in 85 DEG C of vacuum oven thermal polymerization 1.5 hours, then uses eluant, eluent molar ratio by Shi Hou For 3:1 acetic acid and isobutanol mixed solvent by template molecule elution, by magnetic agitation eluted template molecule, until eluent In can't detect template molecule, then wash away the solvent of trace electrode surface with ultrapure water, be then stored in trace electrode ultrapure It is stand-by in water.

Three, the drafting of working curve, the measurement of detection limit

The experiment of molecular engram electrode response characteristic is carried out using differential pulse voltammetry, measures the range of linearity and detection limit.It will Chlorimipramine molecular engram electrode point that cobalt nickel layer shape powder composite material adulterates and that 4- propoxyl group -4'- cyanobiphenyl is modified 6 minutes are cultivated not in the chlorimipramine solution of various concentration, and (bottom liquid is 5.0 mmol/L K₃[Fe(CN)₆]-0.5 mol/L The phosphate buffer solution solution of pH=7.5), then carry out differential pulse voltammetry measurement.Chlorimipramine solution concentration exists 1.5×10^-8 ~ 1.9×10^-4Good linear relationship is presented within the scope of mol/L；Linear equation isIp(μA) = - 0.1079 с (μm ol/L)+23.29, linearly dependent coefficient be R=0.9996, detection limit (S/NIt=3) is 3.2 × 10^-9 mol/L。

Four, chlorimipramine molecular imprinting electrochemical sensor crash resistance is tested

Chlorimipramine molecule that the cobalt nickel layer shape powder composite material of preparation adulterates and that 4- propoxyl group -4'- cyanobiphenyl is modified Trace sensor first carries out falling 5 times on 1.5 meters of high experimental benches, falls every time and is all made of differential pulse voltammetry and is divided The experiment of sub- trace electrode response characteristic, the repetitive rate of the concentration of 5 measurement chlorimipramines is between 95%-98%.

Therefore, chlorimipramine which adulterates and that 4- propoxyl group -4'- cyanobiphenyl is modified Molecular engram electrode has high sensitivity and crash resistance with higher.

Claims (1)

1. a kind of preparation method of chlorimipramine molecular imprinting electrochemical sensor, it is characterised in that with 0.15 mmol/mL~ The chlorimipramine of 0.25 mmol/mL be template molecule, the mmol/mL of 0.30 mmol/mL~0.75 abscisic acid be function list Body, 0.015 mmol/mL azodiisobutyronitrile be initiator, using the isoliquiritigenin of 0.45 mmol/mL as crosslinking agent, The cobalt nickel layer shape powder composite material of the g/mL of 0.0010 g/mL~0.0035 is the third oxygen of 4- of dopant, 0.0010 g/mL Base -4'- cyanobiphenyl is sensing film modifier, and a kind of hydridization cobalt nickel layer shape powder composite material is formed in glassy carbon electrode surface The chlorimipramine molecular imprinting polymer membrane of doping, then using eluant, eluent acetic acid and isobutanol mixed solvent eluted template point Son to obtain the final product；

Specifically carried out by following operation:

<1>taking water as a solvent and preparing 20 mL concentration is that the cobaltous sulfate of 0.25 mol/L, 0.25 mol/L nickel sulfate and concentration are The ascorbic mixed aqueous solution of 0.5 mol/L is that 0.05 mol/L pentaerythrite two is sub- by solvent compound concentration of benzyl alcohol 5 mL of di(2-ethylhexyl)phosphate stearyl, then by 5 mL pentaerythrite diphosphorous acid distearyl ester solutions of preparation with 5 drops/sec of speed Degree be added drop-wise in 20 mL cobaltous sulfates, nickel sulfate and the vitamin C mixed solution of above-mentioned preparation, during dropwise addition with 2500 turns/ Component velocity is vigorously stirred, then carries out reaction 2 hours at 130 DEG C in the hot water kettle of 50 mL, is collected by centrifugation after cooling resulting Precipitating, using dehydrated alcohol wash 3 times, precipitating is collected by centrifugation, by collection be deposited at 50 DEG C be dried in vacuo to get To cobalt nickel layer shape powder composite material；

<2>into 10.0 mL etoh solvents, the mmol template molecule of 1.5 mmol~2.5 chlorimipramine, 3.0 are sequentially added The mmol function monomer of mmol~7.5 abscisic acid, 4.5 mmol crosslinking agent isoliquiritigenins, 0.15 mmol initiator azo two are different The cobalt nickel layer shape powder composite material of the g of 0.0100 g~0.0350 prepared by butyronitrile, step<1>and the third oxygen of 4- of 0.010 g Base -4'- cyanobiphenyl senses film modifier, every to be added a kind of the dissolution of chemical reagent ultrasonic wave 8 minutes；

<3>taking the 8 μ L of mixture of step<2>to be applied to clean smooth diameter is that it is small to place 6 in the glassy carbon electrode surface of 2 mm Electrode after modification is placed in 85 DEG C of vacuum oven thermal polymerization 1.5 hours, then uses eluant, eluent molar ratio by Shi Hou For 3:1 acetic acid and isobutanol mixed solvent by template molecule elution to get.