CN104076074A

CN104076074A - Preparation method of electrochemical sensor for fast selection of magnolol

Info

Publication number: CN104076074A
Application number: CN201410352090.0A
Authority: CN
Inventors: 卢丽敏; 张凯鑫; 徐景坤; 段学民; 朱小飞
Original assignee: Jiangxi Agricultural University
Current assignee: Jiangxi Agricultural University
Priority date: 2014-07-23
Filing date: 2014-07-23
Publication date: 2014-10-01

Abstract

The invention relates to a preparation method of an electrochemical sensor for fast selection of magnolol traditional Chinese medicine utilizing a combined electrode of poly(3,4-ethylene dioxythiophene) and multi-walled carbon nanotubes, i.e., PEDOT and MWCNTs. According to the method, the method of interfacial polymerization is adopted to compound PEDOT and MWCNTs to prepare the compound electrode of the materials; electrochemical detection is performed on magnolol in a solution of which phosphate is supporting electrolyte; the compound electrode shows good electrocatalysis activity on magnolol. The electrochemical sensor prepared by the invention realizes efficient, sensitive, and selective detection on magnolol, and can be successfully applied to detection of magnolol content in different medicament forms; moreover, the electrochemical sensor prepared by the invention has the advantages of easiness in preparation of electrode material, low cost, convenience in operation, quickness, high efficiency, high sensitivity, and the like, and has good application prospect and potential application value in the field of food detection and analysis.

Description

Fast selective detects the preparation method of magnolol electrochemical sensor

Technical field

The invention belongs to electrochemical sensor field, relate to the effective constituent in a kind of Cortex Magnoliae Officinalis---the assay method of magnolol, the preparation method of the electrochemical sensor of Determination of Magnolol in especially a kind of Fast Measurement different dosage form magnolol medicine.

Background technology

Magnolol be sepia to the Magnolia cortex P.E of white fine powder, the effective constituent of antibacterial action in Cortex Magnoliae Officinalis skin.Monomer is colourless acicular crystal (water), 102 ℃ of fusing points.Be dissolved in benzene, ether, chloroform, acetone and conventional organic solvent, be insoluble in water, be soluble in caustic alkali lean solution, obtain sodium salt.It is of flaccid muscles that magnolol has obvious, lasting central, nervous centralis inhibiting effect, and anti-inflammatory, antibacterial, resisting pathogenic microbes, antiulcer, anti-oxidant, antitumor, suppress morphine abstinence syndrome reaction, can suppress the pharmacological actions such as platelet aggregation.Clinically main as eliminating the medicine such as full vexed, the calm nervous centralis of chest abdomen, sportsman are of flaccid muscles, antimycotic, antiulcer.Magnolol has been made into the formulations such as suppository, lotion, tablet, capsule at present, and has obtained clinically propagation and employment.Now set up the assay method of multiple magnolol, the method being wherein widely used is mainly chromatography, as thin-layer chromatography, gas chromatography, liquid chromatography, liquid chromatography and mass spectrometry, gas chromatography and mass spectrometry etc., have in addition enzyme-linked immune detection method and electrochemical detection method, these detection methods have advantage separately.At present domestic the quality control of magnolol standard preparation is also only limited to by chromatography, but the method operates comparatively complexity and cost is higher, is further improved.

Sensor owing to can realize continuously, fast, on-the-spot, online live body detects and analyze, and there is the advantages such as portability, feasibility, specificity, simplicity, sensitivity, high efficiency, low cost and be widely used in the relevant and similar field such as environmental monitoring and control, bio-pharmaceuticals and clinical medicine, food security and biofermentation.That electrochemical sensor can be realized is economic, practical, efficient, special, sensitive, accurately and fast, easy detection and analysis.The relevant research to the Electrochemical Detection of magnolol at present, Wu etc. (T Liu, X Zheng, W Huang, K Wu, Colloids and Surfaces B:Biointerfaces 65 (2008) 226 – 229) utilize mesoporous Al/SiO ₂modified electrode, has studied the cyclic voltammetric characteristic of magnolol on modified electrode, and has utilized differential pulse voltammetry to measure magnolol, and the range of linearity is 7.5 * 10 ⁸~ 2.0 * 10 ⁵mol/L; (the G. Chen such as Chen, X. Xu, Y. Zhu, L.P. Zhang, Journal of Pharmaceutical and Biomedical Analysis 41 (2006) 1479-1484) utilize carbon disk electrode and electrophoretic techniques coupling successfully to measure in Cortex Magnoliae Officinalis the content of magnolol in its root skin.The people such as Zhao (J Zhao, W Huang, X Zheng, Journal of Applied Electrochemistry 39 (2009) 2415-2419) utilize SiO ₂the carbon paste electrode of making has been studied the electrochemical behavior of magnolol in phosphate buffered solution by cyclic voltammetry, and has measured magnolol, and the range of linearity is 20.0 ~ 200.0 μ g/L, and the method is applied to the mensuration of magnolol in Cortex Magnoliae Officinalis.Yet, utilize poly-(3,4-ethylenedioxy thiophene) (PEDOT) and multi-walled carbon nano-tubes (MWCNTs) combination electrode measure the content of magnolol in different dosage form and not yet report, and magnolol electrochemical detection method also remains to be further improved at aspects such as detecting lower limit, sensitivity, selectivity, stability at present.

Summary of the invention

The object of this invention is to provide the preparation method that a kind of simple, practical, efficient, sensitive, accurate, inexpensive fast selective detects the galvanochemistry biography device of magnolol content in different dosage form.

Fast selective of the present invention detects the preparation method of magnolol electrochemical sensor, comprises the following steps:

1, the preparation of PEDOT/MWCNTs compound substance: prepare respectively the chloroformic solution of 3,4-ethylene dioxythiophene (EDOT), and MWCNTs and FeCl ₃mixed aqueous solution, then both are mixed according to the ratio of volume ratio 1:1, form chloroform-water two-phase system, in water-bath, react, then adopt centrifugal method by upper water solution centrifugal, wash, obtain the aqueous dispersions of PEDOT/MWCNTs compound substance;

2, the preparation of PEDOT/MWCNTs combination electrode: get above-mentioned PEDOT/MWCNTs solution and drip and be coated onto the clean glass-carbon electrode of polishing surface, dry, make PEDOT/MWCNTs combination electrode.

Fast selective of the present invention detects the preparation method of magnolol electrochemical sensor, its preparation cost is cheap, technique simple, it is simple and easy to operate, the electrochemical sensor that uses this method to prepare not only can successfully detect magnolol, but also has highly sensitive (detecting the low 0.003 μ mol/L that reaches of lower limit), selectivity by force (to glucose, soluble starch, fructose and Br ^-, Cl ^-, NO ₃ ^-, H ₂pO ₄ ^-, SO ₄ ^2-, Na ⁺, Ca ²⁺, Mg ²⁺, K ⁺, Al ³⁺deng material without response), the feature such as good stability, prepared PEDOT/MWCNTs composite electrode can be used for Magnolia cortex P.E and the assay of magnolol in different dosage form.

Accompanying drawing explanation

Fig. 1 is different modifying electrode: glass-carbon electrode (a), and MWCNTs modified electrode (b), PEDOT modified electrode (c), PEDOT/MWCNTs modified electrode (d) is containing 5.0 mM K ₃fe (CN) ₆/ K ₄fe (CN) ₆(1:1) cyclic voltammogram in He 0.1 mol/L KCl;

Fig. 2 is different modifying electrode: glass-carbon electrode (a), and MWCNTs modified electrode (b), PEDOT modified electrode (c), PEDOT/MWCNTs modified electrode (d) detects response diagram to the cyclic voltammetric of magnolol;

Fig. 3 is the linear graph that PEDOT/MWCNTs modified electrode detects magnolol.

Embodiment

Fast selective detects a preparation method for magnolol electrochemical sensor, comprises the following steps:

1, the preparation of PEDOT/MWCNTs compound substance: prepare respectively the chloroformic solution of 3,4-ethylene dioxythiophene (EDOT) of 25 mg/mL and the FeCl of the multi-walled carbon nano-tubes of 0.5 mg/ml and 1 mol/L ₃mixed aqueous solution, then both are mixed according to the ratio of volume ratio 1:1, form chloroform-water two-phase system, in the water-bath of 50 ℃, react 12 h, finally adopt centrifugal method by upper water solution centrifugal, wash, obtain the aqueous dispersions of PEDOT/MWCNTs compound substance;

2, the preparation of PEDOT/MWCNTs combination electrode: get the above-mentioned PEDOT/MWCNTs solution of 5 μ L and drip and be coated onto the clean glass-carbon electrode of polishing surface, dry, make PEDOT/MWCNTs combination electrode.

The electrochemical gaging of magnolol: the magnolol of variable concentrations adds respectively in the phosphate buffer of pH 7.0, use the linear volt-ampere of PEDOT/MWCNTs combination electrode utilization scanning method to measure magnolol, linear the increasing of peak current shows that this sensing electrode can successfully detect the magnolol of unknown concentration.This electrode pair magnolol has good linear dependence, the wide range of linearity, high sensitivity and low detectability.

Electrochemical sensor detects the Performance Evaluation of magnolol: preparation PEDOT/MWCNTs electrode pair magnolol has very strong selectivity, and the materials such as dopamine, ascorbic acid, mandelic acid, glucose, soluble starch, fructose, organic acid are had to stronger antijamming capability.Even at various zwitterions as Br ^-, Cl ^-, NO ₃ ^-, H ₂pO ₄ ^-, SO ₄ ^2-, Na ⁺, Ca ²⁺, Mg ²⁺, K ⁺, Al ³⁺in simultaneous complex environment, electrochemical response there is no significant change yet, thereby got rid of the interference of some common zwitterions.

Actual sample detects to be analyzed: by the Banxia-Houpu Effervescent Tablets of buying, with absolute ethyl alcohol, carry out ultrasonic dissolution, by the centrifugal insolubles of removing, be mixed with again the phosphate buffered solution containing actual sample, utilize PEDOT/MWCNTs combination electrode to detect analysis to the magnolol containing different analytic samples of the variable concentrations of preparation: its recovery is between 99.2% to 101.8%, its relative standard's difference is between 1% to 3.4%, and this shows that the sensor that builds is feasible for the detection analysis of different dosage form magnolol sample.

Claims

1. fast selective detects a preparation method for magnolol electrochemical sensor, it is characterized in that: it comprises the following steps:

(1) preparation of PEDOT/MWCNTs compound substance: prepare respectively the chloroformic solution of the 3,4-ethylene dioxythiophene of 25 mg/mL, and the FeCl of the multi-walled carbon nano-tubes of 0.5 mg/ml and 1 mol/L ₃mixed aqueous solution, then both are mixed according to the ratio of volume ratio 1:1, form chloroform-water two-phase system, in the water-bath of 50 ℃, react 12 h, then adopt centrifugal method by upper water solution centrifugal, wash, obtain the aqueous dispersions of PEDOT/MWCNTs compound substance;

(2) preparation of PEDOT/MWCNTs combination electrode: get the above-mentioned PEDOT/MWCNTs composite material sol of 5 μ L drop and be coated onto the clean glass-carbon electrode surface of polishing, 60 ℃ dry, makes PEDOT/MWCNTs composite electrode.