CN106556593A - A kind of method of fixing tripyridyl ruthenium and detecting malachite green through electrochemiluminescence - Google Patents
A kind of method of fixing tripyridyl ruthenium and detecting malachite green through electrochemiluminescence Download PDFInfo
- Publication number
- CN106556593A CN106556593A CN201611013822.9A CN201611013822A CN106556593A CN 106556593 A CN106556593 A CN 106556593A CN 201611013822 A CN201611013822 A CN 201611013822A CN 106556593 A CN106556593 A CN 106556593A
- Authority
- CN
- China
- Prior art keywords
- malachite green
- electrode
- green oxalate
- detection
- solution
- 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.)
- Granted
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/76—Chemiluminescence; Bioluminescence
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Plasma & Fusion (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The present invention relates to a kind of method of detection malachite green oxalate, particularly belongs to electrochemiluminescence detection field.Using poly- o-aminophenol sulfonic acid-tris (bipyridine) ruthenium modified glassy carbon electrode as working electrode, used as auxiliary electrode, saturated calomel electrode constitutes three-electrode system as reference electrode to platinum electrode, detects malachite green oxalate with electrochemical luminescence method.The detection range of the method is 5.0 × 10‑8～1.0 × 10‑ 5Mol/L, lowest detection are limited to 1.5 × 10‑8mol/L.The low cost of present invention detection malachite green oxalate, sensitivity are high, simple to operate, and selectivity is good.
Description
Technical field
The present invention relates to a kind of electrochemical luminescence method of detection malachite green oxalate, and in particular to one kind is with poly- o-aminophenol sulphur
Acid-tris (bipyridine) ruthenium modified glassy carbon electrode be working electrode, the electrochemiluminescence analysis side of detection by quantitative water sample Malachite Green
Method.
Background technology
Malachite green oxalate, also known as peacock green, Viride Nitenses, is bottle green crystalline solid, with killing fish body parasite and mycete
And other effects, it is with low cost, therefore obtained the favor at aquaculture family.But malachite green oxalate is a kind of carcinogen, and can be
In aquatic products body, long-time is remained, and the side effect such as carcinogenic, teratogenesis and mutagenesis can be produced to human body by food chain, same with this
The discharge of Shi Hanyou malachite green oxalate breeding wastewaters can cause the pollution of water environment.Malachite green oxalate was listed in by China in 2002《Food
The fisheries drug and its compound inventory of product animal disabling》In, the detection of current malachite green oxalate is with immunological detection and Physico-chemical tests
Based on method, immunology detection mainly uses Enzyme-Linked Immunospot, and the false positive probability of the method detection is big；Physico-chemical tests are mainly wrapped
Combined gas chromatography mass spectrometry, high performance liquid chromatography, liquid chromatography mass Series detectors method are included, these methods have test to be needed
Want professional and technical personnel's operation, time-consuming, high cost the shortcomings of, therefore invent a kind of efficient, highly sensitive and inexpensive detection hole
The method of passeris montani saturati malachite green is most important.
Tris (bipyridine) ruthenium electrochemiluminescence has fast simple to operate, response, sensitivity height, the low advantage of Monitoring lower-cut,
Electrochemiluminescence analysis field is widely applied.The method is used to detect malachite green oxalate, with low cost, detection range
The advantages of width, rapid test.
The content of the invention
The problem that the present invention need to be solved is for the expensive detection of the detection method generally existing needs of existing malachite green oxalate
A kind of the problems such as instrument, testing time length and high cost, there is provided low cost, simple to operate, test rapidly detects malachite green oxalate
Method.
To solve the above problems, the scheme that the present invention is adopted is by poly- o-aminophenol sulfonic acid-tris (bipyridine) ruthenium modification glass carbon
Electrode enters as reference electrode, composition three-electrode system as auxiliary electrode, saturated calomel electrode as working electrode, platinum electrode
Row detection, comprises the following steps that：
(1) preparation of electropolymerization solution
With 0.1mol/L phosphate (PBS) buffer solution of pH=7.0 as supporting electrolyte, o-aminophenol sulfonic acid is prepared
Solution.
(2) preparation of poly- o-aminophenol sulfonic acid-tris (bipyridine) ruthenium modified glassy carbon electrode
The above-mentioned electropolymerization solution of 25mL is taken, in the range of the electrochemical window of -1.5～2.0V, cyclic voltammetry voltolisation is used
Close 20 to enclose；Deionized water is rinsed and is dried, and adsorbs 30min, then spend in being placed on the aqueous solution of 15mL tris (bipyridine) rutheniums
Ionized water is rinsed and is dried, used as the working electrode of electrochemiluminescence test.
(3) preparation of variable concentrations malachite green oxalate standard solution
A certain amount of malachite green oxalate solid is weighed accurately, deionized water prepares 1.0 × 10-3Mol/L standard solution, one
During quantitative criterion solution adds phosphate buffered solution, a series of malachite green oxalate standard solution of variable concentrations, concentration model are obtained
Enclose for 5.0 × 10-8～1.0 × 10-5mol/L。
(4) drafting of standard curve
A series of standard solution of malachite green oxalate that 20mL steps (3) are prepared is measured accurately as solution to be measured, by step
(2), used as working electrode, used as auxiliary electrode, saturated calomel electrode is used as reference electrode, group for platinum electrode for the modified electrode for obtaining
Into three-electrode system, in a series of PBS buffer solution of the malachite green oxalate pH=10 that three-electrode system is placed in variable concentrations,
In the range of the electrochemical window of -1.5～2.0V, photomultiplier tube high pressure 800V sweeps fast 0.1V/s, is circulated volt-ampere and sweeps
Retouch, record E-ECL curves, the luminous intensity difference before and after foundation addition malachite green oxalate is linear with malachite green oxalate log concentration value
Relation, obtains corresponding equation of linear regression.
(5) sample detection
Actual sample is first filtered adjusts pH again, is tested according to the electrochemiluminescence test condition same with step (4), note
Record luminous intensity, gained luminous intensity are calculated with the equation of linear regression corresponding to standard curve obtained by step (4) to be detected
The concentration of sample Malachite Green.
Preferably, the o-aminophenol sulfonic acid concentrations described in step (1) are 4.0 × 10-3mol/L。
Preferably, the tris (bipyridine) ruthenium concentration described in step (2) is 1.0 × 10-4mol/L。
Preferably, the cyclic voltammetry electropolymerizatioconditions conditions described in step (2) are：Sweep limitss：0.1～1.5V；Scanning
Speed：0.1V/s.
Preferably, the buffer solution described in step (3) is the PBS buffer solution of the 0.1mol/L of pH=10.
Beneficial effects of the present invention：The present invention adopts poly- o-aminophenol sulfonic acid come fixing tripyridyl ruthenium, using adjacent amino
The hydrogen bond action existed between phenol sulfonic acid and tris (bipyridine) ruthenium, when particularly o-aminophenol sulfonic acid aggregates into poly- o-aminophenol sulfonic acid
Can be higher with the hydrogen bond action of tris (bipyridine) ruthenium so that o-aminophenol sulfonic acid electropolymerization film being capable of fixing tripyridyl ruthenium well
Modified electrode is obtained, and with excellent absorption property, adsorption, the preparation method letter of its electrode is produced to malachite green oxalate
Single, sensitivity is high.For detecting malachite green oxalate, the concentration in contained malachite green oxalate sample, low cost, spirit can be effectively detected
Sensitivity is high, and favorable reproducibility, detection range width are simple to operate, and test is rapid.
Description of the drawings
Fig. 1 is phosphate of the poly- o-aminophenol sulfonic acid-tris (bipyridine) ruthenium modified glassy carbon electrode in variable concentrations malachite green oxalate
Cyclic voltammetric luminosity curve in buffer solution, the concentration of its Malachite Green are followed successively by from top to bottom by peak of curve height：
5.0×10-8mol/L、1.0×10-7mol/L、5.0×10-7mol/L、1.0×10-6mol/L、5.0×10-6Mol/L and 1.0
×10-5mol/L。
Fig. 2 be add malachite green oxalate before and after luminous intensity difference and the standard curve of malachite green oxalate concentration.
Specific embodiment
The present invention is described in further detail with reference to embodiment：
Embodiment 1：
(1) preparation of poly- o-aminophenol sulfonic acid-tris (bipyridine) ruthenium modified glassy carbon electrode
25mL o-aminophenol sulfonic acid electropolymerization solution is taken, in the range of the electrochemical window of -1.5～2.0V, with circulation volt
Peace method electropolymerization 20 is enclosed, and deionized water is rinsed and dried, and is placed on 15mL 1.0 × 10-4Mol/L tris (bipyridine) rutheniums it is water-soluble
Adsorb 30min in liquid, then deionized water is rinsed and dried, as the working electrode of electrochemiluminescence test.
(2) drafting of standard curve
Using poly- o-aminophenol sulfonic acid-tris (bipyridine) ruthenium modified glassy carbon electrode as working electrode, platinum electrode is used as auxiliary electricity
Pole, saturated calomel electrode constitute three-electrode system as reference electrode, and with the 0.1mol/L PBSs of pH=10 as sky
Three-electrode system is placed in a series of malachite green oxalate concentration (5.0 × 10 by white solution detection luminous intensity-8mol/L、1.0×10- 7mol/L、5.0×10-7mol/L、1.0×10-6mol/L、5.0×10-6Mol/L and 1.0 × 10-5Mol/L) the PBS of pH=10
In buffer solution, in the range of the electrochemical window of -1.5～2.0V, photomultiplier tube high pressure 800V sweeps fast 0.1V/s, carries out
Cyclic voltammetry scan, records E-ECL curves, the luminous intensity difference and malachite green oxalate concentration pair before and after foundation addition malachite green oxalate
The linear relationship of numerical value, obtains corresponding equation of linear regression.The detection range of equation of linear regression is 5.0 × 10-8～1.0 ×
10-5Mol/L, lowest detection are limited to 1.5 × 10-8mol/L。
(3) detection of sample
After taking artificial fish farm water sample filtration, adjust pH to 10 with the PBS buffer solution of 0.1mol/L, take 20mL resulting solutions
Detect for electrochemiluminescence, according to testing to testing sample solution with step (2) identical electrochemical test method, institute
Obtain the equation of linear regression obtained by luminous intensity values difference step (2) corresponding to standard curve and calculate detected sample mesopore
The concentration of passeris montani saturati malachite green, the results are shown in Table 1 for which.
Comparative example 1：
(1) preparation of tris (bipyridine) ruthenium modified glassy carbon electrode
Glass-carbon electrode is placed in into 15mL 1.0 × 10-4Adsorb 30min, Ran Houyong in the aqueous solution of mol/L tris (bipyridine) rutheniums
Deionized water rinsing dries, used as the working electrode of electrochemiluminescence test.
(2) drafting of standard curve
Using tris (bipyridine) ruthenium modified glassy carbon electrode as working electrode, platinum electrode is used as auxiliary electrode, saturated calomel electrode
As reference electrode, three-electrode system is constituted, and it is luminous as blank solution detection with the 0.1mol/L PBSs of pH=10
Three-electrode system is placed in a series of malachite green oxalate concentration (5.0 × 10 by intensity-8mol/L、1.0×10-7mol/L、5.0×10- 7mol/L、1.0×10-6mol/L、5.0×10-6Mol/L and 1.0 × 10-5Mol/L) in the PBS buffer solution of pH=10 ,-
In the range of the electrochemical window of 1.5～2.0V, photomultiplier tube high pressure 800V sweeps fast 0.1V/s, is circulated voltammetric scan, note
Record E-ECL curves, the linear relationship of luminous intensity difference and malachite green oxalate log concentration value before and after foundation addition malachite green oxalate,
Obtain corresponding equation of linear regression.
(3) detection of sample
After taking artificial fish farm water sample filtration, adjust pH to 10 with the PBS buffer solution of 0.1mol/L, take 20mL resulting solutions
Detect for electrochemiluminescence, according to testing to testing sample solution with step (2) identical electrochemical test method, institute
Obtain the equation of linear regression obtained by luminous intensity values difference step (2) corresponding to standard curve and calculate detected sample mesopore
The concentration of passeris montani saturati malachite green, the results are shown in Table 1 for which.
The measurement result of table 1 certain artificial fish farm water sample
Remarks：aFor the meansigma methodss of three measure
As shown in table 1, sample Parallel testing 3 times, relative standard deviation be less than 5%, recovery of standard addition scope be 97%～
101%.Above test result indicate that, modify as substrate without poly- o-aminophenol sulfonic acid and individually modified with tris (bipyridine) ruthenium
Glass-carbon electrode cannot detect malachite green oxalate, and the present invention is used to detect that the malachite green oxalate in artificial fish farm water sample is feasible.
Above example is only used for present invention explanation and uses, not limitation of the present invention, about the technical staff in field
Can also make corresponding various change, therefore all equivalents or equivalent variations without departing from the scope of the present invention
The technical scheme that formed of mode belong to protection scope of the present invention.
Claims (7)
1. it is a kind of detection malachite green oxalate electrochemical luminescence method, it is characterised in that：Methods described is：With poly- o-aminophenol sulphur
Acid-tris (bipyridine) ruthenium modified glassy carbon electrode is working electrode, and, used as auxiliary electrode, saturated calomel electrode is used as reference for platinum electrode
Electrode, composition three-electrode system are detected.
2. it is according to claim 1 detection malachite green oxalate electrochemical luminescence method, it is characterised in that：Methods described is concrete
Step is as follows：
(1) preparation of electropolymerization solution
With the 0.1mol/L phosphate buffered solution of pH=7.0 as supporting electrolyte, o-aminophenol sulfonic acid solutions are prepared；
(2) preparation of poly- o-aminophenol sulfonic acid-tris (bipyridine) ruthenium modified glassy carbon electrode
The above-mentioned electropolymerization solution of 25mL is taken, in the range of the electrochemical window of -1.5～2.0V, with cyclic voltammetry electropolymerization 20
Circle；Deionized water is rinsed and is dried, and adsorbs 30min, then use deionization in being placed on the aqueous solution of 15mL tris (bipyridine) rutheniums
Water is rinsed and is dried, used as the working electrode of electrochemiluminescence test；
(3) preparation of variable concentrations malachite green oxalate standard solution
A certain amount of malachite green oxalate solid is weighed accurately, deionized water prepares 1.0 × 10-3Mol/L standard solution, standard is molten
During liquid adds the phosphate buffered solution of pH=10, a series of concentration ranges are obtained for 5.0 × 10-8～1.0 × 10-5Mol/L's
Malachite green oxalate standard solution；
(4) drafting of standard curve
The standard solution of the malachite green oxalate that 20mL steps (3) are prepared is measured accurately as solution to be measured, repairing that step (2) is obtained
Used as working electrode, used as auxiliary electrode, saturated calomel electrode constitutes three electrode bodies as reference electrode to platinum electrode to decorations electrode
System, three-electrode system is placed in a series of phosphate buffered solution of malachite green oxalate concentration, in the electrochemistry of -1.5～2.0V
In window ranges, photomultiplier tube high pressure 800V sweeps fast 0.1V/s, is circulated voltammetric scan, and record current potential-luminous intensity is bent
Line, the luminous intensity difference before and after foundation addition malachite green oxalate and the linear relationship of malachite green oxalate log concentration value, obtain corresponding
Equation of linear regression；
(5) actual sample detection
Actual sample is first filtered adjusts pH again, calculates the concentration of malachite green oxalate according to the equation of linear regression in step (4).
3. it is according to claim 2 detection malachite green oxalate electrochemical luminescence method, it is characterised in that：Step (1) is described
O-aminophenol sulfonic acid solutions concentration be 4.0 × 10-3mol/L。
4. it is according to claim 2 detection malachite green oxalate electrochemical luminescence method, it is characterised in that：Step (2) is described
Tris (bipyridine) ruthenium concentration of aqueous solution be 1.0 × 10-4mol/L。
5. it is according to claim 2 detection malachite green oxalate electrochemical luminescence method, it is characterised in that：Step (2) is described
Cyclic voltammetry sweep limitss be 0.1～1.5V.
6. it is according to claim 2 detection malachite green oxalate electrochemical luminescence method, it is characterised in that：Step (2) is described
Cyclic voltammetry scanning speed be 0.1V/s.
7. it is according to claim 2 detection malachite green oxalate electrochemical luminescence method, it is characterised in that：Step (3) is described
PH=10 phosphate buffered solution concentration be 0.1mol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611013822.9A CN106556593B (en) | 2016-11-18 | 2016-11-18 | A kind of method of fixing tripyridyl ruthenium and detecting malachite green through electrochemiluminescence |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611013822.9A CN106556593B (en) | 2016-11-18 | 2016-11-18 | A kind of method of fixing tripyridyl ruthenium and detecting malachite green through electrochemiluminescence |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106556593A true CN106556593A (en) | 2017-04-05 |
| CN106556593B CN106556593B (en) | 2019-03-22 |
Family
ID=58443203
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611013822.9A Active CN106556593B (en) | 2016-11-18 | 2016-11-18 | A kind of method of fixing tripyridyl ruthenium and detecting malachite green through electrochemiluminescence |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106556593B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108344618A (en) * | 2018-01-10 | 2018-07-31 | 武汉市农业科学院 | A kind of malachite green fast detecting method |
| CN110296980A (en) * | 2019-07-16 | 2019-10-01 | 常州大学 | A kind of method of Electrochemiluminescince detection furazolidone |
| CN110308142A (en) * | 2019-07-25 | 2019-10-08 | 常州大学 | A kind of tetracycline flexibility class goldleaf electrochemical luminescence sensor and preparation method thereof and detection method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102854183A (en) * | 2012-09-04 | 2013-01-02 | 上海师范大学 | Method for detecting melamine through solid-state electrochemiluminescence |
| CN103695551A (en) * | 2013-12-24 | 2014-04-02 | 华南师范大学 | Nucleic acid detection method based on polymer electrochemiluminescence signal amplification technology |
| US20150268232A1 (en) * | 2009-02-27 | 2015-09-24 | The Regents Of The University Of Michigan | Functionalized Polydiacetylene Sensors |
-
2016
- 2016-11-18 CN CN201611013822.9A patent/CN106556593B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150268232A1 (en) * | 2009-02-27 | 2015-09-24 | The Regents Of The University Of Michigan | Functionalized Polydiacetylene Sensors |
| CN102854183A (en) * | 2012-09-04 | 2013-01-02 | 上海师范大学 | Method for detecting melamine through solid-state electrochemiluminescence |
| CN103695551A (en) * | 2013-12-24 | 2014-04-02 | 华南师范大学 | Nucleic acid detection method based on polymer electrochemiluminescence signal amplification technology |
Non-Patent Citations (2)
| Title |
|---|
| 刘凤玉 等: "三联吡啶钌电致化学发光检测隐性孔雀石绿", 《第十三届全国有机分子电化学及工业学术会议论文摘要》 * |
| 曾凯: "《湖南大学硕士学位论文》", 31 December 2011 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108344618A (en) * | 2018-01-10 | 2018-07-31 | 武汉市农业科学院 | A kind of malachite green fast detecting method |
| CN108344618B (en) * | 2018-01-10 | 2020-12-01 | 武汉市农业科学院 | Quick malachite green detection method |
| CN110296980A (en) * | 2019-07-16 | 2019-10-01 | 常州大学 | A kind of method of Electrochemiluminescince detection furazolidone |
| CN110296980B (en) * | 2019-07-16 | 2022-02-11 | 常州大学 | Method for detecting furazolidone by electrochemical luminescence method |
| CN110308142A (en) * | 2019-07-25 | 2019-10-08 | 常州大学 | A kind of tetracycline flexibility class goldleaf electrochemical luminescence sensor and preparation method thereof and detection method |
| CN110308142B (en) * | 2019-07-25 | 2021-07-27 | 常州大学 | Tetracycline flexible gold-like foil electrochemical luminescence sensor and preparation method and detection method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106556593B (en) | 2019-03-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101458223B (en) | Preparation of quantitative rapid detecting sensor of microcapsule algae toxin and applications | |
| CN110618177B (en) | Preparation method and application of streptomycin electrochemical-photoelectrochemical dual-method ratiometric aptamer sensor | |
| CN106556593B (en) | A kind of method of fixing tripyridyl ruthenium and detecting malachite green through electrochemiluminescence | |
| CN105424787A (en) | Preparation method of silk screen printing sensor for detecting tetracycline and oxytetracycline at same time | |
| CN113376235A (en) | Preparation method and detection device of tetracycline photoelectrochemistry aptamer sensor | |
| Yilmaz et al. | Determination of Gallic acid by differential pulse polarography: Application to fruit juices | |
| CN106596666B (en) | A kind of fixing tripyridyl ruthenium and electrochemical luminescence detection lure red method | |
| CN105738441B (en) | A kind of modified glassy carbon electrode and its preparation method and application | |
| CN101806741B (en) | Quick detection method of meat freshness and detection platform thereof | |
| CN112816639B (en) | Construction method of photoelectrochemical aptamer sensor for sensitive detection of enrofloxacin | |
| CN104155289A (en) | Solid electrochemical luminescence sensor for detecting mercury ions and preparation method and application of solid electrochemical luminescence sensor for detecting mercury ions | |
| CN109900767B (en) | Method for detecting freshness of chicken by utilizing electrochemistry | |
| CN103983733A (en) | Method for detecting biogenic amine in yellow wine by using chromatographic sheet | |
| CN104020205B (en) | The imprinted polymer membrane electrode of parachloroanilinum, its preparation method and application process | |
| CN102914526A (en) | Method for detecting concentration of mercury ions through dansyl acid as fluorescent probe | |
| CN104569119A (en) | Method for synergically enriching and detecting naphthol isomers | |
| CN101509892A (en) | Method for rapidly identifying cysteine and cystine by utilizing electrochemical technique | |
| CN111304716B (en) | Preparation method of pencil graphite modified electrode and method for detecting benzenediol isomer in water body | |
| CN110715921A (en) | Method for detecting gallic acid by electrochemical luminescence based on graphene quantum dots | |
| CN106525935A (en) | Melamine test method applying immobilized rucbpy and electrochemiluminescence | |
| CN110296980B (en) | Method for detecting furazolidone by electrochemical luminescence method | |
| CN103196898A (en) | Method for determining trace levamisole by bipyridine ruthenium electrochemiluminescence method | |
| CN101650330A (en) | Preparation method and application of didodecyldimethylammonium bromide modified glassy carbon electrode | |
| US20220404307A1 (en) | Water ph detection sensor and use of ruthenium-iridium electrode as ph sensing material | |
| CN110376265A (en) | A method of detection ascorbic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |