CN103575778A - Method for preparing core-shell molecular imprinting electrochemical sensor for detecting tert-butyl hydroquinone and application of core-shell molecular imprinting electrochemical sensor - Google Patents

Method for preparing core-shell molecular imprinting electrochemical sensor for detecting tert-butyl hydroquinone and application of core-shell molecular imprinting electrochemical sensor Download PDF

Info

Publication number
CN103575778A
CN103575778A CN201310521322.6A CN201310521322A CN103575778A CN 103575778 A CN103575778 A CN 103575778A CN 201310521322 A CN201310521322 A CN 201310521322A CN 103575778 A CN103575778 A CN 103575778A
Authority
CN
China
Prior art keywords
solution
electrochemical sensor
core
tbhq
molecular imprinting
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.)
Pending
Application number
CN201310521322.6A
Other languages
Chinese (zh)
Inventor
崔敏
黄加栋
刘素
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Jinan
Original Assignee
University of Jinan
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by University of Jinan filed Critical University of Jinan
Priority to CN201310521322.6A priority Critical patent/CN103575778A/en
Publication of CN103575778A publication Critical patent/CN103575778A/en
Pending legal-status Critical Current

Links

Landscapes

  • Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)

Abstract

The invention provides a method for preparing a core-shell molecular imprinting electrochemical sensor for detecting tert-butyl hydroquinone and application of the core-shell molecular imprinting electrochemical sensor, which belong to the field of nano functional materials and food safety. The method for preparing the core-shell molecular imprinting electrochemical sensor comprises the following steps: modifying a prepared GO-MnO2 and IL-MWCNTs compound to the surface of an electrode through an electrode surface modification technology; combining the prepared GO-MnO2 and IL-MWCNTs compound with a prepared core-shell molecular imprinting compound (AuNPs@SiO2-MIP) to construct the electrochemical sensor; and connecting the prepared electrochemical sensor, which serves as a working electrode, to an electrochemical workstation, wherein the tert-butyl hydroquinone can be detected by the sensor. The core-shell molecular imprinting electrochemical sensor is high in selectivity, high in sensitivity, easy and quick to operate, and suitable for detection of the tert-butyl hydroquinone in food.

Description

A kind of preparation method and application thereof that detects core-shell molecular imprinting electrochemical sensor of tertiary butylated hydroquinone
Technical field
The invention belongs to nano material and food additives detection field, a kind of preparation method and application thereof that detects the molecular imprinting electrochemical sensor of tertiary butylated hydroquinone is provided, can be for the detection of tertiary butylated hydroquinone in food (TBHQ).
Background technology
Tertiary butylated hydroquinone (TBHQ), formal name used at school TBHQ, is a kind of very important antioxidant, belongs to a kind of of food additives.Because it can effectively extend food, occur corrupt period, and have that stability is high, low cost and other advantages, in the production run of the food such as various plant oils, animal oils, meat, tertiary butylated hydroquinone is widely used.Recent studies have found that, the long-term food that contains tertiary butylated hydroquinone that uses can bring potential harm to the mankind, such as, can cause the disappearance of nutrient in human body etc.A lot of countries all to tertiary butylated hydroquinone make to be used as restriction regulation, such as, in China, the U.S., Australia and New Zealand, the highest the limiting the quantity of that is allowed to add to the tertiary butylated hydroquinone in food is 200 mg/Kg; In European Union and Japan, in food, forbid adding tertiary butylated hydroquinone.Therefore, need to set up a kind of quick, sensitive, easy, method of detecting exactly tertiary butylated hydroquinone in food.
The method of the detection tertiary butylated hydroquinone of report mainly comprises high performance liquid chromatography, gas chromatography etc. at present.This research has realized a kind of method of utilizing core-shell molecular imprinting electrochemical sensor to detect the tertiary butylated hydroquinone in food, has the characteristic highly sensitive, analysis speed is fast, simple to operate and with low cost.By strengthening a series of compounds of electrochemical signals in glass-carbon electrode finishing, connect core-shell molecularly imprinted polymer, wash away template molecule (TBHQ) and build electrochemical sensor, for detection of the sample solution that contains tertiary butylated hydroquinone, utilize the combination of tertiary butylated hydroquinone and electrochemical sensor to cause the variation of current signal to analyze the content of measuring tertiary butylated hydroquinone in liquid to be measured.
Summary of the invention
One of content of the present invention has been to provide the preparation method of core-shell molecular imprinting electrochemical sensor of tertiary butylated hydroquinone (TBHQ) in a kind of detection food.
Two of content of the present invention is by prepared molecular imprinting electrochemical sensor, for detection of the tertiary butylated hydroquinone in food.
Technical scheme of the present invention, comprises the following steps:
1, a preparation method for core-shell molecular imprinting electrochemical sensor of tertiary butylated hydroquinone (TBHQ) in food, is characterized in that, comprises the following steps:
(1) GO-MnO 2the preparation of compound:
Preparation GO; 50 mgGO and 50 ml KMnO 4(0.05 M) solution mixes, ultrasonic 1 h, and under stirring condition, heated solution to 160 ℃; Add the citric acid of 3 ml (0.1 M) to above-mentioned solution; By gained solution 12 h that reflux, be cooled to room temperature, filter, washing, dry, obtain GO-MnO 2nano-complex;
(2) preparation of IL-MWCNTs compound:
50 mg MWCNTs are scattered in 40 ml H 2sO 4/ HNO 3in (V/V, 3:1) mixed liquor, ultrasonic 4 h; Gained homogeneous solution is filtered, washed, until pH value is neutral, the dry MWCNTs-COOH that obtains; Get 20 mg MWCNTs-COOH and be immersed in respectively 1 h in 0.5 ml EDC/NHS (V/V, 1:1) and ethylenediamine solution, gained solution is carried out centrifugal, dry; 1 mg MWCNTs-NH 2be dissolved in 1 ml dimethyl formamide with 1 ml IL, ultrasonic 1 h, obtains IL-MWCNTs uniform solution;
(3) AuNPsSiO of tertiary butylated hydroquinone trace (TBHQ) 2core-shell nano-complex (AuNPsSiO 2-MIP) preparation:
The uniform HAuCl of 174 mL 4(0.2 g/mL) solution joins in 287 mL distilled water, is heated to boiling under stirring condition; Add fast appropriate citric acid, keep heating until solution colour changes claret into; The colloidal nano gold of gained is cooled to room temperature, 4 ℃ of preservations; 16 mg polyvinylpyrrolidones (PVP) are scattered in 65 ml distilled water, ultrasonic 15 min; The PVP homogeneous solution obtaining is joined in above-mentioned colloidal nano gold solution to stirring at room 24 h; The centrifugal AuNPs-PVP that obtains, before carrying out next step, AuNPs-PVP should preserve at least 2 days in water; 1 ml AuNPs-PVP is scattered in (containing 4.2% ammoniacal liquor) in 2 mL ethanolic solutions, adds the tertiary butylated hydroquinone solution of 300 μ l 0.1 M, stirring at room 2 h; Add 30 μ l solution 1 (800 μ l TMOS+21, μ l ethanol+80 μ l PTMOS+100 μ l TBHQ (0.1 M)), stir 2 h; Add 30 μ l solution 2 (840 μ l PTMOS+28, TMOS+21, μ l ethoxyethanol+84 ultrapure water+28 HCl (0.1 M)+100 μ l TBHQ (0.1 M)), stir 12 h (solution 1 and solution 2 should stir respectively 2 h before using); Gained solution is carried out centrifugal, ethanol washing, obtains the AuNPsSiO of tertiary butylated hydroquinone trace 2core-shell nano-complex (AuNPsSiO 2-MIP);
(4) detect the preparation method of the molecular imprinting electrochemical sensor of tertiary butylated hydroquinone (TBHQ), step is as follows:
1) drip the GO-MnO of 6 μ l 2nano-complex uniform solution, in glass carbon working electrode surface, is spent the night and is dried;
2) the IL-MWCNTs uniform solution that drips 6 μ l is in 1) working electrode surface, spends the night and dries;
3) drip the AuNPsSiO of 6 μ l 2-MIP uniform solution is in 2) working electrode surface, spends the night and dries;
4) adopt the hydrochloric acid solution of 0.1 mol/L to wash away the template molecule (TBHQ) on sensor surface, spend the night and dry, standby.
2, preparation as above a kind of detects the molecular imprinting electrochemical sensor of tertiary butylated hydroquinone, as follows for the detecting step of tertiary butylated hydroquinone:
1) take Ag/AgCL as contrast electrode, take Pt electrode as to electrode, core-shell molecular imprinting electrochemical sensor is working electrode, be connected to electrochemical workstation, in potassium ferricyanide solution, scanning current potential is 0.3-0.5 V, detects the timing electric current of the TBHQ standard solution of variable concentrations, with the difference between current before and after electrochemical sensor wash-out and absorption template molecule and the relation of TBHQ concentration, drawing curve;
2) testing sample solution is replaced to TBHQ standard solution, according to the method for drafting of working curve, detect.
Described a kind of molecular imprinting electrochemical sensor that detects tertiary butylated hydroquinone, raw materials Jun chemical reagents corporation or biopharmaceutical company buy.
Advantage and feature that the present invention embodies are:
(1) GO-MnO that the present invention adopts 2nano-complex and IL-MWCNTs compound electric conductivity are strong, become the excellent material that builds electrochemical sensor;
(2) the core-shell molecularly imprinted polymer surface area that prepared by the present invention is large, high adsorption capacity, adsorption site are many, becomes the excellent material that builds molecularly imprinted polymer;
(3) transducer sensitivity that prepared by the present invention is high, and detection speed is fast, only needs a few minutes just can complete a basic testing process;
(4) the present invention detects the method for tertiary butylated hydroquinone, simple to operate, quick, sensitive, is convenient to Site Detection.
Embodiment
Below in conjunction with specific embodiment, further illustrate the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition, should also be understood that those skilled in the art can make various changes or modification to the present invention after having read the content that the present invention lectures, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
A preparation method for core-shell molecular imprinting electrochemical sensor of tertiary butylated hydroquinone, step is as follows:
(1) drip the GO-MnO of 6 μ l 2nano-complex uniform solution, in glass carbon working electrode surface, is spent the night and is dried;
(2) the IL-MWCNTs uniform solution that drips 6 μ l is in 1) working electrode surface, spends the night and dries;
(3) drip the AuNPsSiO of 6 μ l 2-MIP uniform solution is in 2) working electrode surface, spends the night and dries;
(4) adopt the template molecule (TBHQ) on the hydrochloric acid solution wash-out sensor surface of 0.1 mol/L, elution time is 10 min, spends the night and dries;
(5) take Ag/AgCL as contrast electrode, take Pt electrode as to electrode, (4) the gained sensor of take is working electrode, connects electrochemical workstation, and scanning current potential is 0.5 V, the electric current while adopting instant current method to detect equilibration time.
Embodiment 2
A preparation method for core-shell molecular imprinting electrochemical sensor of tertiary butylated hydroquinone, step is as follows:
(1) drip the GO-MnO of 6 μ l 2nano-complex uniform solution, in glass carbon working electrode surface, is spent the night and is dried;
(2) the IL-MWCNTs uniform solution that drips 6 μ l is in 1) working electrode surface, spends the night and dries;
(3) drip the AuNPsSiO of 6 μ l 2-MIP uniform solution is in 2) working electrode surface, spends the night and dries;
(4) adopt the template molecule (TBHQ) on the hydrochloric acid solution wash-out sensor surface of 0.1 mol/L, elution time is 20 min, spends the night and dries.
(5) take Ag/AgCL as contrast electrode, take Pt electrode as to electrode, (4) the gained sensor of take is working electrode, connects electrochemical workstation, and scanning current potential is 0.5 V, the electric current while adopting chronoamperometry to detect equilibration time.
Embodiment 3
By a kind of core-shell molecular imprinting electrochemical sensor of tertiary butylated hydroquinone that detects of preparation, for the detection of tertiary butylated hydroquinone, step is as follows:
(1) drip the GO-MnO of 6 μ l 2nano-complex uniform solution, in glass carbon working electrode surface, is spent the night and is dried;
(2) the IL-MWCNTs uniform solution that drips 6 μ l is in 1) working electrode surface, spends the night and dries;
(3) drip the AuNPsSiO of 6 μ l 2-MIP uniform solution is in 2) working electrode surface, spends the night and dries;
(4) adopt the template molecule (TBHQ) on the hydrochloric acid solution wash-out sensor surface of 0.1 mol/L, spend the night and dry;
(5) core-shell molecular imprinting electrochemical sensor (4) being obtained is soaked in the PBS damping fluid of the PH 5 that contains variable concentrations template molecule (TBHQ);
(6) take Ag/AgCL as contrast electrode, take Pt electrode as to electrode, (5) the gained electrochemical sensor of take is working electrode, be connected to electrochemical workstation, in potassium ferricyanide solution, scanning current potential is 0.5 V, detects the timing electric current of the tertiary butylated hydroquinone standard solution of variable concentrations, according to working electrode after wash-out with electric current difference and the relation of tertiary butylated hydroquinone concentration in conjunction with after template molecule, the working curve of drafting tertiary butylated hydroquinone.
Embodiment 4
By a kind of core-shell molecular imprinting electrochemical sensor of tertiary butylated hydroquinone that detects of preparation, for the detection of tertiary butylated hydroquinone, step is as follows:
(1) drip the GO-MnO of 6 μ l 2nano-complex uniform solution, in glass carbon working electrode surface, is spent the night and is dried;
(2) the IL-MWCNTs uniform solution that drips 6 μ l is in 1) working electrode surface, spends the night and dries;
(3) drip the AuNPsSiO of 6 μ l 2-MIP uniform solution is in 2) working electrode surface, spends the night and dries;
(4) adopt the template molecule (TBHQ) on the hydrochloric acid solution wash-out sensor surface of 0.1 mol/L, spend the night and dry;
(5) core-shell molecular imprinting electrochemical sensor (4) being obtained is soaked in the PBS damping fluid of the PH 6 that contains variable concentrations template molecule (TBHQ);
(6) take Ag/AgCL as contrast electrode, take Pt electrode as to electrode, (5) the gained electrochemical sensor of take is working electrode, be connected to electrochemical workstation, in potassium ferricyanide solution, scanning current potential is 0.5 V, detects the timing electric current of the tertiary butylated hydroquinone standard solution of variable concentrations, according to working electrode after wash-out with electric current difference and the relation of tertiary butylated hydroquinone concentration in conjunction with after template molecule, the working curve of drafting tertiary butylated hydroquinone.
Embodiment 5
By a kind of core-shell molecular imprinting electrochemical sensor of tertiary butylated hydroquinone that detects of preparation, for the detection of tertiary butylated hydroquinone, step is as follows:
(1) drip the GO-MnO of 6 μ l 2nano-complex uniform solution, in glass carbon working electrode surface, is spent the night and is dried;
(2) the IL-MWCNTs uniform solution that drips 6 μ l is in 1) working electrode surface, spends the night and dries;
(3) drip the AuNPsSiO of 6 μ l 2-MIP uniform solution is in 2) working electrode surface, spends the night and dries;
(4) adopt the template molecule (TBHQ) on the hydrochloric acid solution wash-out sensor surface of 0.1 mol/L, spend the night and dry;
(5) core-shell molecular imprinting electrochemical sensor (4) being obtained is soaked in the PBS damping fluid of the PH 6 that contains variable concentrations template molecule (TBHQ), hatches 25 min;
(6) take Ag/AgCL as contrast electrode, take Pt electrode as to electrode, (5) the gained electrochemical sensor of take is working electrode, be connected to electrochemical workstation, in potassium ferricyanide solution, scanning current potential is 0.4 V, detects the timing electric current of the tertiary butylated hydroquinone standard solution of variable concentrations, according to working electrode after wash-out with electric current difference and the relation of tertiary butylated hydroquinone concentration in conjunction with after template molecule, the working curve of drafting tertiary butylated hydroquinone.
Embodiment 6
By a kind of core-shell molecular imprinting electrochemical sensor of tertiary butylated hydroquinone that detects of preparation, for the detection of tertiary butylated hydroquinone, step is as follows:
(1) drip the GO-MnO of 6 μ l 2nano-complex uniform solution, in glass carbon working electrode surface, is spent the night and is dried;
(2) the IL-MWCNTs uniform solution that drips 6 μ l is in 1) working electrode surface, spends the night and dries;
(3) drip the AuNPsSiO of 6 μ l 2-MIP uniform solution is in 2) working electrode surface, spends the night and dries;
(4) adopt the template molecule (TBHQ) on the hydrochloric acid solution wash-out sensor surface of 0.1 mol/L, spend the night and dry;
(5) core-shell molecular imprinting electrochemical sensor (4) being obtained is soaked in the PBS damping fluid of the PH 6 that contains variable concentrations template molecule (TBHQ), hatches 30 min;
(6) take Ag/AgCL as contrast electrode, take Pt electrode as to electrode, (5) the gained electrochemical sensor of take is working electrode, be connected to electrochemical workstation, in potassium ferricyanide solution, scanning current potential is 0.5 V, detects the timing electric current of the tertiary butylated hydroquinone standard solution of variable concentrations, according to working electrode after wash-out with electric current difference and the relation of tertiary butylated hydroquinone concentration in conjunction with after template molecule, the working curve of drafting tertiary butylated hydroquinone.
Embodiment 7
By a kind of core-shell molecular imprinting electrochemical sensor of tertiary butylated hydroquinone that detects of preparation, for the detection of actual sample tertiary butylated hydroquinone, step is as follows:
(1) drip the GO-MnO of 6 μ l 2nano-complex uniform solution, in glass carbon working electrode surface, is spent the night and is dried;
(2) the IL-MWCNTs uniform solution that drips 6 μ l is in 1) working electrode surface, spends the night and dries;
(3) drip the AuNPsSiO of 6 μ l 2-MIP uniform solution is in 2) working electrode surface, spends the night and dries;
(4) adopt the template molecule (TBHQ) on the hydrochloric acid solution wash-out sensor surface of 0.1 mol/L, spend the night and dry;
(5) core-shell molecular imprinting electrochemical sensor (4) being obtained is soaked in the PBS damping fluid of the PH 6 that contains variable concentrations template molecule (TBHQ), hatches 30 min;
(6) take Ag/AgCL as contrast electrode, take Pt electrode as to electrode, (5) the gained electrochemical sensor of take is working electrode, be connected to electrochemical workstation, in potassium ferricyanide solution, scanning current potential is the timing electric current that 0.5 V detects the tertiary butylated hydroquinone standard solution of variable concentrations, according to working electrode wash-out after with electric current difference in conjunction with after template molecule and the relation of tertiary butylated hydroquinone concentration, the working curve of drafting tertiary butylated hydroquinone.
(7) testing sample solution is replaced to tertiary butylated hydroquinone standard solution, according to the method for drafting of above-mentioned working curve, detect; Tertiary butylated hydroquinone is 2 * 10 -8mol/L to 1 * 10 -5within the scope of mol/L, become new relationship with its concentration, lowest detection is limited to 1.8 * 10 -8mol/L.The recovery of recovery testu is between 97.6%-103.0%.
(8) adopt core-shell molecular imprinting electrochemical sensor of preparation to detect bottled vegetable oil sample 1, Parallel testing 5 times, had not detected tertiary butylated hydroquinone in vegetable oil sample, belong to qualified samples; Recovery testu, its relative deviation is 3.8%.
Embodiment 8
By a kind of core-shell molecular imprinting electrochemical sensor of tertiary butylated hydroquinone that detects of preparation, for the detection of actual sample tertiary butylated hydroquinone, step is as follows:
(1) take Ag/AgCL as contrast electrode, take Pt electrode as to electrode, the prepared molecular imprinting electrochemical sensor of take is working electrode, be connected to electrochemical workstation, in potassium ferricyanide solution, scanning current potential is the timing electric current that 0.5 V detects the tertiary butylated hydroquinone standard solution of variable concentrations, according to working electrode wash-out after with electric current difference in conjunction with after template molecule and the relation of tertiary butylated hydroquinone concentration, the working curve of drafting tertiary butylated hydroquinone.
(2) testing sample solution is replaced to tertiary butylated hydroquinone standard solution, according to the method for drafting according to above-mentioned working curve, detect;
(3) adopt core-shell molecular imprinting electrochemical sensor of preparation to detect bottled vegetable oil sample 2, Parallel testing 5 times, had not detected tertiary butylated hydroquinone in vegetable oil sample, belong to qualified samples; The recovery of recovery testu is between 95.9%-101.0%.
Embodiment 9
By a kind of core-shell molecular imprinting electrochemical sensor of tertiary butylated hydroquinone that detects of preparation, for the detection of actual sample tertiary butylated hydroquinone, step is as follows:
(1) take Ag/AgCL as contrast electrode, take Pt electrode as to electrode, the prepared molecular imprinting electrochemical sensor of take is working electrode, be connected to electrochemical workstation, in potassium ferricyanide solution, scanning current potential is the timing electric current that 0.5 V detects the tertiary butylated hydroquinone standard solution of variable concentrations, according to working electrode wash-out after with electric current difference in conjunction with after template molecule and the relation of tertiary butylated hydroquinone concentration, the working curve of drafting tertiary butylated hydroquinone.
(2) testing sample solution is replaced to tertiary butylated hydroquinone standard solution, according to the method for drafting according to above-mentioned working curve, detect;
(3) adopt core-shell molecular imprinting electrochemical sensor of preparation to detect bottled vegetable oil sample 3, Parallel testing 5 times, had not detected tertiary butylated hydroquinone in vegetable oil sample, belong to qualified samples; The recovery of recovery testu is between 96.1%-101.2%.

Claims (2)

1. core-shell molecular imprinting electrochemical sensor of novel detection tertiary butylated hydroquinone, is characterized in that, comprises the following steps:
(1) GO-MnO 2the preparation of nano-complex: the first, reference literature method is prepared GO; The second, 50 mg GO and 50 ml KMnO 4(0.05 M) solution mixes, ultrasonic 1 h, and under stirring condition, heated solution to 160 ℃; The 3rd, add the citric acid of 3 ml (0.1 M) to above-mentioned solution; Finally, by gained solution 12 h that reflux, be cooled to room temperature, filter, washing, dry, obtain GO-MnO 2nano-complex;
(2) preparation of IL-MWCNTs compound:
First, preparation MWCNTs-NH 2: 50 mg MWCNTs are scattered in 40 ml H 2sO 4/ HNO 3in (V/V, 3:1) mixed liquor, ultrasonic 4 h; Secondly, gained homogeneous solution is filtered, washed, until pH value is neutral, the dry MWCNTs-COOH that obtains; Finally, get 20 mg MWCNTs-COOH and be immersed in respectively 1 h in 0.5 ml EDC/NHS (V/V, 1:1) and ethylenediamine solution, gained solution is carried out centrifugal, dry, obtain MWCNTs-NH 2; The second, 1 mg MWCNTs-NH 2be dissolved in 1 ml dimethyl formamide with 1 ml IL, ultrasonic 1 h, obtains IL-MWCNTs uniform solution;
(3) AuNPsSiO of tertiary butylated hydroquinone trace (TBHQ) 2core-shell nano-complex (AuNPsSiO 2-MIP) preparation:
The first, the synthetic uniform HAuCl of AuNPs:174 mL 4(0.2 g/mL) solution joins in 287 mL distilled water, is heated to boiling under stirring condition; Add fast appropriate citric acid, keep heating until solution colour changes claret into; The colloidal nano gold of gained is cooled to room temperature, 4 ℃ of preservations; The second, preparation AuNPs-PVP:16 mg polyvinylpyrrolidone (PVP) is scattered in 65 ml distilled water, ultrasonic 15 min; The PVP homogeneous solution obtaining is joined in above-mentioned colloidal nano gold solution to stirring at room 24 h; The centrifugal AuNPs-PVP that obtains, before carrying out next step, AuNPs-PVP should preserve at least 2 days in water; Finally, core-shell nano-complex of synthesizing tertiary butyl quinhydrones (TBHQ) molecular engram: 1 ml AuNPs-PVP is scattered in (containing 4.2% ammoniacal liquor) in 2 mL ethanolic solutions, adds the tertiary butylated hydroquinone solution of 300 μ l 0.1 M, stirring at room 2 h; Add 30 μ l solution 1 (800 μ l TMOS+21, μ l ethanol+80 μ l PTMOS+100 μ l TBHQ (0.1 M)), stir 2 h; Add 30 μ l solution 2 (840 μ l TMOS+21, μ l ethoxyethanol+84 μ l ultrapure water+28, μ l PTMOS+28 μ l HCl (0.1 M)+100 μ l TBHQ (0.1 M)), stir 12 h (solution 1 and solution 2 should stir respectively 2 h before using); Gained solution is carried out centrifugal, ethanol washing, obtains the AuNPsSiO of tertiary butylated hydroquinone trace 2core-shell nano-complex (AuNPsSiO 2-MIP);
(4) preparation method of molecular imprinting electrochemical sensor, step is as follows:
1 mg GO-MnO 2nano-complex is dissolved in 1 ml ethanol, and ultrasonic 1 h obtains uniform solution, gets 6 μ l GO-MnO 2uniform solution modified glassy carbon electrode surface, ambient temperature overnight is dried; Getting 6 μ l IL-MWCNTs uniform solution drips in GO-MnO 2the electrode surface of modified, ambient temperature overnight is dried; 1 mg AuNPsSiO 2-MIP is dissolved in the chitosan solution of 1ml 0.1 wt%, and ultrasonic 1 h obtains uniform solution, gets 6 μ l AuNPsSiO 2-MIP uniform solution is modified electrode obtained above, and ambient temperature overnight is dried; Adopt the hydrochloric acid solution of 0.1 mol/L to wash away the template molecule (TBHQ) on sensor surface.
2. the novel electrochemical sensor of a kind of detection tertiary butylated hydroquinone of preparation as claimed in claim 1 (TBHQ), as follows for the detecting step of TBHQ:
(1) with Ag/AgCL contrast electrode, take Pt electrode as to electrode, molecular imprinting electrochemical sensor is working electrode, be connected to electrochemical workstation, in potassium ferricyanide solution, scanning current potential is 0.5 V, detects the timing electric current of the TBHQ standard solution of variable concentrations, with the difference between current before and after electrochemical sensor wash-out and absorption template molecule and the relation of TBHQ concentration, drawing curve;
(2) testing sample solution is replaced to TBHQ standard solution, according to the method for drafting of working curve, detect.
CN201310521322.6A 2013-10-30 2013-10-30 Method for preparing core-shell molecular imprinting electrochemical sensor for detecting tert-butyl hydroquinone and application of core-shell molecular imprinting electrochemical sensor Pending CN103575778A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310521322.6A CN103575778A (en) 2013-10-30 2013-10-30 Method for preparing core-shell molecular imprinting electrochemical sensor for detecting tert-butyl hydroquinone and application of core-shell molecular imprinting electrochemical sensor

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310521322.6A CN103575778A (en) 2013-10-30 2013-10-30 Method for preparing core-shell molecular imprinting electrochemical sensor for detecting tert-butyl hydroquinone and application of core-shell molecular imprinting electrochemical sensor

Publications (1)

Publication Number Publication Date
CN103575778A true CN103575778A (en) 2014-02-12

Family

ID=50048006

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310521322.6A Pending CN103575778A (en) 2013-10-30 2013-10-30 Method for preparing core-shell molecular imprinting electrochemical sensor for detecting tert-butyl hydroquinone and application of core-shell molecular imprinting electrochemical sensor

Country Status (1)

Country Link
CN (1) CN103575778A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107167504A (en) * 2017-06-15 2017-09-15 安徽师范大学 The detection method of trace electrochemical sensor and preparation method thereof and TBHQ
CN110559455A (en) * 2019-08-27 2019-12-13 深圳大学 Nano diagnosis and treatment agent based on gold nanorods, preparation method and application
CN114062337A (en) * 2021-11-23 2022-02-18 福州大学 Method for detecting tert-butyl hydroquinone based on up-conversion nanoparticles of core-shell structure

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107167504A (en) * 2017-06-15 2017-09-15 安徽师范大学 The detection method of trace electrochemical sensor and preparation method thereof and TBHQ
CN110559455A (en) * 2019-08-27 2019-12-13 深圳大学 Nano diagnosis and treatment agent based on gold nanorods, preparation method and application
CN110559455B (en) * 2019-08-27 2022-04-01 深圳大学 Nano diagnosis and treatment agent based on gold nanorods, preparation method and application
CN114062337A (en) * 2021-11-23 2022-02-18 福州大学 Method for detecting tert-butyl hydroquinone based on up-conversion nanoparticles of core-shell structure
CN114062337B (en) * 2021-11-23 2023-03-17 福州大学 Method for detecting tert-butyl hydroquinone based on up-conversion nanoparticles of core-shell structure

Similar Documents

Publication Publication Date Title
US10895552B1 (en) Method for preparing ratiometric electrochemical aptasensor for Vaniline based on nanocomposite modified electrode
CN101458223B (en) Preparation of quantitative rapid detecting sensor of microcapsule algae toxin and applications
CN105223243A (en) The preparations and applicatio of the trace electrochemical sensor that a kind of carbon point compound substance is modified
CN103575783A (en) Preparation method of molecularly-imprinted electrochemical transducer for detecting propylgallate as well as application thereof
CN112034026B (en) Electrochemical sensor for detecting nitrite, preparation method and application
CN103698373A (en) Preparation method of molecular-imprinting electrochemical sensor for detecting 2,6-butylated hydroxytoluene and application thereof
CN105738448B (en) It is a kind of for detecting the molecular imprinting electrochemical sensor of micro olaquindox
CN103343126B (en) Ractopamine hydrochloride aptamers and the aptamers electrochemica biological sensor detecting Ractopamine hydrochloride
CN108732218B (en) Electrochemical sensor for measuring 2,4, 6-trichlorophenol and preparation and application thereof
CN103822949A (en) Preparation method and application of electrochemical immunosensor for detecting escherichia coli
CN103713026A (en) Preparation method and applications of aptamer electrochemical sensor for detecting malachite green (MG)
CN103575778A (en) Method for preparing core-shell molecular imprinting electrochemical sensor for detecting tert-butyl hydroquinone and application of core-shell molecular imprinting electrochemical sensor
CN103837588A (en) Preparation method of aptamer sensor for detecting antibiotic residue
CN105223244A (en) A kind of preparation method and application detecting the trace electrochemical sensor of vanillic aldehyde
CN106198667A (en) A kind of molecular imprinting electrochemical sensor for detecting trace bisphenol-A
CN105403612A (en) Method for rapidly detecting pesticide residue based on plant esterase
CN101793862A (en) L-cysteine/chitosan-modified electrochemical sensor and use thereof
CN108776160A (en) Method that is a kind of while detecting bisphenol-A and bisphenol S
CN103543189A (en) Modified electrode for detecting hydroquinone and catechol
CN104165909A (en) Biological electrochemical detection method of fumaric acid
CN107102052B (en) Based on the uric acid electrochemical sensor containing active copper carbon dots and its application
CN103698383A (en) Preparation method and application of electrochemical immunosensor for detecting diethylstilbestrol
CN105866211B (en) A kind of preparation method and application of ampicillin molecular engram sensor
CN104020205B (en) The imprinted polymer membrane electrode of parachloroanilinum, its preparation method and application process
CN108107091B (en) A kind of preparation method and application of chirality MOF membrane material

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20140212