CN102507684A - Modified glassy carbon electrode, preparation method for same and application thereof in nitrite detection - Google Patents
Modified glassy carbon electrode, preparation method for same and application thereof in nitrite detection Download PDFInfo
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Abstract
The invention provides a modified glassy carbon electrode, which is an L-cysteine modified glassy carbon electrode or a platinum/L-cysteine modified glassy carbon electrode. The preparation method for the L-cysteine modified glassy carbon electrode includes the steps: firstly, treating a glassy carbon electrode into a bare glassy carbon electrode; secondly, drying the bare glassy carbon electrode and inserting the bare glassy carbon electrode into electrolyte solution for cyclic voltammetry scanning to obtain treated glassy carbon electrode; and thirdly, placing the treated glassy carbon electrode into buffer solution containing L-cysteine for electro-polymerization, and obtaining the L-cysteine modified glassy carbon electrode after cleaning and drying the treated glassy carbon electrode. Besides, the platinum/L-cysteine modified glassy carbon electrode is obtained by placing the L-cysteine modified glassy carbon electrode into sulfuric acid solution containing chloroplatinic acid for electro-deposition and after cleaning and drying the L-cysteine modified glassy carbon electrode. The invention further provides application of the modified glassy carbon electrode in the nitrite detection. The modified glassy carbon electrode is capable of promoting electron transfer, current response is enhanced, a modification method is simple and convenient, and the modified glassy carbon electrode is simple in operation, fine in responsiveness and applicable to nitrite detection.
Description
Technical field
The present invention relates to a kind of modified glassy carbon electrode, the invention still further relates to the preparation method and its application in detecting nitrite anions of this modified glassy carbon electrode.
Background technology
Nitrite anions is a kind of objectionable impurities that extensively is present in the environment, and in food industry, nitrite anions Chang Zuowei colour former has antibiotic antisepsis, but nitrite anions can generate strong carcinogenic nitrosamine after getting into human body.The reinforcement of Along with people's environmental consciousness and food security consciousness, nitrite anions have become the project that must detect in environment measuring and the food analysis.At present, nitrite anions Determination on content method mainly contains Continuous Flow Analysis method, AAS, fluorometric method, chromatography, electrochemical gaging etc., and Comparatively speaking, electrochemical gaging nitrite anions content has advantages such as highly sensitive, quick, that instrument and equipment is simple.
L-halfcystine (L-cys) is a kind of important amino acid, because this amino acid contains sulfydryl, self assembly forms the unimolecular layer with specific function on gold electrode easily, has been used to the mensuration of materials such as dopamine, ascorbic acid based on these characteristics.But because its reactive group concentration is low, usable range receives certain restriction.Still L-cys is not fixed to the report that glass-carbon electrode forms L-cys modified glassy carbon electrode and platinum/L-cysteine modified glass-carbon electrode at present.
Summary of the invention
The present invention provides a kind of modified glassy carbon electrode; This modified glassy carbon electrode can be fixed to the L-halfcystine and form L-cysteine modified glass-carbon electrode and platinum/L-cysteine modified glass-carbon electrode on the glass-carbon electrode, and the present invention also provides the preparation method and its application in detecting nitrite anions of this modified glassy carbon electrode.
The present invention provides a kind of modified glassy carbon electrode to achieve these goals, and said modified glassy carbon electrode is L-cysteine modified glass-carbon electrode or platinum/L-cysteine modified glass-carbon electrode.
Another object of the present invention provides a kind of preparation method of modified glassy carbon electrode, and the preparation method of said L-cysteine modified glass-carbon electrode is following:
1), glass-carbon electrode is processed into naked glass-carbon electrode;
2) the naked glass-carbon electrode that, step 1) is obtained dries up; Insertion fills in the electrolyte solution that contains the potassium ferricyanide; In the three-electrode system that with naked glass-carbon electrode is working electrode, carry out cyclic voltammetry scan; The spike potential difference is at 64mV-80 mV in the gained cyclic voltammogram, and as far as possible near 64 mV, the glass-carbon electrode after obtaining handling;
3), with step 2) glass-carbon electrode after the processing that obtains places the NaH that contains the L-halfcystine
2PO
4-Na
2HPO
4In the buffer solution, carry out electropolymerization with cyclic voltammetry, with polymerization the glass-carbon electrode after the processing of L-halfcystine clean and to obtain L-cysteine modified glass-carbon electrode after drying.
Further, the condition of electropolymerization described in the step 3) is: sweep velocity 100 mV/s, and current potential-0.6V-2.0V, the electropolymerization number of turns is the 10-20 circle; Said NaH
2PO
4-Na
2HPO
4The pH value of buffer solution is 6.0.
Because the isoelectric point of L-halfcystine is a pH value 6.0, so the pH value selection 6.0 of buffer solution during electropolymerization L-halfcystine.
Further, the number of turns of electropolymerization described in the step 3) is 10 circles.
The 3rd purpose of the present invention provides the preparation method of another kind of modified glassy carbon electrode, and the preparation method of said platinum/L-cysteine modified glass-carbon electrode is following:
A), glass-carbon electrode is processed into naked glass-carbon electrode;
B), the naked glass-carbon electrode that step a) is obtained dries up; Insertion fills in the electrolyte solution that contains the potassium ferricyanide; In the three-electrode system that with naked glass-carbon electrode is working electrode, carry out cyclic voltammetry scan; The spike potential difference is at 64mV-80 mV in the gained cyclic voltammogram, and as far as possible near 64 mV, the glass-carbon electrode after obtaining handling;
C), the glass-carbon electrode after the processing that step b) is obtained places the NaH that contains the L-halfcystine
2PO
4-Na
2HPO
4In the buffer solution, carry out electropolymerization with cyclic voltammetry, with polymerization the glass-carbon electrode after the processing of L-halfcystine clean and to obtain L-cysteine modified glass-carbon electrode after drying;
D), the L-cysteine modified glass-carbon electrode that step c) is obtained places the sulfuric acid solution that contains chloroplatinic acid; Carry out electro-deposition with cyclic voltammetry, the L-cysteine modified glass-carbon electrode that has deposited platinum is cleaned obtained platinum/L-cysteine modified glass-carbon electrode after drying.
Further, the condition of electro-deposition described in the step d) is: sweep velocity 50 mV/s, and current potential 0.4V--0.25V, the electro-deposition number of turns is the 10-15 circle.
Further, the number of turns of electro-deposition described in the step d) is 10 circles.
The 4th purpose of the present invention provides the application of this modified glassy carbon electrode in detecting nitrite anions.
Further, the method for said application is following: modified glassy carbon electrode is placed the NaH that contains nitrite anions
2PO
4-Na
2HPO
4In the buffer solution, in the three-electrode system that with the modified glassy carbon electrode is working electrode, carry out cyclic voltammetry scan, the pH value of wherein said buffer solution is 2.5-4.0.
Further, the pH value of said buffer solution is 3.0.
The beneficial effect that the technical scheme that the embodiment of the invention provides is brought is:
1, the present invention's electropolymerization L-halfcystine on glass-carbon electrode is compared with self-assembling method, has increased reactive group, makes it can promote electron transfer.
2, the present invention on the glass-carbon electrode of having modified the L-halfcystine further on the electropolymerization nano platinum particle, both have promoted the transfer of electronics jointly, have increased current-responsive.
3, the method for modifying of electrode of the present invention is easy, and is simple to operate and response good, is applicable to the detection of nitrite anions.
4, nitrite anions has higher oxidation overpotential on naked glass-carbon electrode; The oxidation overpotential obviously reduces on L-cysteine modified glass-carbon electrode of the present invention, and current potential is negative to have moved 80 mV, and current-responsive significantly increases, and explains that the L-halfcystine has good electrocatalysis to nitrite anions; Current potential is shuffled slightly on platinum of the present invention/L-cysteine modified glass-carbon electrode than on L-cysteine modified glass-carbon electrode of the present invention, and current-responsive further increases, and explains that platinum also plays a positive role to the catalysis of nitrite anions.Experimental result shows: compare the oxidation response of nitrite anions on modified glassy carbon electrode of the present invention with naked glass-carbon electrode and be greatly improved; Modified glassy carbon electrode of the present invention has good electrocatalysis to nitrite anions; Wherein, platinum of the present invention/L-cysteine modified glass-carbon electrode is better to the electrocatalysis of nitrite anions than L-cysteine modified glass-carbon electrode of the present invention.
Description of drawings
Fig. 1 uses three kinds of cyclic voltammograms that different operating electrode pair nitrite anions detects; Wherein: a is that naked glass-carbon electrode, b are L-cysteine modified glass-carbon electrode of the present invention, and c is platinum of the present invention/L-cysteine modified glass-carbon electrode.
Fig. 2 is when other conditions are identical, the current-responsive of Different L-halfcystine voltolisation resultant; Wherein horizontal ordinate is the L-halfcystine electropolymerization number of turns, and ordinate is electric current (μ A).
Fig. 3 is when other conditions are identical, the current-responsive of different nano platinum particle electrodeposition weights; Wherein horizontal ordinate is the nano platinum particle electro-deposition number of turns, and ordinate is electric current (μ A).
D is when other conditions are identical among Fig. 4, NaH
2PO
4-Na
2HPO
4The graph of a relation of different pH values and peak current in the buffer solution;
E is when other conditions are identical, NaH
2PO
4-Na
2HPO
4The graph of a relation of different pH values and spike potential in the buffer solution; Wherein horizontal ordinate is the pH value, and left coordinate is current potential (V), and right coordinate is electric current (μ A).
Embodiment
The water that uses in the experimentation of the present invention is redistilled water, test used reagent be analyze pure.Experiment is all at room temperature carried out.Cyclic voltammetry scan of the present invention and the scanning of differential pulse volt-ampere all are under logical 99.999% nitrogen, to carry out.
Instrument and reagent that the present invention uses:
Multi-channel electrochemical workstation (VMP2, U.S. Princeton instrument company) is used for cyclic voltammetry experiment;
The automatic dual pure water distiller of quartz ampoule heated type (1810B, Asian-Pacific Glass-Tech. Co., Shanghai City) is used to steam redistilled water; Electronic balance (Beijing Sai Duolisi Instr Ltd.) is used for the weighing medicine;
Ultrasonic cleaner (Kunshan Ultrasonic Instruments Co., Ltd.);
(purity is 99.999% (O to high pure nitrogen
2≤0.001%));
Alundum (Al polishing powder (0.30 μ m, 0.05 μ m, Shanghai occasion China instrument reagent company) is used to handle glass-carbon electrode; Ag/AgCl (CHI III, U.S. CH instrument company) is a contrast electrode;
Platinum is to electrode;
Sodium nitrite (Beijing chemical industry).
The preparation method of
, L-cysteine modified glass-carbon electrode is following.
(1) glass-carbon electrode being polished to minute surface with the alundum (Al suspension of 0.3 μ m, 0.05 μ m successively, is ethanol, the redistilled water ultrasonic cleaning of 95 % through volume fraction more successively, obtains naked glass-carbon electrode;
(2) be after 99.999% nitrogen dries up with naked glass-carbon electrode through purity; The volumetric molar concentration that insertion contains the potassium ferricyanide probe molecule of 5 mmol/L is in the 0.1 mol/L potassium chloride electrolyte solution; And adopt with naked glass-carbon electrode be working electrode, with platinum electrode for being that the three-electrode system of contrast electrode carries out cyclic voltammetry scan to electrode, with the Ag/AgCl electrode; Spike potential difference in the gained cyclic voltammogram is between 64 mV-80 mV; And as far as possible near 64 mV, electrode can use, the glass-carbon electrode after obtaining handling;
(3) L-cysteine modified glass-carbon electrode: the glass-carbon electrode after the said processing is inserted the NaH that contains the L-halfcystine
2PO
4-Na
2HPO
4In the buffer solution, wherein, the volumetric molar concentration of L-halfcystine is 5 mmol/L, and the volumetric molar concentration of buffer solution is 0.1 mol/L, and pH is 6.0.And adopt with the glass-carbon electrode after handling be working electrode, with platinum for being that the three-electrode system of contrast electrode is in-0.6～2.0V potential range to electrode, with Ag/AgCl; Carry out electropolymerization with cyclic voltammetry under sweep velocity 100 mV/s; The number of turns of electropolymerization is 10 circles; After accomplishing electropolymerization, clean, obtain L-cysteine modified glass-carbon electrode after drying with redistilled water.
The preparation method of
two, platinum/L-cysteine modified glass-carbon electrode is following.
The L-cysteine modified glass-carbon electrode of the present invention's preparation is placed the sulfuric acid solution that contains 2 mmol/L chloroplatinic acids; Wherein the concentration of sulfuric acid solution is 0.5 mol/L; And adopt with L-cysteine modified glass-carbon electrode be working electrode, with platinum for to electrode, with Ag/AgCl be the three-electrode system of contrast electrode 0.4～-the 0.25V potential range in; Carry out electro-deposition with cyclic voltammetry under sweep velocity 50 mV/s, the number of turns of electro-deposition is 10 circles, after the completion electro-deposition; Clean with redistilled water, obtain platinum/L-cysteine modified glass-carbon electrode after drying.
three, the experiment of using different working electrode detection solution Central Asia nitrate radical content.
Naked glass-carbon electrode, L-cysteine modified glass-carbon electrode and platinum/L-cysteine modified glass-carbon electrode respectively as working electrode, is placed working electrode and contains 1 * 10
-3The NaH of the sodium nitrite of mol/L
2PO
4-Na
2HPO
4In the buffer solution, and with platinum for to electrode, with Ag/AgCl be the three-electrode system of contrast electrode in 0.4～1.3V potential range, follow under sweep velocity 50 mV/s and carry out cyclic voltammetry scan, adopt the mapping of origin8.0 software, draw current fitting curve.The result sees Fig. 1.
Can be known by Fig. 1: nitrite anions has higher oxidation overpotential on naked glass-carbon electrode; The oxidation overpotential obviously reduces on L-cysteine modified glass-carbon electrode of the present invention, and current potential is negative to have moved 80 mV, and current-responsive significantly increases, and explains that the L-halfcystine has good electrocatalysis to nitrite anions; Current potential is shuffled slightly on platinum of the present invention/L-cysteine modified glass-carbon electrode than on L-cysteine modified glass-carbon electrode of the present invention, and current-responsive further increases, and explains that platinum also plays a positive role to the catalysis of nitrite anions.Experimental result shows: compare the oxidation response of nitrite anions on modified glassy carbon electrode of the present invention with naked glass-carbon electrode and be greatly improved; Modified glassy carbon electrode of the present invention has good electrocatalysis to nitrite anions; Wherein, platinum of the present invention/L-cysteine modified glass-carbon electrode is better to the electrocatalysis of nitrite anions than L-cysteine modified glass-carbon electrode of the present invention.
The optimization of the voltolisation resultant of L-halfcystine in
four, the platinum/L-cysteine modified glass-carbon electrode.
Prepare platinum/L-cysteine modified glass-carbon electrode by method of the present invention; Keep the amount of platinum electrodeposition nano particle constant; Be equal electro-deposition 10 circles; Only change the amount of the L-halfcystine of electropolymerization: be respectively electropolymerization 2 circle, 5 circles, 10 circles, 15 circles and 20 circles, platinum/L-cysteine modified glass-carbon electrode of preparation inserted contain 1 * 10
-4The NaH of the nitrite anions of mol/L
2PO
4-Na
2HPO
4In the buffer solution; The concentration of buffer solution is 0.1mol/L; The pH value is 3.0; And adopt with L-cysteine modified glass-carbon electrode be working electrode, with platinum for to electrode, with Ag/AgCl be the three-electrode system of contrast electrode in 0.45～1.1V potential range, carry out the scanning of differential pulse volt-ampere under sweep velocity 50 mV/s, the glass-carbon electrode of Pt/L-cysteine modified that obtains different L-halfcystine voltolisation resultants is 10
-4Differential pulse voltammogram in the nitrite anions solution of mol/L; Adopt the mapping of origin8.0 software, obtain the number of turns of different electric polymerization L-halfcystine and the graph of a relation of current-responsive, see Fig. 2.Can be known by Fig. 2: the response of electropolymerization 10 loop currents is best.
The optimization of the electrodeposition weight of nano platinum particle in
five, the platinum/L-cysteine modified glass-carbon electrode.
Prepare platinum/L-cysteine modified glass-carbon electrode by method of the present invention; Keep the amount of electropolymerization L-halfcystine constant; Be equal electropolymerization 10 circles; Only change the amount of the nano platinum particle of electro-deposition: be respectively electro-deposition 2 circle, 5 circles, 10 circles, 20 circles and 25 circles, platinum/L-cysteine modified glass-carbon electrode of preparation inserted contain 1 * 10
-4The NaH of the nitrite anions of mol/L
2PO
4-Na
2HPO
4In the buffer solution, the concentration of buffer solution is 0.1mol/L, and the pH value is 3.0.And adopt with L-cysteine modified glass-carbon electrode be working electrode, with platinum for being that the three-electrode system of contrast electrode is in 0.45～1.1V potential range to electrode, with Ag/AgCl; Carry out differential pulse volt-ampere scanning under sweep velocity 50 mV/s, the glass-carbon electrode of Pt/L-cysteine modified that obtains different nano platinum particle electrodeposition weights is 10
-4Differential pulse voltammogram in the nitrite anions solution of mol/L; Adopt the mapping of origin8.0 software, obtain the number of turns of different electric deposition nano platinum particle and the graph of a relation of current-responsive, see Fig. 3.Can be known by Fig. 3: the response of electro-deposition 10 loop currents is best.
Used NaH when six, detecting nitrite anions
2
PO
4
-Na
2
HPO
4
The optimization of the pH value of buffer solution.
Platinum/L-cysteine modified the glass-carbon electrode that will obtain with the amount (being electropolymerization L-halfcystine 10 circles, platinum electrodeposition nano particle 10 circles) of optimum inserts and contains 1 * 10
-3The NaH of the sodium nitrite of mol/L
2PO
4-Na
2HPO
4In the buffer solution, the concentration of buffer solution is 0.1mol/L, and the pH value is respectively 1.5,2.5,3.0,3.5,4.0,4.5,5.0,6.0.And adopt with Pt/L-cysteine modified glass-carbon electrode be working electrode, with platinum for being that the three-electrode system of contrast electrode is in 0.45～1.1V potential range to electrode, with Ag/AgCl; Carry out the scanning of differential pulse volt-ampere under sweep velocity 50 mV/s; Adopt the mapping of origin8.0 software, the graph of a relation that obtains peak current and different pH values (sees that Fig. 4 a) and the graph of a relation of spike potential and different pH values (seeing Fig. 4 b).
Can be known by Fig. 4: when the pH value was 1.5-3.0, with the rising of pH, current-responsive progressively improved, and potential value is less; Greater than 3.0 o'clock, current-responsive reduced in the pH value, and current potential is shuffled slightly, and hence one can see that, and optimum pH value is 3.0.
Seven, platinum/L-cysteine modified glass-carbon electrode is to the mechanism of nitrite anions detection
Because the isoelectric point of L-halfcystine is a pH value 6.0, at the optimum pH value that detects 3.0 times, the amino protonated positive charge of being with, can attract the material such as the nitrite anions of negative charge, thus the promotion electron transport, the raising current-responsive.And nano platinum particle has good catalytic action, and both actings in conjunction have further increased the current-responsive to nitrite anions.
The above is merely preferred embodiment of the present invention, and is in order to restriction the present invention, not all within spirit of the present invention and principle, any modification of being done, is equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. modified glassy carbon electrode, it is characterized in that: said modified glassy carbon electrode is L-cysteine modified glass-carbon electrode or platinum/L-cysteine modified glass-carbon electrode.
2. the preparation method of a modified glassy carbon electrode, it is characterized in that: the preparation method of said L-cysteine modified glass-carbon electrode is following:
1), glass-carbon electrode is processed into naked glass-carbon electrode;
2) the naked glass-carbon electrode that, step 1) is obtained dries up; Insertion fills in the electrolyte solution that contains the potassium ferricyanide; In the three-electrode system that with naked glass-carbon electrode is working electrode, carry out cyclic voltammetry scan; The spike potential difference is at 64mV-80 mV in the gained cyclic voltammogram, and as far as possible near 64 mV, the glass-carbon electrode after obtaining handling;
3), with step 2) glass-carbon electrode after the processing that obtains places the NaH of the acidity that contains the L-halfcystine
2PO
4-Na
2HPO
4In the buffer solution, carry out electropolymerization with cyclic voltammetry, with polymerization the glass-carbon electrode after the processing of L-halfcystine clean and to obtain L-cysteine modified glass-carbon electrode after drying.
3. the preparation method of modified glassy carbon electrode according to claim 2, it is characterized in that: the condition of electropolymerization described in the step 3) is: sweep velocity 100 mV/s, current potential-0.6V-2.0V, the electropolymerization number of turns is the 10-20 circle; Said NaH
2PO
4-Na
2HPO
4The pH value of buffer solution is 6.0.
4. the preparation method of modified glassy carbon electrode according to claim 3 is characterized in that: the number of turns of electropolymerization described in the step 3) is 10 circles.
5. the preparation method of a modified glassy carbon electrode, it is characterized in that: the preparation method of said platinum/L-cysteine modified glass-carbon electrode is following:
A), glass-carbon electrode is processed into naked glass-carbon electrode;
B), the naked glass-carbon electrode that step a) is obtained dries up; Insertion fills in the electrolyte solution that contains the potassium ferricyanide; In the three-electrode system that with naked glass-carbon electrode is working electrode, carry out cyclic voltammetry scan; The spike potential difference is at 64mV-80 mV in the gained cyclic voltammogram, and as far as possible near 64 mV, the glass-carbon electrode after obtaining handling;
C), the glass-carbon electrode after the processing that step b) is obtained places the NaH that contains the L-halfcystine
2PO
4-Na
2HPO
4In the buffer solution, carry out electropolymerization with cyclic voltammetry, with polymerization the glass-carbon electrode after the processing of L-halfcystine clean and to obtain L-cysteine modified glass-carbon electrode after drying;
D), the L-cysteine modified glass-carbon electrode that step c) is obtained places the sulfuric acid solution that contains chloroplatinic acid; Carry out electro-deposition with cyclic voltammetry, the L-cysteine modified glass-carbon electrode that has deposited platinum is cleaned obtained platinum/L-cysteine modified glass-carbon electrode after drying.
6. the preparation method of modified glassy carbon electrode according to claim 5, it is characterized in that: the condition of electro-deposition described in the step d) is: sweep velocity 50 mV/s, current potential 0.4V--0.25V, the electro-deposition number of turns is the 10-15 circle.
7. the preparation method of modified glassy carbon electrode according to claim 6 is characterized in that: the number of turns of electro-deposition described in the step d) is 10 circles.
8. the application of the described modified glassy carbon electrode of claim 1 in detecting nitrite anions.
9. application according to claim 8 is characterized in that: the method for said application is following: modified glassy carbon electrode is placed the NaH that contains nitrite anions
2PO
4-Na
2HPO
4In the buffer solution, in the three-electrode system that with the modified glassy carbon electrode is working electrode, carry out cyclic voltammetry scan, the pH value of wherein said buffer solution is 2.5-4.0.
10. application according to claim 9 is characterized in that: the pH value of said buffer solution is 3.0.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103558210A (en) * | 2013-10-25 | 2014-02-05 | 江南大学 | Method for binding and fixing ionic type iridium coordination compound based on covalent bond |
| CN105738441A (en) * | 2016-02-26 | 2016-07-06 | 运城学院 | Modified glassy carbon electrode and preparation method and application thereof |
| CN113916966A (en) * | 2021-10-20 | 2022-01-11 | 蚌埠学院 | Preparation method and application of sensor based on L-cysteine/cobalamin composite membrane |
| CN114034754A (en) * | 2021-10-20 | 2022-02-11 | 蚌埠学院 | Preparation method and application of sensor based on cobalamin/potassium ferricyanide composite membrane |
| CN116908273A (en) * | 2023-09-14 | 2023-10-20 | 宁波检验检疫科学技术研究院(宁波国检贸易便利化服务中心) | Method for rapidly detecting harmful substances in food |
-
2011
- 2011-10-31 CN CN2011103380206A patent/CN102507684A/en active Pending
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103558210A (en) * | 2013-10-25 | 2014-02-05 | 江南大学 | Method for binding and fixing ionic type iridium coordination compound based on covalent bond |
| CN105738441A (en) * | 2016-02-26 | 2016-07-06 | 运城学院 | Modified glassy carbon electrode and preparation method and application thereof |
| CN105738441B (en) * | 2016-02-26 | 2018-06-05 | 运城学院 | A kind of modified glassy carbon electrode and its preparation method and application |
| CN113916966A (en) * | 2021-10-20 | 2022-01-11 | 蚌埠学院 | Preparation method and application of sensor based on L-cysteine/cobalamin composite membrane |
| CN114034754A (en) * | 2021-10-20 | 2022-02-11 | 蚌埠学院 | Preparation method and application of sensor based on cobalamin/potassium ferricyanide composite membrane |
| CN113916966B (en) * | 2021-10-20 | 2023-12-19 | 蚌埠学院 | Preparation method and application of sensor based on L-cysteine/cobalamin composite membrane |
| CN116908273A (en) * | 2023-09-14 | 2023-10-20 | 宁波检验检疫科学技术研究院(宁波国检贸易便利化服务中心) | Method for rapidly detecting harmful substances in food |
| CN116908273B (en) * | 2023-09-14 | 2023-11-28 | 宁波检验检疫科学技术研究院(宁波国检贸易便利化服务中心) | Method for rapidly detecting harmful substances in food |
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Application publication date: 20120620 |