CN106680354A - Electrochemical method for determining methyl parahydroxybenzoats - Google Patents
Electrochemical method for determining methyl parahydroxybenzoats Download PDFInfo
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Abstract
The invention relates to the field of the detection of methylparaben, and particularly discloses an electrochemical method for determining methyl parahydroxybenzoats in food, drugs and cosmetics. The electrochemical method for determining the methyl parahydroxybenzoats is characterized by comprising the following steps: polishing and washing a glassy carbon electrode, then placing the glassy carbon electrode into a solution prepared by PBS, azodicarbonamide and secondary distilled water, circularly scanning by adopting the glassy carbon electrode as a working electrode, an Ag/AgCl electrode as a reference electrode and a platinum wire electrode as a counter electrode, thus obtaining an azodicarbonamide-modified electrode; and adding a PBS buffer solution, secondary distilled water and the methylparaben into a beaker, circularly scanning by adopting a differential pulse voltammetry and by adopting the azodicarbonamide-modified electrode as a working electrode, the Ag/AgCl electrode as a reference electrode and the platinum wire electrode as the counter electrode, and recording a peak potential and a peak current. The electrochemical method has the advantages of simplicity, feasibility, good selectivity, high sensitivity, low expense and the like.
Description
（One）Technical field
The present invention relates to the detection field of methyl hydroxybenzoate, more particularly to a kind of to determine para hydroxybenzene in food, medicine and cosmetics
The electrochemical method of methyl formate.
（Two）Background technology
Methyl parahydroxybenzoate, also referred to as methyl hydroxybenzoate or methyl hydroxybenzoate, its chemical structural formula is as follows：。
Methyl hydroxybenzoate is the preservative that a class is applied to acid system, is mainly used as organic synthesiss, food, cosmetics, doctor
The disinfection preservative of medicine, used also as in feed anticorrosion agent.They have good inhibiting effect to antibacterial, yeast and mold,
Once because hypotoxicity, it is nonirritant the features such as be widely used.But recently it is reported that methyl hydroxybenzoate can also cause contact
Dermatitis, and there are some researches show that methyl hydroxybenzoate has certain relation with the risk that suffers from breast cancer.China cosmetic hygienic practice 2007
Specify that paraben preservative single ester highest limitation in cosmetics is 0.4% in year version.
At present the detection method of methyl hydroxybenzoate has high performance liquid chromatography and gas chromatography-mass spectrography method, efficient liquid
Phase chromatograph-ultraviolet method, high performance liquid chromatography mass spectrography, in addition with TLC scanning method, Capillary Micellar Electrokinetic Chromatography
Deng.The operating procedure of this several method is complicated, and detection time is long, and testing cost is high, and high to instrument requirements.Hence set up one
Plant and simply, efficiently detect that methyl hydroxybenzoate method is extremely important.
（Three）The content of the invention
The present invention is in order to make up the deficiencies in the prior art, there is provided the measure that a kind of simple possible, selectivity are good, sensitivity is high is right
The electrochemical method of methyl hydroxybenzoate.
The present invention is achieved through the following technical solutions：
A kind of electrochemical method for determining methyl parahydroxybenzoate, comprises the steps：
（1）To be placed in the solution that PBS, azodicarbonamide and redistilled water are made into after glass-carbon electrode polishing, cleaning, shake
Even, with glass-carbon electrode as working electrode, Ag/AgCl electrodes are reference electrode, and platinum electrode is to electrode, in 1.3-2.1V current potentials
In the range of, with 20mV/s sweep speeds scan round 16 weeks, take out and use second distillation water wash electrode surface, dry, that is, it is worth
Azodicarbonamide modified electrode；
（2）PBS, redistilled water and methyl hydroxybenzoate that pH is 4.0 are sequentially added in beaker, with azodicarbonamide
Modified electrode is working electrode, and Ag/AgCl electrodes are reference electrode, and platinum electrode is, to electrode, 10s to be stirred, in 0.6-1.2V
In potential range, scanning, record spike potential and peak current are circulated using differential pulse voltammetry；Every time after the end of scan,
Electrode is disappeared as scan round in blank dropping liquid to peak, is rinsed with redistilled water, after filter paper is blotted, you can carry out next
Secondary measure.
The present invention more excellent technical scheme be：
Step（1）In, a diameter of 3.8mm of glass-carbon electrode.
Step（1）In, glass-carbon electrode is polished on the abrasive paper for metallograph of moistening, then it is polished on the aluminium oxide of moistening
Minute surface, is cleaned by ultrasonic, then is used distilled water wash with salpeter solution, dehydrated alcohol, secondary quartzy sub-boiling distillation water successively；Metallographic sand
The granularity of paper is 2000, and the particle diameter of aluminium oxide is 0.05 μm, and the glass-carbon electrode cleaning after polishing is 30s/ time.
Step（1）In, the glass-carbon electrode after cleaning is put into PBS buffer solution, the 2mL 0.01mol/L that 10mLpH is 7.0
Azodicarbonamide solution and the solution that is made into of 8mL redistilled waters in.
Using differential pulse voltammetry drawing curve.Under optimum experimental condition, in 0.6-1.2V potential ranges,
The methyl hydroxybenzoate standard solution of variable concentrations is measured with differential pulse voltammetry.
The present invention is prepared for azodicarbonamide modified electrode to detect methyl hydroxybenzoate using electrochemical method, with simple
Feasible, selectivity is good, and sensitivity is high, the advantages of low cost.
（Four）Description of the drawings
Below in conjunction with the accompanying drawings the present invention is further illustrated.
Fig. 1 is methyl hydroxybenzoate of the present invention in bare glassy carbon electrode（1）With azodicarbonamide modified electrode（2）On circulation volt
Antu；
Fig. 2 is differential pulse volt of the methyl hydroxybenzoate of variable concentrations under optimum experimental condition in azodicarbonamide modified electrode
Antu；
Fig. 3 is standard curve electric current and concentration logarithmic diagram；
Fig. 4 is 2.0 × 10-5The circulation volt that parallel assay of the mol/L methyl hydroxybenzoate in azodicarbonamide modified electrode is 6 times
Peace curve；
Fig. 5 is glassy carbon electrode surface scanning electron microscope (SEM) photograph；
Fig. 6 is azodicarbonamide modified electrode surface scan electron microscope.
（Five）Specific embodiment
Embodiment：
（1）Instrument and reagent
CHI660D type electrochemical analysis systems (Shanghai Chen Hua companies)；KH-100DB type ultrasonic cleaner (city of Kunshan's Ultrasound Instrument
Device company limited)；The high-purity water distillation apparatus (Jing Bo experimental apparatus factory of Jintan City) of the sub- boiling of SYZ-550 types quartz；ESJ180-4 electronics
Analytical balance；Microsyringe；Electrochemistry experiment three-electrode system, Ag/AgCl electrodes be reference electrode, azodicarbonamide
Modified electrode is working electrode, and 213 type platinum electrodes (Shanghai Russell Science and Technology Ltd.) are to electrode.
1.0×10-3Methyl hydroxybenzoate (Ao Ruiqi groups of the Sigma) standard solution of mol/L keeps in dark place；0.01mol/L idols
Nitrogen diformamide (fine chemistry industry institute is recovered in Tianjin) solution keeps in dark place；0.2mol/L disodium phosphate solns (Shanghai
Reagent factory), 0.1mol/L citric acid solutions (Shanghai Pu Zhen bio tech ltd) prepare phosphate buffered solution
(PBS, pH be 2.2~8.0)；Dehydrated alcohol (Laiyang economic and technological development zone Fine Chemical Works)；Reagent is analyzes pure, experiment
Secondary quartzy sub-boiling distillation water is with water.
（2）The preparation of azodicarbonamide modified electrode
Glass-carbon electrode (Φ=3.8mm) is polished on the abrasive paper for metallograph (granularity is 2000) of moistening, then in the Al of moistening2O3
Minute surface is polished on (0.05 μm), HNO is used successively3(1:1, V/V), dehydrated alcohol, secondary quartzy sub-boiling distillation water are cleaned by ultrasonic
(30s/ time), then with distilled water wash after, be put into 10.00mL PBS (pH=7.0), 2.00mL (0.01mol/L) azo diformazan
In the solution that amide and 8.00mL redistilled waters are made into, shake up, with glass-carbon electrode as working electrode, Ag/AgCl electrodes are ginseng
Than electrode, platinum electrode be to electrode, in -1.3~2.1V potential ranges, with 20mV/s sweep speeds scan round 16 weeks,
Take out and use second distillation water wash electrode surface, dry, that is, azodicarbonamide modified electrode is obtained.
（3）Detection method
PBS buffer solution, redistilled water and the methyl hydroxybenzoate of a certain amount of pH=4.0 are sequentially added in beaker.With azo diformazan
Amide modified electrode is working electrode, and Ag/AgCl electrodes are reference electrode, and platinum electrode is to electrode, to stir 10s, 0.6~
In 1.2V potential ranges, scanning, record spike potential and peak current are circulated using differential pulse voltammetry.Each end of scan
Afterwards, electrode is placed in into scan round in blank bottom liquid to disappear to peak, is rinsed with redistilled water, after filter paper is blotted, you can carry out
Determine next time.
（4）Technical specification
Using differential pulse voltammetry drawing curve.Under optimum experimental condition, in 0.6-1.2V potential ranges, with difference
Pulse voltammetry is divided to be measured the methyl hydroxybenzoate standard solution of variable concentrations.As a result show, methyl hydroxybenzoate standard solution exists
Concentration range 6.0 × 10-6-4.0×10-4Logarithm value in mol/L has good linear pass with methyl hydroxybenzoate oxidation peak current
It is that its equation of linear regression isi pa=8.11×10-6+ 1.54lgc(μmol·L-1), correlation coefficient is R=0.9906, detection limit
For 4.0 × 10-6mol·L-1。
With azodicarbonamide modified electrode to 2.0 × 10-3mol·L-1Methyl hydroxybenzoate standard solution is measured 6 times,
It is 1.6% to measure result RSD, and showing the measure of the electrode pair methyl hydroxybenzoate has preferable repeatability, as shown in Figure 4.
Accompanying drawing 1 be methyl hydroxybenzoate respectively on bare glassy carbon electrode (1), azodicarbonamide modified electrode (2) when circulation
Volt-ampere response diagram, as seen from the figure：Current value of the methyl hydroxybenzoate in bare glassy carbon electrode be:i pa1 =5.39μA.And electrode Jing azos
Current value after diformamide chemical modification on azodicarbonamide modified electrode is：i pa2 =21.8μA.With bare glassy carbon electrode
Compare, the oxidation peak current on azodicarbonamide modified electrode significantly increases about 4 times, and this is likely due to azodicarbonamide
Modified membrane has good catalytic action to methyl hydroxybenzoate electrochemical oxidation film.
In accompanying drawing 2, the concentration from a to j is respectively:6.0×10-6, 8.0 × 10-6, 1.0 × 10-5, 2.0 × 10-5, 4.0 ×
10-5, 6.0 × 10-5, 8.0 × 10-5, 1.0 × 10-4, 2.0 × 10-4, 4.0 × 10-4mol·L-1。
With azodicarbonamide modified electrode to 2.0 × 10-3mol·L-1Methyl hydroxybenzoate standard solution is measured 6 times,
It is 1.6% to measure result RSD, and showing the measure of the electrode pair methyl hydroxybenzoate has preferable repeatability, as shown in Figure 4.
The scanning electron microscope comparison diagram of accompanying drawing 5 and accompanying drawing 6, it was demonstrated that azodicarbonamide has been modified glassy carbon electrode surface.
（5）The measure of the response rate
Can detect that the response rate is in 96%-103% to methyl hydroxybenzoate in medicine, cosmetics and food using the method for the present invention
Between.
Claims (5)
1. it is a kind of determine methyl parahydroxybenzoate electrochemical method, it is characterized by, comprise the steps：（1）By glass carbon electricity
It is placed in the solution that PBS, azodicarbonamide and redistilled water are made into after pole polishing, cleaning, shakes up, with glass-carbon electrode as work
Make electrode, Ag/AgCl electrodes are reference electrode, and platinum electrode is, to electrode, in 1.3-2.1V potential ranges, to sweep with 20mV/s
Retouch rate loop to scan 16 weeks, take out and use second distillation water wash electrode surface, dry, that is, be worth azodicarbonamide modification electricity
Pole；（2）PBS, redistilled water and methyl hydroxybenzoate that pH is 4.0 are sequentially added in beaker, with azodicarbonamide
Modified electrode is working electrode, and Ag/AgCl electrodes are reference electrode, and platinum electrode is, to electrode, 10s to be stirred, in 0.6-1.2V
In potential range, scanning, record spike potential and peak current are circulated using differential pulse voltammetry；Every time after the end of scan,
Electrode is disappeared as scan round in blank dropping liquid to peak, is rinsed with redistilled water, after filter paper is blotted, you can carry out next
Secondary measure.
2. it is according to claim 1 determine methyl parahydroxybenzoate electrochemical method, it is characterised in that：Step（1）
In, a diameter of 3.8mm of glass-carbon electrode.
3. it is according to claim 1 determine methyl parahydroxybenzoate electrochemical method, it is characterised in that：Step（1）
In, glass-carbon electrode is polished on the abrasive paper for metallograph of moistening, then minute surface is polished on the aluminium oxide of moistening, nitric acid is used successively
Solution, dehydrated alcohol, secondary quartzy sub-boiling distillation water are cleaned by ultrasonic, then use distilled water wash.
4. according to claim 1 measure methyl parahydroxybenzoate electrochemical method, it is characterised in that：Step（1）
In, the glass-carbon electrode after cleaning be put into the PBS buffer solution that 10mLpH is 7.0,2mL 0.01mol/L azodicarbonamide it is molten
In the solution that liquid and 8mL redistilled waters are made into.
5. it is according to claim 3 determine methyl parahydroxybenzoate electrochemical method, it is characterised in that：Step（1）
In, the granularity of abrasive paper for metallograph is 2000, and the particle diameter of aluminium oxide is 0.05 μm, and the glass-carbon electrode cleaning after polishing is 30s/ time.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102565174A (en) * | 2012-02-20 | 2012-07-11 | 浙江大学 | Ionic liquid polyaniline modified electrode-electro chemical analysis system |
| CN103642063A (en) * | 2013-11-04 | 2014-03-19 | 江苏大学 | Preparation method of mythyl p-hydroxybenzoate molecular imprinting composite membrane and application thereof |
| CN105223260A (en) * | 2015-10-20 | 2016-01-06 | 信阳师范学院 | Trace is electrochemical sensor detecting butyl p-hydroxybenzoate and preparation method thereof fast |
| CN105572189A (en) * | 2014-10-17 | 2016-05-11 | 南京理工大学 | Polyglutamic acid modified electrode and application thereof to detection of content of drug paracetamol |
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2016
- 2016-12-09 CN CN201611128276.3A patent/CN106680354B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102565174A (en) * | 2012-02-20 | 2012-07-11 | 浙江大学 | Ionic liquid polyaniline modified electrode-electro chemical analysis system |
| CN103642063A (en) * | 2013-11-04 | 2014-03-19 | 江苏大学 | Preparation method of mythyl p-hydroxybenzoate molecular imprinting composite membrane and application thereof |
| CN105572189A (en) * | 2014-10-17 | 2016-05-11 | 南京理工大学 | Polyglutamic acid modified electrode and application thereof to detection of content of drug paracetamol |
| CN105223260A (en) * | 2015-10-20 | 2016-01-06 | 信阳师范学院 | Trace is electrochemical sensor detecting butyl p-hydroxybenzoate and preparation method thereof fast |
Non-Patent Citations (3)
| Title |
|---|
| ERIC DE S. GIL,ET AL.: "Cyclic Voltammetry and Computational Chemistry Studies on the Evaluation of the Redox Behavior of Parabens and other Analogues", 《J. BRAZ. CHEM. SOC.》 * |
| KEERTI M.NAIK,ET AL.: "Electroanalytical method for the determination of methylparaben", 《SENSORS AND ACTUATORS A》 * |
| SEYFULLAH MADAKBAS, ET AL.: "Determination of Methylparaben by Differential Pulse Voltammetry Using a Glassy Carbon Electrode Modified with Polypyrrole", 《JOURNAL OF ANALYTICAL CHEMISTRY》 * |
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