CN103926303A - Method for simultaneously determining aminophenol isomers - Google Patents
Method for simultaneously determining aminophenol isomers Download PDFInfo
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- CN103926303A CN103926303A CN201410184401.7A CN201410184401A CN103926303A CN 103926303 A CN103926303 A CN 103926303A CN 201410184401 A CN201410184401 A CN 201410184401A CN 103926303 A CN103926303 A CN 103926303A
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- amino phenol
- isomeride
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Abstract
The invention relates to the technical field of the analysis and determination of a geometric isomer, in particular to a method for preparing a hexadecyl functionalized mesoporous silicone modified glass carbon electrode by utilizing a constant-current deposition method and also for simultaneously determining three geometric isomers of aminophenol. The electrode is simple to produce, the price of raw materials is low, the stability is good, no toxicity exits, and the environment is not polluted; moreover, by adopting the determination method, the interference of coexisting substances can be effectively reduced, the selectivity is good, and the sensitivity is high.
Description
Technical field
The present invention relates to isomers analysis determining technology field, particularly relate to a kind of galvanostatic deposition legal system of utilizing for the functional mesoporous silicon modified glassy carbon electrode of cetyl and for measure the method for amino phenol isomeride simultaneously.
Background technology
Amino phenol (AP) is a kind of important chemical intermediate, is widely used in the aspects such as biology, medicine, printing, dyestuff.Due to its contaminated environment, and human body is had to certain toxic and side effect, therefore detect its content tool and be of great significance.Being emitted on of phenolic wastewater has strict standard both at home and abroad.Therefore to realize in environment trace phenols organic contaminant detection with separate higher necessity and practicality.More and more analytical work persons utilize chemically modified electrode p-aminophenol to measure in recent years, wherein utilize carbon nanotube polymer modified electrode p-aminophenol isomeride to carry out the more of Study of recognition, but the required electrode material of this method is synthetic complicated, carbon nano-tube is expensive, electrode be difficult for upgrade and reappearance poor, and detection selectivity and sensitivity not high.Galvanostatic deposition legal system involved in the present invention makes electrode production process easier for the functional mesoporous silicon modified glassy carbon electrode of cetyl, and modified electrode material price is cheap, good stability, and selectivity is good, highly sensitive.In addition, the present invention has advantages of better stability and can use for a long time compared with early stage introduced mesoporous material NH2-SBA15 modified electrode.
Cetyl trimethoxy silane belongs to the one of long-chain alkoxy base silane class, belong to the special silane coupling agent of a class, in its structure, contain silicon hydroxyl, can there is chemical reaction with many functional groups, be easy to functional modification, in addition, long chain silane can be given full play to the hydrophobic effect between adjacent R groups.In addition, mesoporous material has larger pore volume, specific surface area, even adjustable aperture within the scope of 2-50 nm, surface can functionalization, and the series of advantages such as the mesoscopic structure of high-sequential, the structure of electrochemical sensor uses mesoporous material, can give full play to it and represent excellent properties in the field such as adsorptive separation, catalysis.
Summary of the invention
Object of the present invention is exactly to provide for the shortcoming in above-mentioned amino phenol isomerism body measurement.A kind of galvanostatic deposition legal system of utilizing is for the functional mesoporous silicon modified glassy carbon electrode of cetyl and for measure the method for amino phenol isomeride simultaneously.Electrode fabrication is easier, and material price is cheap, and good stability is nontoxic, free from environmental pollution, and this assay method effectively lowered the interference of coexisting substances, and selectivity is good, highly sensitive.
Technical scheme of the present invention is: a kind of for measure the method for amino phenol isomeride simultaneously, and utilize galvanostatic deposition legal system for the functional mesoporous silicon modified glassy carbon electrode of cetyl and for measure the method for amino phenol isomeride simultaneously.
This galvanostatic deposition legal system is for the functional mesoporous silicon modified glassy carbon electrode of cetyl, its concrete making step is, get solution 20 mL that ethanol and intermediate water are made into, (0.11 g), (1.19 g), (1.89 g) and cetyl triethoxysilane, then uses 0.1 mol × L for TEOS for CTAB to add successively KCl
-1hCl regulate pH to n TEOS:n CTAB=1:0.36 in 3.0(solution) as deposit solution; In electrolytic cell, add 10.00 mL deposit solutions, taking glass-carbon electrode as working electrode, platinum electrode deposits 200 s as auxiliary electrode, Ag/AgCl electrode as contrast electrode at continuous current 26 mA; Take out after electrode intermediate water rinses and put into drying box, spend the night with 130 DEG C of oven dry, cooling, put into ethanol and within static ten minutes, slough template and obtain the functional mesoporous silicon modified glassy carbon electrode of cetyl.
Utilize the functional mesoporous silicon modified glassy carbon electrode of described cetyl to measure the method for three kinds of isomerss of amino phenol, concrete steps are:
1. with microsyringe respectively by a certain amount of
o-AP,
m-AP,
p-AP solution accurately moves in the electrolytic cell of the PBS buffer solution that contains 10 mL pH 8.0, and taking the functional mesoporous silicon modified glassy carbon electrode of described electrode cetyl as working electrode, Ag/AgCl electrode is contrast electrode, and platinum electrode is to electrode; Experiment is carried out on CHI625B Electrochemical Comprehensive Tester, and its attached computer software is made for the acquisition and processing of experimental data; In-0.2～0.8 V potential range, carry out differential pulse scanning, record stable differential pulse voltammetry voltammogram;
2. will
o-AP,
m-AP,
pthe concentration of-AP is separately fixed at 1.0 × 10
-5mol/L, and change one of them concentration, along with the increase of this concentration, oxidation peak current increases, and can obtain
o-AP,
m-AP,
p-AP linear relationship curve; According to the mensuration principle of associated sensitivity, measure its three's detection limit simultaneously;
The top condition of identification amino phenol isomeride is: supporting electrolyte is selected PBS damping fluid, and best pH is 8.0, and the concentration that records three kinds of isomerss by voltammetry is all good linear relationship with peak current within the specific limits;
othe range of linearity of-AP is 1.0 × 10
-6～8.0 × 10
-4mol/L, linear equation is I
p=0.00379+5.77 × 10
4c, c is concentration, unit is mol/L, peak current I
punit is mA, and linearly dependent coefficient r=0.9976, detects and be limited to 1.0 × 10
-7mol/L;
mthe range of linearity of-AP is 1.0 × 10
-6～1.0 × 10
-4mol/L, linear equation is I
p=0.09391+1.66 × 10
4c, c is concentration, unit is mol/L, peak current I
punit is mA, and linearly dependent coefficient r=0.9984, detects and be limited to 3.0 × 10
-7mol/L;
pthe range of linearity of-AP is 1.0 × 10
-6～4.0 × 10
-4mol/L, linear equation is I
p=0.0471-3.81 × 10
3c, c is concentration, unit is mol/L, peak current I
punit is mA, and property correlation coefficient r=0.9981, detects and be limited to 3.0 × 10
-7mol/L;
3. in conjunction with above-mentioned linear equation, the amino phenol isomers mixed solution sample of unknown concentration is measured, calculated the concentration of each isomeride; By unknown concentration
o-AP,
m-AP,
p-AP tri-component mixed solutions are placed in electrolytic cell, and taking the functional mesoporous silicon modified glassy carbon electrode of described electrode cetyl as working electrode, Ag/AgCl electrode is contrast electrode, and platinum electrode is to electrode; Experiment is carried out on CHI625B Electrochemical Comprehensive Tester, and its attached computer software is made for the acquisition and processing of experimental data; In-0.2～0.8 V potential range, carry out differential pulse scanning, record respectively the I of different isomerss at different spike potentials place
pvalue; By measured I
pin the linear equation of the above-mentioned gained of value difference substitution, calculate
o-AP,
m-AP,
p-AP concentration separately.
Beneficial effect of the present invention is: this galvanostatic deposition legal system of utilizing makes electrode fabrication process easier for the functional mesoporous silicon modified glassy carbon electrode of cetyl, and modified electrode material price is cheap, and good stability is nontoxic, free from environmental pollution; Wherein
p-AP,
othe difference of-AP oxidation peak current potential is 96 mV,
o-AP and
mthe difference of-AP oxidation peak current potential is 401 mV, can obviously distinguish three kinds of isomerss of amino phenol, and this assay method selectivity is good, highly sensitive.Can be used for measuring the sample containing three kinds of isomerss of amino phenol simultaneously.
brief description of the drawings:
Figure 1 shows that the cyclic voltammogram of amino phenol isomeride on Different electrodes;
Figure 2 shows that the differential pulse voltammetry voltammogram of amino phenol isomeride on Different electrodes;
Figure 3 shows that under variable concentrations
o-AP differential pulse voltammetry voltammogram;
Figure 4 shows that under variable concentrations
m-AP differential pulse voltammetry voltammogram;
Figure 5 shows that under variable concentrations
p-AP differential pulse voltammetry voltammogram.
Wherein, 1-
o-AP, 2-
m-AP, 3-
p-AP, the naked glass-carbon electrode of 4-, the functional mesoporous silicon modified glassy carbon electrode of 5-electrode cetyl of the present invention.
embodiment:
In order to understand better the present invention, describe technical scheme of the present invention in detail with instantiation below, but the present invention is not limited thereto.
Embodiment 1
1. galvanostatic deposition legal system is for the functional mesoporous silicon modified glassy carbon electrode of cetyl
Utilize the making step of galvanostatic deposition legal system for the functional mesoporous silicon modified electrode of cetyl: get solution 20 mL that ethanol and intermediate water are made into, (0.11 g), (1.19 g), (1.89 g) and cetyl triethoxysilane, then uses 0.1 mol × L for TEOS for CTAB to add successively KCl
-1hCl regulate pH to n TEOS:n CTAB=1:0.36 in 3.0(solution) as deposit solution; In electrolytic cell, add 10.00 mL deposit solutions, taking glass-carbon electrode as working electrode, platinum electrode deposits 200 s as auxiliary electrode, Ag/AgCl electrode as contrast electrode at continuous current 26 mA; Take out after electrode intermediate water rinses and put into drying box, spend the night with 130 DEG C of oven dry, cooling, put into ethanol and within static ten minutes, slough template and obtain the functional mesoporous silicon modified glassy carbon electrode of cetyl;
2. three kinds of isomers determination steps of amino phenol:
1. with microsyringe respectively by a certain amount of
o-AP,
m-AP,
p-AP solution accurately moves in the electrolytic cell of the PBS buffer solution that contains 10 mL pH 8.0, and taking the functional mesoporous silicon modified glassy carbon electrode of described electrode cetyl as working electrode, Ag/AgCl electrode is contrast electrode, and platinum electrode is to electrode; Experiment is carried out on CHI625B Electrochemical Comprehensive Tester, and its attached computer software is made for the acquisition and processing of experimental data; In-0.2～0.8 V potential range, carry out differential pulse scanning, record stable differential pulse voltammetry voltammogram;
2. will
o-AP,
m-AP,
pthe concentration of-AP is separately fixed at 1.0 × 10
-5mol/L, and change one of them concentration, along with the increase of this concentration, oxidation peak current increases, and can obtain
o-AP,
m-AP,
p-AP linear relationship curve; According to the mensuration principle of associated sensitivity, measure its three's detection limit simultaneously;
The top condition of identification amino phenol isomeride is: supporting electrolyte is selected PBS damping fluid, and best pH is 8.0, and the concentration that records three kinds of isomerss by voltammetry is all good linear relationship with peak current within the specific limits;
othe range of linearity of-AP is 1.0 × 10
-6～8.0 × 10
-4mol/L, linear equation is I
p=0.00379+5.77 × 10
4c, c is concentration, unit is mol/L, peak current I
punit is mA, and linearly dependent coefficient r=0.9976, detects and be limited to 1.0 × 10
-7mol/L;
mthe range of linearity of-AP is 1.0 × 10
-6～1.0 × 10
-4mol/L, linear equation is I
p=0.09391+1.66 × 10
4c, c is concentration, unit is mol/L, peak current I
punit is mA, and linearly dependent coefficient r=0.9984, detects and be limited to 3.0 × 10
-7mol/L;
pthe range of linearity of-AP is 1.0 × 10
-6～4.0 × 10
-4mol/L, linear equation is I
p=0.0471-3.81 × 10
3c, c is concentration, unit is mol/L, peak current I
punit is mA, and property correlation coefficient r=0.9981, detects and be limited to 3.0 × 10
-7mol/L;
3. in conjunction with above-mentioned linear equation, the amino phenol isomers mixed solution sample of unknown concentration is measured, calculated the concentration of each isomeride; By unknown concentration
o-AP,
m-AP,
p-AP tri-component mixed solutions are placed in electrolytic cell, and taking the functional mesoporous silicon modified glassy carbon electrode of described electrode cetyl as working electrode, Ag/AgCl electrode is contrast electrode, and platinum electrode is to electrode; Experiment is carried out on CHI625B Electrochemical Comprehensive Tester, and its attached computer software is made for the acquisition and processing of experimental data; In-0.2～0.8 V potential range, carry out differential pulse scanning, record respectively the I of different isomerss at different spike potentials place
pvalue; By measured I
pin the linear equation of the above-mentioned gained of value difference substitution, calculate
o-AP,
m-AP,
p-AP concentration separately.
The present invention utilizes hydrophobic effect and the absorption recognition reaction between adjacent hexadecyl group, has widened the spike potential difference of amino phenol isomeride on modified electrode.Differential pulse voltammetry voltammogram from amino phenol isomeride at the functional mesoporous silicon modified glassy carbon electrode of cetyl, the oxidation peak of p-AP comes across 1 mV, and the oxidation peak of o-AP appears at 97 mV, and the oxidation peak of m-AP appears at 498 mV.Wherein the difference of p-AP, o-AP oxidation peak current potential is 96 mV, and the difference of o-AP and m-AP oxidation peak current potential is 401 mV, when this modified electrode can be realized three kinds of amino phenol isomeride as seen.This modified electrode adopts the mode of galvanostatic deposition to prepare to make electrode production process easier, and the material price of modified electrode is cheap, and good stability is nontoxic, free from environmental pollution, can be directly applied to the sample of measuring containing amino phenol isomeride.
Claims (3)
1. for measure a method for amino phenol isomeride simultaneously, it is characterized in that utilizing galvanostatic deposition legal system for the functional mesoporous silicon modified glassy carbon electrode of cetyl and for measure amino phenol isomeride simultaneously.
2. according to claim 1 a kind of for measure the method for amino phenol isomeride simultaneously, it is characterized in that, its making step is: get solution 20 mL that ethanol and intermediate water are made into, (0.11 g), (1.19 g), (1.89 g) and cetyl triethoxysilane, then uses 0.1 mol × L for TEOS for CTAB to add successively KCl
-1hCl regulate pH to n TEOS:n CTAB=1:0.36 in 3.0(solution) as deposit solution; In electrolytic cell, add 10.00 mL deposit solutions, taking glass-carbon electrode as working electrode, platinum electrode deposits 200 s as auxiliary electrode, Ag/AgCl electrode as contrast electrode at continuous current 26 mA; Take out after electrode intermediate water rinses and put into drying box, spend the night with 130 DEG C of oven dry, cooling, put into ethanol and within static ten minutes, slough template and obtain the functional mesoporous silicon modified glassy carbon electrode of cetyl.
3. utilize a kind of described in claim 1 to it is characterized in that for measure the method for amino phenol isomeride simultaneously, concrete steps are:
1. with microsyringe respectively by a certain amount of o-amino phenol (
o-AP), m-amino phenol (
m-AP), p-Aminophenol (
p-AP) solution accurately moves in the electrolytic cell of the PBS buffer solution that contains 10 mL pH 8.0, and taking electrode described in claim 1 as working electrode, Ag/AgCl electrode is contrast electrode, and platinum electrode is to electrode; Experiment is carried out on CHI625B Electrochemical Comprehensive Tester, and its attached computer software is made for the acquisition and processing of experimental data; In-0.2～0.8 V potential range, carry out differential pulse scanning, record stable differential pulse voltammetry voltammogram;
2. will
o-AP,
m-AP,
pthe concentration of-AP is separately fixed at 1.0 × 10
-5mol × L
-1, and change one of them concentration, along with the increase of this concentration, oxidation peak current increases, and can obtain
o-AP,
m-AP,
p-AP linear relationship curve; According to the mensuration principle of associated sensitivity, measure its three's detection limit simultaneously;
The top condition of identification amino phenol isomeride is: supporting electrolyte is selected PBS damping fluid, and best pH is 8.0, and the concentration that records three kinds of isomerss by voltammetry is all good linear relationship with peak current within the specific limits;
othe range of linearity of-AP is 1.0 × 10
-6～8.0 × 10
-4m mol × L
-1, linear equation is I
p=0.00379+5.77 × 10
4c, c is concentration, unit is mol × L
-1, peak current I
punit is mA, and linearly dependent coefficient r=0.9976, detects and be limited to 1.0 × 10
-7mol × L
-1;
mthe range of linearity of-AP is 1.0 × 10
-6～1.0 × 10
-4mol × L
-1, linear equation is I
p=0.09391+1.66 × 10
4c, c is concentration, unit is mol × L
-1, peak current I
punit is mA, and linearly dependent coefficient r=0.9984, detects and be limited to 3.0 × 10
-7mol × L
-1;
pthe range of linearity of-AP is 1.0 × 10
-6～4.0 × 10
-4mol × L
-1, linear equation is I
p=0.0471-3.81 × 10
3c, c is concentration, unit is mol × L
-1, peak current I
punit is mA, and property correlation coefficient r=0.9981, detects and be limited to 3.0 × 10
-7mol × L
-1;
3. in conjunction with above-mentioned linear equation, the amino phenol isomers mixed solution sample of unknown concentration is measured, calculated the concentration of each isomeride; By unknown concentration
o-AP,
m-AP,
p-AP tri-component mixed solutions are placed in electrolytic cell, and taking electrode described in claim 1 as working electrode, Ag/AgCl electrode is contrast electrode, and platinum electrode is to electrode; Experiment is carried out on CHI625B Electrochemical Comprehensive Tester, and its attached computer software is made for the acquisition and processing of experimental data; In-0.2～0.8 V potential range, carry out differential pulse scanning, record respectively the I of different isomerss at different spike potentials place
pvalue; By measured I
pin the linear equation of the above-mentioned gained of value difference substitution, calculate
o-AP,
m-AP,
p-AP concentration separately.
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| CN201410184401.7A CN103926303B (en) | 2014-05-05 | 2014-05-05 | A kind of method for Simultaneously test amino phenol isomeride |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105004779A (en) * | 2015-07-13 | 2015-10-28 | 南京师范大学 | Stable porous silicon electrode-based BPA enrichment and detection method |
| CN106483183A (en) * | 2016-10-12 | 2017-03-08 | 广西民族师范学院 | A kind of detection method of metronidazole |
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| CN101949881A (en) * | 2010-09-14 | 2011-01-19 | 济南大学 | Functionalized mesoporous material modified electrode and method for measuring aminophenol isomer |
| CN102091605A (en) * | 2010-12-01 | 2011-06-15 | 中国科学院生态环境研究中心 | Preparation and application of high-capacity magnetic mesoporous silica gel solid phase extracting agent |
| CN102384933A (en) * | 2010-09-03 | 2012-03-21 | 中国科学院海洋研究所 | L-serine/chitosan modified acetaminophen electrochemical sensor and application thereof |
| CN103217462A (en) * | 2013-02-22 | 2013-07-24 | 上海大学 | Electrochemical drug sensor used for detecting acetaminophen, and preparation method thereof |
-
2014
- 2014-05-05 CN CN201410184401.7A patent/CN103926303B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102384933A (en) * | 2010-09-03 | 2012-03-21 | 中国科学院海洋研究所 | L-serine/chitosan modified acetaminophen electrochemical sensor and application thereof |
| CN101949881A (en) * | 2010-09-14 | 2011-01-19 | 济南大学 | Functionalized mesoporous material modified electrode and method for measuring aminophenol isomer |
| CN102091605A (en) * | 2010-12-01 | 2011-06-15 | 中国科学院生态环境研究中心 | Preparation and application of high-capacity magnetic mesoporous silica gel solid phase extracting agent |
| CN103217462A (en) * | 2013-02-22 | 2013-07-24 | 上海大学 | Electrochemical drug sensor used for detecting acetaminophen, and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 王宗花等: ""碳纳米管修饰电极对对氨基苯酚异构体的识别及选择性测定"", 《分析测试学报》, vol. 27, no. 5, 31 May 2008 (2008-05-31), pages 531 - 533 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105004779A (en) * | 2015-07-13 | 2015-10-28 | 南京师范大学 | Stable porous silicon electrode-based BPA enrichment and detection method |
| CN105004779B (en) * | 2015-07-13 | 2017-10-10 | 南京师范大学 | A kind of method based on stable Porous Silicon Electrode enrichment and detection BPA |
| CN106483183A (en) * | 2016-10-12 | 2017-03-08 | 广西民族师范学院 | A kind of detection method of metronidazole |
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| CN103926303B (en) | 2016-04-20 |
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