CN103217468B - Preparation method and application of current type electrochemical sensor for detecting bisphenol A - Google Patents
Preparation method and application of current type electrochemical sensor for detecting bisphenol A Download PDFInfo
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Abstract
The invention provides a preparation method and an application of a current type electrochemical sensor for detecting bisphenol A, belonging to the field of a nano functional material and environmental detection. The preparation method of the bisphenol A electrochemical sensor utilizes an electrode surface modification technology to modify a prepared PtRu nano porous alloy material and a chitosan solution on the surface of an electrode, and takes the electrode which is successfully modified as a working electrode to be connected to an electrochemical work station, so as to detect the bisphenol A. The electrochemical sensor disclosed by the invention has the advantages of strong selectivity, high sensitivity, and simplicity and rapidness in operation, and is suitable for detecting the bisphenol A in a water sample.
Description
Technical field
The invention belongs to nano-functional material and environment measuring field, provide a kind of preparation method and the application that detect the amperometric electrochemical sensor of bisphenol-A, for the quick detection of bisphenol-A in water sample.
Background technology
Bisphenol-A, formal name used at school 2,2-bis-(4-hydroxy phenyl) propane, is a kind of very important industrial chemicals, belongs to environmental hormone, is the primary raw material producing epoxy resin, polycarbonate and polyoxy phenol etc.Animal experiment finds that bisphenol-A has the estrogenic effect of simulation, even if very low dosage also can make animal produce the effects such as female sex premature, sperm count decline, prostate growth.In addition, there is data to show bisphenol-A and there is certain embryotoxicity and teratogenesis, obviously can increase the generation of the cancers such as animal ovary cancer, prostate cancer, leukaemia.American National Environmental Protection Agency lists it in the blacklist of priority pollutants already as emphasis, therefore, need to set up a kind of quick, sensitive, easy, method of detecting bisphenol-A in water exactly.
The method of the detection bisphenol-A of current report mainly contains high performance liquid chromatography, gas chromatography mass spectrometry method, LC/MS method, oscilloscopic polarography, single sweep polarography, thin layer quantitative test, euzymelinked immunosorbent assay (ELISA) and electrochemical sensor etc.Wherein, electrochemical sensor has characteristic highly sensitive, that analysis speed is fast, easy and simple to handle and with low cost, has become a kind of important analysis means at present.Containing phenolic hydroxyl group in bisphenol-A molecule, can be electrochemically oxidized under certain condition, but its electrochemical response on naked glass-carbon electrode is poor, mensuration sensitivity is low, the present invention is by the nanoporous alloy modified electrode of three-dimensional co-continuous, improve the oxidation current of bisphenol-A significantly, provide a kind of sensitive height, measure the method for bisphenol-A exactly.
Summary of the invention
An object of the present invention is to provide a kind of preparation method of amperometric electrochemical sensor of testing environment endocrine disruptors bisphenol-A.
Two of object of the present invention is by prepared electrochemical sensor, for testing environment endocrine disruptors bisphenol-A.
Technical scheme of the present invention, comprises the following steps.
1. detect a preparation method for the amperometric electrochemical sensor of bisphenol-A, it is characterized in that, comprise the following steps:
(1) PtRu nanoporous alloy suspension preparation
PtRuAl ternary alloy three-partalloy is placed in the sodium hydroxide solution of 1.5 ~ 1.8 mol/L, corrosion 2 ~ 4 h, are washed till neutrality with ultrapure water, dry, obtained PtRu nanoporous alloy; Take 2.5 ~ 15 mg PtRu nanoporous alloys, add 5mL ultrapure water, ultrasonic 3min, obtained PtRu nanoporous alloy suspension; Described PtRu nanoporous alloy, Pt and Ru mass ratio is 1: (0.5 ~ 2), and in described ternary alloy three-partalloy, Al massfraction is 81 ~ 85%.
(2) chitosan solution preparation
(2) chitosan solution preparation
Shitosan and NaCl being joined volume fraction is dissolve in the glacial acetic acid aqueous solution of 0.3%, makes chitosan solution, and the massfraction of described solution chitosan-containing is 0.5%, is 0.3 ~ 0.5mol/L containing NaCl concentration;
(3) detect the preparation method of the amperometric electrochemical sensor of bisphenol-A, step is as follows:
1) the PtRu nanoporous alloy suspension dripping painting 4 ~ 8 μ L, in glass carbon working electrode surface, dries;
2) drip painting 4 ~ 8 μ L, massfraction be that the chitosan solution of 0.5% is in 1) in working electrode surface on, dry, obtained a kind of amperometric electrochemical sensor detecting bisphenol-A, for subsequent use.
2. a kind of amperometric electrochemical sensor detecting bisphenol-A of preparation as above, for the detection of bisphenol-A, step is as follows:
(1) take saturated calomel electrode as contrast electrode, platinum filament is to electrode, amperometric electrochemical sensor is as working electrode, be connected to electrochemical workstation, in the PBS solution of pH 5.5 ~ 9.5, scanning current potential is 0.55 ~ 0.65V, detects the chrono-amperometric of variable concentrations bisphenol-A standard solution, the relation of foundation current differential and bisphenol A concentration, draws the working curve of bisphenol-A;
(2) testing sample solution is replaced bisphenol-A standard solution, detect according to the method for drafting of the working curve of described bisphenol-A.
Described a kind of amperometric electrochemical sensor detecting bisphenol-A, raw materials all can be bought in chemical reagents corporation or biopharmaceutical company.
The advantage that the present invention embodies and feature are:
(1) the nanoporous alloy material electric conductivity of the present invention's employing is strong, becomes the excellent sensing material building electrochemical immunosensor;
(2) transducer sensitivity prepared of the present invention is high, detects fast, only needs 1 ~ 2 min can complete a basic Detection task;
(3) the present invention detects the method for bisphenol-A, easy and simple to handle, quick, sensitive, is convenient to Site Detection.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.Should be understood that those skilled in the art can make various change or amendment to the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction in addition.
embodiment 1
(1) PtRu nanoporous alloy suspension preparation
PtRuAl ternary alloy three-partalloy is placed in the sodium hydroxide solution of 1.5 mol/L, corrodes 4 h, be washed till neutrality with ultrapure water, dry, obtained PtRu nanoporous alloy; Take 2.5 mg PtRu nanoporous alloys, add 5mL ultrapure water, ultrasonic 3min, obtained PtRu nanoporous alloy suspension; Wherein, PtRu nanoporous alloy, Pt and Ru mass ratio is 1: 0.5, and in ternary alloy three-partalloy, Al massfraction is 81%.
(2) chitosan solution preparation
Shitosan and NaCl being joined volume fraction is dissolve in the glacial acetic acid aqueous solution of 0.3%, makes chitosan solution, and the massfraction of described solution chitosan-containing is 0.5%, is 0.3mol/L containing NaCl concentration.
embodiment 2
(1) PtRu nanoporous alloy suspension preparation
PtRuAl ternary alloy three-partalloy is placed in the sodium hydroxide solution of 1.6 mol/L, corrodes 3 h, be washed till neutrality with ultrapure water, dry, obtained PtRu nanoporous alloy; Take 7.5 mg PtRu nanoporous alloys, add 5mL ultrapure water, ultrasonic 3min, for subsequent use; Wherein, PtRu nanoporous alloy, Pt and Ru mass ratio is 1: 1; In ternary alloy three-partalloy, Al massfraction is 83%.
(2) chitosan solution preparation
Shitosan and NaCl being joined volume fraction is dissolve in the glacial acetic acid aqueous solution of 0.3%, makes chitosan solution, and the massfraction of described solution chitosan-containing is 0.5%, is 0.4mol/L containing NaCl concentration.
embodiment 3
(1) PtRu nanoporous alloy suspension preparation
PtRuAl ternary alloy three-partalloy is placed in the sodium hydroxide solution of 1.8 mol/L, corrodes 2 h, be washed till neutrality with ultrapure water, dry, obtained PtRu nanoporous alloy; Take 15 mg PtRu nanoporous alloys, add 5mL ultrapure water, ultrasonic 3min, for subsequent use; Wherein, PtRu nanoporous alloy, Pt and Ru mass ratio is 1: 2, and in ternary alloy three-partalloy, Al massfraction is 85%.
(2) chitosan solution preparation
Shitosan and NaCl being joined volume fraction is dissolve in the glacial acetic acid aqueous solution of 0.3%, makes chitosan solution, and the massfraction of described solution chitosan-containing is 0.5 %, is 0.5mol/L containing NaCl concentration.
embodiment 4
Detect a preparation method for the amperometric electrochemical sensor of bisphenol-A, step is as follows:
(1) the PtRu nanoporous alloy suspension dripping painting 4 μ L, in glass carbon working electrode surface, dries;
(2) drip painting 4 μ L, massfraction is on the working electrode surface of chitosan solution in (1) of 0.5%, dry, obtained a kind of amperometric electrochemical sensor detecting bisphenol-A, for subsequent use.
embodiment 5
Detect a preparation method for the amperometric electrochemical sensor of bisphenol-A, step is as follows:
(1) the PtRu nanoporous alloy suspension dripping painting 6 μ L, in glass carbon working electrode surface, dries;
(2) drip painting 6 μ L, massfraction is on the working electrode surface of chitosan solution in (1) of 0.5%, dry, obtained a kind of amperometric electrochemical sensor detecting bisphenol-A, for subsequent use.
embodiment 6
Detect a preparation method for the amperometric electrochemical sensor of bisphenol-A, step is as follows:
(1) the PtRu nanoporous alloy suspension dripping painting 8 μ L, in glass carbon working electrode surface, dries;
(2) drip painting 8 μ L, massfraction is on the working electrode surface of chitosan solution in (1) of 0.5%, dry, obtained a kind of amperometric electrochemical sensor detecting bisphenol-A, for subsequent use.
embodiment 7
By a kind of amperometric electrochemical sensor detecting bisphenol-A of preparation, for the detection of bisphenol-A, step is as follows:
(1) take saturated calomel electrode as contrast electrode, platinum filament is to electrode, amperometric electrochemical sensor is as working electrode, be connected to electrochemical workstation, in the PBS solution of pH 5.5, scanning current potential is 0.65V, detects the chrono-amperometric of variable concentrations bisphenol-A standard solution, the relation of foundation current differential and bisphenol A concentration, draws the working curve of bisphenol-A;
(2) testing sample solution is replaced bisphenol-A standard solution, detect according to the method for drafting of the working curve of described bisphenol-A.
embodiment 8
By a kind of amperometric electrochemical sensor detecting bisphenol-A of preparation, for the detection of bisphenol-A, step is as follows:
(1) take saturated calomel electrode as contrast electrode, platinum filament is to electrode, amperometric electrochemical sensor is as working electrode, be connected to electrochemical workstation, in the PBS solution of pH 8.5, scanning current potential is 0.60V, detects the chrono-amperometric of variable concentrations bisphenol-A standard solution, the relation of foundation current differential and bisphenol A concentration, draws the working curve of bisphenol-A;
(2) testing sample solution is replaced bisphenol-A standard solution, detect according to the method for drafting of the working curve of described bisphenol-A.
Bisphenol-A is linear at the logarithm of 0.114 ~ 19.4 ng/mL and 19.4 ~ 138 ng/mL scopes and its concentration, and lowest detection is limited to 0.027ng/mL.The recovery of recovery testu is between 93.0% ~ 95.9%.
(3) adopt a kind of amperometric electrochemical sensor detecting bisphenol-A of preparation to detect bottled mineral water sample 1, Parallel testing 7 times, does not detect bisphenol-A in water sample, belongs to qualified water sample; Recovery testu, its relative standard deviation is 3.8%.
embodiment 9
By a kind of amperometric electrochemical sensor detecting bisphenol-A of preparation, for the detection of bisphenol-A, step is as follows:
(1) take saturated calomel electrode as contrast electrode, platinum filament is to electrode, amperometric electrochemical sensor is as working electrode, be connected to electrochemical workstation, in the PBS solution of pH 9.5, scanning current potential is 0.55V, detects the chrono-amperometric of variable concentrations bisphenol-A standard solution, the relation of foundation current differential and bisphenol A concentration, draws the working curve of bisphenol-A;
(2) testing sample solution is replaced bisphenol-A standard solution, detect according to the method for drafting of the working curve of described bisphenol-A;
(3) adopt a kind of amperometric electrochemical sensor detecting bisphenol-A of preparation to detect bottled mineral water sample 2, Parallel testing 7 times, does not detect bisphenol-A in water sample, belongs to qualified water sample; Recovery testu, its relative standard deviation is 4.3 %, and the recovery of recovery testu is between 95.9% ~ 104 %.
embodiment 10
By a kind of amperometric electrochemical sensor detecting bisphenol-A of preparation, for the detection of bisphenol-A, step is as follows:
(1) take saturated calomel electrode as contrast electrode, platinum filament is to electrode, amperometric electrochemical sensor is as working electrode, be connected to electrochemical workstation, in the PBS solution of pH 7.4, scanning current potential is 0.61V, detects the chrono-amperometric of variable concentrations bisphenol-A standard solution, the relation of foundation current differential and bisphenol A concentration, draws the working curve of bisphenol-A;
(2) testing sample solution is replaced bisphenol-A standard solution, detect according to the method for drafting of the working curve of described bisphenol-A.
(3) adopt a kind of amperometric electrochemical sensor detecting bisphenol-A of preparation to detect the bottled mineral water sample 3 placing 12h under 60 DEG C of conditions, Parallel testing 7 times, detecting bisphenol-A in water sample is 12.5 ng/mL, belongs to qualified water sample; Recovery testu, its relative standard deviation is 3.7 %, and the recovery of recovery testu is between 93.1% ~ 102 %.
Claims (2)
1. detect a preparation method for the amperometric electrochemical sensor of bisphenol-A, it is characterized in that, comprise the following steps:
(1) PtRu nanoporous alloy suspension preparation
PtRuAl ternary alloy three-partalloy is placed in the sodium hydroxide solution of 1.5 ~ 1.8 mol/L, corrosion 2 ~ 4 h, are washed till neutrality with ultrapure water, dry, obtained PtRu nanoporous alloy; Take 2.5 ~ 15 mg PtRu nanoporous alloys, add 5mL ultrapure water, ultrasonic 3min, obtained PtRu nanoporous alloy suspension; Described PtRu nanoporous alloy, Pt and Ru mass ratio is 1: (0.5 ~ 2), and in described ternary alloy three-partalloy, Al massfraction is 81 ~ 85%;
(2) chitosan solution preparation
Shitosan and NaCl being joined volume fraction is dissolve in the glacial acetic acid aqueous solution of 0.3%, makes chitosan solution, and the massfraction of described solution chitosan-containing is 0.5%, and the concentration containing NaCl is 0.3 ~ 0.5mol/L;
(3) detect the preparation method of the amperometric electrochemical sensor of bisphenol-A, step is as follows:
1) the PtRu nanoporous alloy suspension dripping painting 4 ~ 8 μ L, in glass carbon working electrode surface, dries;
2) drip painting 4 ~ 8 μ L, massfraction be that the chitosan solution of 0.5% is in 1) in working electrode surface on, dry, obtained a kind of amperometric electrochemical sensor detecting bisphenol-A, for subsequent use.
2. the application of sensor in bisphenol-A detects prepared of preparation method as claimed in claim 1, step is as follows:
(1) preparation method according to claim 1 prepares a kind of amperometric electrochemical sensor detecting bisphenol-A;
(2) take saturated calomel electrode as contrast electrode, platinum filament is to electrode, amperometric electrochemical sensor is as working electrode, be connected to electrochemical workstation, in the PBS solution of pH 5.5 ~ 9.5, scanning current potential is 0.55 ~ 0.65V, detects the chrono-amperometric of variable concentrations bisphenol-A standard solution, the relation of foundation current differential and bisphenol A concentration, draws the working curve of bisphenol-A;
(3) testing sample solution is replaced bisphenol-A standard solution, detect according to the method for drafting of the working curve of described bisphenol-A.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105241869A (en) * | 2015-09-29 | 2016-01-13 | 江南大学 | Bisphenol A electrochemiluminescent aptamer sensor based on upper conversion nano material |
| CN107271518B (en) * | 2017-07-31 | 2019-05-07 | 首都师范大学 | A kind of amperometric electrochemical sensor and its preparation method and application |
| CN112485317A (en) * | 2020-11-11 | 2021-03-12 | 苏州健雄职业技术学院 | Electrochemical method and device for detecting bisphenol A |
| CN112485318A (en) * | 2020-11-11 | 2021-03-12 | 苏州健雄职业技术学院 | Electrochemical method and device for detecting bisphenol A by nano platinum modified electrode |
| CN112763560B (en) * | 2020-12-04 | 2023-10-03 | 陕西师范大学 | Preparation method of electrochemical biosensor based on Hemin@CNF composite material and method for detecting bisphenol A in wine |
| CN113480411B (en) * | 2021-06-18 | 2024-03-08 | 北京市农林科学院 | Depolymerization method and electrochemical detection method of polycarbonate microplastic |
| CN115165990B (en) * | 2022-06-27 | 2023-08-08 | 江南大学 | Electrochemical sensing analysis method for detecting bisphenol A |
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