CN106680354B - A kind of electrochemical method measuring methyl p-hydroxybenzoate - Google Patents
A kind of electrochemical method measuring methyl p-hydroxybenzoate Download PDFInfo
- Publication number
- CN106680354B CN106680354B CN201611128276.3A CN201611128276A CN106680354B CN 106680354 B CN106680354 B CN 106680354B CN 201611128276 A CN201611128276 A CN 201611128276A CN 106680354 B CN106680354 B CN 106680354B
- Authority
- CN
- China
- Prior art keywords
- electrode
- methyl
- hydroxybenzoate
- distilled water
- glass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Sampling And Sample Adjustment (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The present invention relates to the detection field of methyl hydroxybenzoate, particularly disclose a kind of measurement food, in drug and cosmetics methyl p-hydroxybenzoate electrochemical method.The electrochemical method of the measurement methyl p-hydroxybenzoate, it is characterized in that: glass-carbon electrode polishing, cleaning are placed in the solution that PBS, azodicarbonamide and secondary distilled water are made into, using glass-carbon electrode as working electrode, Ag/AgCl electrode is reference electrode, platinum electrode is to electrode, scan round is worth azodicarbonamide modified electrode；PBS buffer solution, secondary distilled water and methyl hydroxybenzoate are sequentially added into beaker, using azodicarbonamide modified electrode as working electrode, Ag/AgCl electrode is reference electrode, and platinum electrode is to electrode, scan round is carried out using differential pulse voltammetry, records spike potential and peak current.The present invention has the advantages that simple possible, selectively good, high sensitivity, low-cost.
Description
(1) technical field
The present invention relates to the detection field of methyl hydroxybenzoate, in particular to hydroxyl in a kind of measurement food, drug and cosmetics
The electrochemical method of yl benzoic acid methyl esters.
(2) background technique
Methyl p-hydroxybenzoate, also referred to as methylparaben or methyl hydroxybenzoate, chemical structural formula are as follows:
。
Methyl hydroxybenzoate is a kind of preservative for being suitable for acid system, is mainly used as organic synthesis, food, cosmetics, doctor
The disinfection preservative of medicine, used also as in feed anticorrosion agent.They have good inhibiting effect to bacterium, yeast and mold,
Once it was widely used because of hypotoxicity, nonirritant the features such as.But recently it is reported that methyl hydroxybenzoate can also cause contact
Dermatitis, and some researches show that methyl hydroxybenzoate and suffer from breast cancer that there are certain relationships for risk.China cosmetic hygienic practice 2007
Regulation paraben preservative single ester highest limitation in cosmetics is 0.4% in year version.
The detection method of methyl hydroxybenzoate has high performance liquid chromatography and gas chromatography-mass spectrography method, efficient liquid at present
Phase chromatography-ultraviolet method, high performance liquid chromatography mass spectrography, in addition there are thin layer chromatography, Capillary Micellar Electrokinetic Chromatography
Deng.The operating procedure of these types of method is complicated, and detection time is long, and testing cost is high, and to instrument requirements height.Therefore one is established
Kind is simple, efficiently detection methyl hydroxybenzoate method is extremely important.
(3) summary of the invention
In order to compensate for the shortcomings of the prior art, the present invention provides a kind of simple possibles, good, high sensitivity the survey of selectivity
Determine the electrochemical method of methyl p-hydroxybenzoate.
The present invention is achieved through the following technical solutions:
A kind of electrochemical method measuring methyl p-hydroxybenzoate, includes the following steps:
(1) glass-carbon electrode polishing, cleaning are placed in the solution that PBS, azodicarbonamide and secondary distilled water are made into,
It shakes up, using glass-carbon electrode as working electrode, Ag/AgCl electrode is reference electrode, and platinum electrode is to electrode, in 1.3-2.1V electricity
In the range of position, with 20mV/s sweep speed scan round 16 weeks, taking-up eluted electrode surface with secondary distilled water, dries, that is, be worth
Obtain azodicarbonamide modified electrode；
(2) PBS buffer solution, secondary distilled water and methyl hydroxybenzoate that pH is 4.0 are sequentially added, into beaker with azo diformazan
Amide modified electrode is working electrode, and Ag/AgCl electrode is reference electrode, and platinum electrode is 10s to be stirred, in 0.6- to electrode
In 1.2V potential range, scan round is carried out using differential pulse voltammetry, records spike potential and peak current；Each end of scan
Afterwards, electrode is disappeared as scan round in blank dropping liquid to peak, is rinsed with secondary distilled water, after filter paper blots, can be carried out
It measures next time.
More excellent technical solution of the invention are as follows:
In step (1), the diameter of glass-carbon electrode is 3.8mm.
In step (1), glass-carbon electrode is polished on wet abrasive paper for metallograph, is then polished on wet aluminium oxide
Mirror surface is successively cleaned by ultrasonic with nitric acid solution, dehydrated alcohol, secondary quartzy sub-boiling distillation water, then is washed with distilled water；Metallographic sand
The granularity of paper is 2000, and the partial size of aluminium oxide is 0.05 μm, and the glass-carbon electrode cleaning after polishing is 30s/ times.
In step (1), 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 secondary distilled water in.
Working curve is drawn using differential pulse voltammetry.Under optimum experimental condition, in 0.6-1.2V potential range,
It is measured with methyl hydroxybenzoate standard solution of the differential pulse voltammetry to various concentration.
The present invention is prepared for azodicarbonamide modified electrode using electrochemical method to detect methyl hydroxybenzoate, has simple
It is feasible, selectivity good, high sensitivity, it is low-cost the advantages that.
(4) Detailed description of the invention
The present invention will be further described below with reference to the drawings.
Fig. 1 is circulation volt of the methyl hydroxybenzoate of the present invention in bare glassy carbon electrode (1) and azodicarbonamide modified electrode (2)
Antu；
Fig. 2 is difference arteries and veins of the methyl hydroxybenzoate of various concentration under optimum experimental condition in azodicarbonamide modified electrode
Rush voltammogram；
Fig. 3 is standard curve electric current and concentration logarithmic diagram；
Fig. 4 is 2.0 × 10-5The circulation that parallel determination of the mol/L methyl hydroxybenzoate in azodicarbonamide modified electrode is 6 times
Volt-ampere curve；
Fig. 5 is glassy carbon electrode surface scanning electron microscope (SEM) photograph；
Fig. 6 is azodicarbonamide modified electrode surface scan electron microscope.
(5) specific embodiment
Embodiment:
(1) instrument and reagent
CHI660D type electrochemical analysis system (Shanghai Chen Hua company)；(city of Kunshan is super for KH-100DB type ultrasonic cleaner
Sound Instrument Ltd.)；SYZ-550 type quartz is sub- to boil high-purity water distillation apparatus (Jing Bo laboratory apparatus factory of Jintan City)； ESJ180-4
Electronic analytical balance；Microsyringe；Electrochemistry experiment three-electrode system, Ag/AgCl electrode are reference electrode, azo diformazan
Amide 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 group of Sigma) standard solution of mol/L is kept in dark place；0.01mol/L is even
Nitrogen diformamide (fine chemistry industry research institute is recovered in Tianjin) solution is kept in dark place；0.2mol/L disodium phosphate soln (Shanghai
Reagent factory), 0.1mol/L citric acid solution (Shanghai Pu Zhen Biotechnology Co., Ltd) prepare phosphate buffer solution
(PBS, pH are 2.2~8.0)；Dehydrated alcohol (Laiyang economic and technological development zone Fine Chemical Works)；Reagent is that analysis is pure, experiment
It is secondary quartzy sub-boiling distillation water with water.
(2) preparation of azodicarbonamide modified electrode
Glass-carbon electrode (Φ=3.8mm) is polished on wet abrasive paper for metallograph (granularity 2000), then wet
Al2O3It is polished to mirror surface on (0.05 μm), successively uses HNO3(1:1, V/V), dehydrated alcohol, secondary quartzy sub-boiling distillation water ultrasound
It cleans (30s/ times), then after being washed with distilled water, is put into 10.00mL PBS (pH=7.0), 2.00mL (0.01mol/L) azo
In the solution that diformamide and 8.00mL secondary distilled water are made into, shake up, using glass-carbon electrode as working electrode, Ag/AgCl electrode
For reference electrode, platinum electrode is to electrode, in -1.3~2.1V potential range, with 20mV/s sweep speed scan round 16
Week, taking-up elute electrode surface with secondary distilled water, dry, obtain azodicarbonamide modified electrode.
(3) detection method
PBS buffer solution, secondary distilled water and the methyl hydroxybenzoate of a certain amount of pH=4.0 are sequentially added into beaker.With azo
Diformamide modified electrode is working electrode, and Ag/AgCl electrode is reference electrode, and platinum electrode is to stir 10s to electrode,
In 0.6~1.2V potential range, scan round is carried out using differential pulse voltammetry, records spike potential and peak current.It sweeps every time
After retouching, electrode is placed in scan round to peak in the liquid of blank bottom and is disappeared, is rinsed with secondary distilled water, after filter paper blots, i.e.,
It can be measured next time.
(4) technical indicator
Working curve is drawn using differential pulse voltammetry.Under optimum experimental condition, in 0.6-1.2V potential range,
It is measured with methyl hydroxybenzoate standard solution of the differential pulse voltammetry to various concentration.The result shows that methyl hydroxybenzoate standard is molten
Liquid is in concentration range 6.0 × 10-6-4.0×10-4Logarithm and methyl hydroxybenzoate oxidation peak current in mol/L have good linear
Relationship, equation of linear regression arei pa=8.11×10-6+ 1.54lgc(μmol·L-1), related coefficient is R=0.9906, detection
It is limited to 4.0 × 10-6mol·L-1。
With azodicarbonamide modified electrode to 2.0 × 10-3mol·L-1Methyl hydroxybenzoate standard solution is measured 6 times,
Measuring result RSD is 1.6%, shows that the electrode has preferable reproducibility to the measurement of methyl hydroxybenzoate, as shown in Fig. 4.
Attached drawing 1 is methyl hydroxybenzoate circulation when on bare glassy carbon electrode (1), azodicarbonamide modified electrode (2) respectively
Volt-ampere response diagram, as seen from the figure: current value of the methyl hydroxybenzoate in bare glassy carbon electrode are as follows:i pa1 =5.39μA.And electrode is through azo
Current value after diformamide chemical modification on azodicarbonamide modified electrode are as follows:i pa2 =21.8μA.With bare glassy carbon electrode
It compares, the oxidation peak current on azodicarbonamide modified electrode significantly increases about 4 times, this may be due to azodicarbonamide
Modified membrane has good catalytic action to methyl hydroxybenzoate electrochemical oxidation film.
In attached drawing 2, the concentration from a to j is respectively as follows: 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,
Measuring result RSD is 1.6%, shows that the electrode has preferable reproducibility to the measurement of methyl hydroxybenzoate, as shown in Fig. 4.
The scanning electron microscope comparison diagram of attached drawing 5 and attached drawing 6, it was demonstrated that azodicarbonamide has been modified glassy carbon electrode surface.
(5) measurement of the rate of recovery
Methyl hydroxybenzoate in drug, cosmetics and food can be detected using method of the invention, the rate of recovery is in 96%-
Between 103%.
Claims (5)
1. a kind of electrochemical method for measuring methyl p-hydroxybenzoate, it is characterized in that, include the following steps: (1) by glass carbon electricity
Pole polishing, cleaning are placed in the solution that phosphate buffer solution, azodicarbonamide and secondary distilled water are made into, and are shaken up, with
Glass-carbon electrode is working electrode, and Ag/AgCl electrode is reference electrode, and platinum electrode is to electrode, in 1.3-2.1V potential range
Interior, with 20mV/s sweep speed scan round 16 weeks, taking-up eluted electrode surface with secondary distilled water, dries, obtain azo
Diformamide modified electrode；(2) pH is sequentially added into beaker for 4.0 phosphate buffer solution, secondary distilled water and to hydroxyl
Yl benzoic acid methyl esters, using azodicarbonamide modified electrode as working electrode, Ag/AgCl electrode is reference electrode, platinum electrode
To stir 10s to electrode, in 0.6-1.2V potential range, scan round, record peak electricity are carried out using differential pulse voltammetry
Position and peak current；After each end of scan, electrode is disappeared as scan round in the liquid of blank bottom to peak, is rushed with secondary distilled water
It washes, after filter paper blots, can be measured next time.
2. the electrochemical method of measurement methyl p-hydroxybenzoate according to claim 1, it is characterised in that: step (1)
In, the diameter of glass-carbon electrode is 3.8mm.
3. the electrochemical method of measurement methyl p-hydroxybenzoate according to claim 1, it is characterised in that: step (1)
In, glass-carbon electrode is polished on wet abrasive paper for metallograph, then mirror surface is polished on wet aluminium oxide, successively uses nitric acid
Solution, dehydrated alcohol, secondary quartzy sub-boiling distillation water ultrasonic cleaning, then be washed with distilled water.
4. the electrochemical method of measurement methyl p-hydroxybenzoate according to claim 1, it is characterised in that: step (1)
In, it is molten that the glass-carbon electrode after cleaning is put into the PBS buffer solution that 10mLpH is 7.0, the azodicarbonamide of 2mL 0.01mol/L
In the solution that liquid and 8mL secondary distilled water are made into.
5. the electrochemical method of measurement methyl p-hydroxybenzoate according to claim 3, it is characterised in that: step (1)
In, the granularity of abrasive paper for metallograph is 2000, and the partial size of aluminium oxide is 0.05 μm, and the glass-carbon electrode cleaning after polishing is 30s/ times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611128276.3A CN106680354B (en) | 2016-12-09 | 2016-12-09 | A kind of electrochemical method measuring methyl p-hydroxybenzoate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611128276.3A CN106680354B (en) | 2016-12-09 | 2016-12-09 | A kind of electrochemical method measuring methyl p-hydroxybenzoate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106680354A CN106680354A (en) | 2017-05-17 |
| CN106680354B true CN106680354B (en) | 2019-02-01 |
Family
ID=58867907
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611128276.3A Active CN106680354B (en) | 2016-12-09 | 2016-12-09 | A kind of electrochemical method measuring methyl p-hydroxybenzoate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106680354B (en) |
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 |
-
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 |
|---|
| Cyclic Voltammetry and Computational Chemistry Studies on the Evaluation of the Redox Behavior of Parabens and other Analogues;Eric de S. Gil,et al.;《J. Braz. Chem. Soc.》;20120131;第23卷(第3期);565-572 |
| Determination of Methylparaben by Differential Pulse Voltammetry Using a Glassy Carbon Electrode Modified with Polypyrrole;Seyfullah Madakbas, et al.;《Journal of Analytical Chemistry》;20150630;第70卷(第6期);725-730 |
| Electroanalytical method for the determination of methylparaben;Keerti M.Naik,et al.;《Sensors and Actuators A》;20140330;第212卷;127-132 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106680354A (en) | 2017-05-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xiao et al. | Sensitive voltammetric determination of chloramphenicol by using single-wall carbon nanotube–gold nanoparticle–ionic liquid composite film modified glassy carbon electrodes | |
| CN101458223B (en) | Preparation of quantitative rapid detecting sensor of microcapsule algae toxin and applications | |
| CN102288669B (en) | Electrochemical method based on graphene-modified electrode for simultaneous determination of rutin and quercetin | |
| Huang et al. | Electrochemical behavior and voltammetric determination of tryptophan based on 4-aminobenzoic acid polymer film modified glassy carbon electrode | |
| Zhan et al. | Application of ionic liquid modified carbon ceramic electrode for the sensitive voltammetric detection of rutin | |
| Du et al. | Stripping voltammetric analysis of organophosphate pesticides based on solid-phase extraction at zirconia nanoparticles modified electrode | |
| Wu et al. | Amperometric cholesterol biosensor based on zinc oxide films on a silver nanowire–graphene oxide modified electrode | |
| CN102507683A (en) | Modified electrode based on functionalized multi-walled carbon nanotube, electrochemical system and application thereof | |
| CN107064277A (en) | A kind of preparation method and application of electrochemical sensor | |
| Węgiel et al. | A graphene oxide modified carbon ceramic electrode for voltammetric determination of gallic acid | |
| WO2012134408A1 (en) | Electrochemical detection of capsaicinoid compounds in a sample | |
| Babaei et al. | A sensitive determination of acetaminophen in pharmaceutical preparations and biological samples using multi-walled carbon nanotube modified glassy carbon electrode | |
| Shangguan et al. | A pre-anodized inlaying ultrathin carbon paste electrode for simultaneous determination of uric acid and folic acid | |
| Liu et al. | Simultaneous and sensitive voltammetric determination of acetaminophen and its degradation product for pharmaceutical quality control and pharmacokinetic research by using ultrathin poly (calconcarboxylic acid) film modified glassy carbon electrode | |
| CN103645237A (en) | Electrochemical sensor for detecting content of carbendazim in fog drops as well as preparation and application methods | |
| Salimi et al. | Sol–gel derived carbon ceramic composite electrode containing a ruthenium complex for amperometric detection of insulin at physiological pH | |
| Hua et al. | Electrochemical behavior of 5-fluorouracil on a glassy carbon electrode modified with bromothymol blue and multi-walled carbon nanotubes | |
| Tian et al. | Electrodes with extremely high hydrogen overvoltages as substrate electrodes for stripping analysis based on bismuth-coated electrodes | |
| CN102680549A (en) | Method for measuring 9-hydroxy fluorine based on electrochemistry hairpin DNA biosensor | |
| Balasoiu et al. | Carbon and diamond paste microelectrodes based on Mn (III) porphyrins for the determination of dopamine | |
| Hou et al. | Multi-walled carbon nanotubes modified glass carbon electrode and its electrocatalytic activity towards oxidation of paracetamol | |
| CN106198497A (en) | A kind of electrochemiluminescence method for sensing for histamine detection | |
| CN105223260B (en) | Electrochemical sensor of trace quick detection butyl p-hydroxybenzoate and preparation method thereof | |
| CN106680354B (en) | A kind of electrochemical method measuring methyl p-hydroxybenzoate | |
| CN106610400B (en) | Utilize the method for amaranth in porous graphene detection food |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |