CN106198697A - A kind of electrochemical method simultaneously detecting three kinds of isomerss of nitroaniline - Google Patents
A kind of electrochemical method simultaneously detecting three kinds of isomerss of nitroaniline Download PDFInfo
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- CN106198697A CN106198697A CN201610515778.5A CN201610515778A CN106198697A CN 106198697 A CN106198697 A CN 106198697A CN 201610515778 A CN201610515778 A CN 201610515778A CN 106198697 A CN106198697 A CN 106198697A
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Abstract
The invention discloses a kind of electrochemical method simultaneously detecting three kinds of isomerss of nitroaniline.Graphene quantum dot prepared by the present invention and beta cyclodextrin complex modified electrode well achieve the Electrochemical separation of three kinds of isomerss of nitroaniline, and can carry out quantitative analysis by three kinds of isomerss of paranitroanilinum simultaneously.Modified electrode prepared by the present invention is highly sensitive, selectivity good, range of linearity width, it is not necessary to be previously isolated from, and can be used for quickly detecting while three kinds of isomerss of nitroaniline in actual sample.
Description
Technical field
The present invention relates to a kind of electrochemical method simultaneously detecting three kinds of isomerss of nitroaniline, belong to analytical chemistry
Field and environmental analysis detection technique field.
Background technology
Nitroaniline isomers includes ortho-nitraniline, meta nitro aniline and paranitroanilinum, is nitryl aromatic amine
Derivant.Nitroaniline isomers is the environmental contaminants closely bound up with mankind's activity, is mainly derived from dyestuff, agriculture
During medicine, the production of herbicide and use.Nitroaniline isomers is the Organic substance that a class toxicity is bigger, and is difficult to
Biodegradation in the environment.The toxicity strong due to it and doubtful carcinogenecity, listed in priority pollutant list by many countries.Cause
This, need a kind of easier, quick and practical method to realize the monitoring in the environment of nitroaniline isomers.
Owing to structure and character are quite similar, detection nitroaniline isomers is highly difficult simultaneously.Now,
Certain methods is had to be used for the detection of nitroaniline isomers, such as high performance liquid chromatography, capillary electric chromatogram, fluorescence sense
Device etc..But these methods have the shortcomings such as expensive equipment, operation is complicated, sensitivity is low, limit them at environmental and biological materials
Application in product analysis.Electrochemical sensor due to low cost, highly sensitive, selectivity good, be well suited for for detecting Nitrobenzol
Amine isomers.
Summary of the invention
It is an object of the invention to provide a kind of electrochemical method simultaneously detecting three kinds of isomerss of nitroaniline.
Graphene quantum dot and beta-schardinger dextrin-complex modified glassy carbon electrode are the method comprises the steps of firstly, preparing, it is proposed that Yi Zhongjian
Just, detect the electrochemical method of three kinds of isomerss of nitroaniline the most simultaneously.The present invention is simple to operate, detection is quick and
Highly sensitive, electrochemical response is good, can directly detect three kinds of isomerss of the nitroaniline in actual sample.
A kind of electrochemical method simultaneously detecting three kinds of isomerss of nitroaniline, comprises the following steps:
1) graphene quantum dot is dissolved in distilled water obtains the graphene quantum dot solution that mass body volume concentrations is 1mg/mL, will
Beta-schardinger dextrin-is dissolved in distilled water and obtains the beta-schardinger dextrin-solution that mass body volume concentrations is 10mg/mL, then by Graphene quantum
Point solution and beta-schardinger dextrin-solution are mixed to get composite solution；The glass-carbon electrode cleaned up is immersed gained composite
In solution, cyclic voltammetry scanning 20 circle in the range of-1.0 ~ 2.0V, electro-deposition obtains stable graphene quantum dot and β-ring
Dextrin composite modified glassy carbon electrode；
2) using three-electrode system, graphene quantum dot and beta-schardinger dextrin-composite modified glassy carbon electrode are working electrode, platinum
Silk electrode is auxiliary electrode, and silver/silver chloride electrode is reference electrode；The potassium dihydrogen phosphate of pH=6.8 and disodium hydrogen phosphate buffering are molten
Containing concentration in liquid is 0.6 ~ 20 μ g/mL nitroaniline isomerism liquid solution, uses differential pulse voltametry at 0.2 ~-0.6V
Being scanned, the spike potential of three kinds of isomerss of nitroaniline is followed successively by-0.02V ,-0.22V ,-0.43V, according to oxidation peak
Linear relationship between electric current and nitroaniline isomers concentration in the solution, carries out nitroaniline in sample different with dividing
The quantitative analysis of structure bulk concentration；The supporting electrolyte of described buffer solution is 0.1M potassium chloride.
In described composite solution, the volume ratio of graphene quantum dot solution and beta-schardinger dextrin-solution is 1:10.
Described modified electrode, when detecting ortho-nitraniline, detects linearly at 0.6 ~ 20 μ g/mL, and detection is limited to 6.625
×10-12M；When detecting meta nitro aniline, detecting linearly at 0.6 ~ 20 μ g/mL, detection is limited to 1.005 × 10-7M；In detection
During paranitroanilinum, detecting linearly at 0.6 ~ 20 μ g/mL, detection is limited to 1.876 × 10-10M。
The present invention compared with prior art has the advantage that:
Graphene quantum dot of the present invention and beta-schardinger dextrin-three kinds of mappings of composite modified glassy carbon electrode paranitroanilinum are different
Structure body has preferable selectivity, and method is simple, accurate, highly sensitive, range of linearity width, can detect the nitre in actual sample simultaneously
Three kinds of enantiomers of base aniline.
Accompanying drawing explanation
Fig. 1 be glass-carbon electrode (curve a), modified by graphene quantum dot glass-carbon electrode (curve b), graphene quantum dot and β-
(curve c) is 20 μ g/mL ortho-nitranilines, meta nitro aniline and to nitre to cyclodextrin composite modified glassy carbon electrode to concentration
The differential pulse voltammogram of base aniline.
Detailed description of the invention
Embodiment 1
Respectively with naked glass-carbon electrode, modified by graphene quantum dot glass-carbon electrode, graphene quantum dot and beta-schardinger dextrin-composite
Modified glassy carbon electrode is working electrode, at the phosphate buffer solution equipped with 5mL pH=6.8, three kinds of nitroaniline isomerss
Mass concentration is in the solution of 20 μ g/mL, carries out differential pulse scanning, obtain differential arteries and veins in 0.2 ~-0.6V potential range
Rush voltammogram.As it is shown in figure 1, at naked glass-carbon electrode, (curve three kinds of isomerss of a) surface nitro groups aniline occur in that two oxygen
Change peak, fail to separate three kinds of isomerss of nitroaniline.Modified by graphene quantum dot glass-carbon electrode (curve b) surface,
Three kinds of nitroaniline isomerss realize Electrochemical separation, but modify with graphene quantum dot and beta-schardinger dextrin-composite
(curve c) compares glass-carbon electrode, can substantially observe, on graphene quantum dot and beta-schardinger dextrin-composite modified electrode three kinds
The separation of nitroaniline isomers becomes apparent from, and oxidation peak current intensity is the biggest.
Embodiment 2
The concentration of three kinds of nitroaniline isomerss is fixed on 0.6 μ g/mL respectively, and change one of which nitroaniline is with dividing
The concentration of isomer, along with the increase of concentration, oxidation peak current increases, can respectively obtain three kinds of isomerss of nitroaniline
Linear relationship curve；According to relevant sensitivity determination principle, measure its detection line；In the phosphate buffer solution of pH=6.8,
Differential pulse voltametry records the concentration of three kinds of isomerss and presents the most linear closing the most within the specific limits with peak current
System；
The range of linearity of ortho-nitraniline is 0.6 ~ 20 μ g/mL, and equation of linear regression is ip=1.853 + 0.319c (μg/mL,
R2=0.995), detection is limited to 6.625 × 10-12M；
The range of linearity of meta nitro aniline is 0.6 ~ 20 μ g/mL, and equation of linear regression is ip=0.433 + 0.015c (μg/mL,
R2=0.997), detection is limited to 1.005 × 10-7M；
The range of linearity of paranitroanilinum is 0.6 ~ 20 μ g/mL, and equation of linear regression is ip=0.273 + 0.035c (μg/mL,
R2=0.999), detection is limited to 1.876 × 10-10M。
Embodiment 3
Main component in pesticide carbendazim is N-(2-benzimidazole base)-methyl carbamate, and toxicity is faint, but wherein
Containing a small amount of nitroaniline enantiomer.Taking a small amount of carbendazim and be dissolved in distilled water, multiple times of filtration, to clarification, adds a certain amount of
Potassium dihydrogen phosphate and disodium hydrogen phosphate are made into the solution to be measured (supporting electrolyte 0.1M potassium chloride) of pH=6.8.This solution will be added
Enter nitroaniline enantiomer standard solution, use mark-on method to measure the nitroaniline enantiomerism body burden in sample.Inspection
Survey result and can be shown in Table 1, table 2 and table 3.
The mensuration (n=5) of ortho-nitraniline in table more than 1 spirit bacterium
The mensuration (n=5) of table more than 2 spirit bacterium intermediate nitro aniline
The mensuration (n=5) of paranitroanilinum in table more than 3 spirit bacterium
Embodiment 4
Main component in herbicide trifluralin is 2,6-dinitro-N, N-dipropyl-4-5-trifluoromethylaniline, low to people and animals
Poison, but wherein contain a small amount of nitroaniline enantiomer.Taking a small amount of trefanocide and be dissolved in distilled water, multiple times of filtration, to clarification, adds
Enter a certain amount of potassium dihydrogen phosphate and disodium hydrogen phosphate is made into the solution to be measured (supporting electrolyte 0.1M potassium chloride) of pH=6.8.Will
This solution adds nitroaniline enantiomer standard solution, uses mark-on method to measure the nitroaniline enantiomerism in sample
Body burden.Testing result can be shown in Table 4, table 5 and table 6.
The mensuration (n=5) of ortho-nitraniline in table 4 trefanocide
The mensuration (n=5) of table 5 trefanocide intermediate nitro aniline
The mensuration (n=5) of paranitroanilinum in table 6 trefanocide
。
Claims (3)
1. detect an electrochemical method for three kinds of isomerss of nitroaniline simultaneously, comprise the following steps:
1) graphene quantum dot is dissolved in distilled water obtains the graphene quantum dot solution that mass body volume concentrations is 1mg/mL, will
Beta-schardinger dextrin-is dissolved in distilled water and obtains the beta-schardinger dextrin-solution that mass body volume concentrations is 10mg/mL, then by Graphene quantum
Point solution and beta-schardinger dextrin-solution are mixed to get composite solution；The glass-carbon electrode cleaned up is immersed gained composite
In solution, cyclic voltammetry scanning 20 circle in the range of-1.0 ~ 2.0V, electro-deposition obtains stable graphene quantum dot and β-ring
Dextrin composite modified glassy carbon electrode；
2) using three-electrode system, graphene quantum dot and beta-schardinger dextrin-composite modified glassy carbon electrode are working electrode, platinum
Silk electrode is auxiliary electrode, and silver/silver chloride electrode is reference electrode；The potassium dihydrogen phosphate of pH=6.8 and disodium hydrogen phosphate buffering are molten
Containing concentration in liquid is 0.6 ~ 20 μ g/mL nitroaniline isomerism liquid solution, uses differential pulse voltametry at 0.2 ~-0.6V
Being scanned, the spike potential of three kinds of isomerss of nitroaniline is followed successively by-0.02V ,-0.22V ,-0.43V, according to oxidation peak
Linear relationship between electric current and nitroaniline isomers concentration in the solution, carries out nitroaniline in sample different with dividing
The quantitative analysis of structure bulk concentration；The supporting electrolyte of described buffer solution is 0.1M potassium chloride.
2. the method for claim 1, it is characterised in that graphene quantum dot solution and β in described composite solution-
The volume ratio of cyclodextrin solution is 1:10.
3. the method for claim 1, it is characterised in that described modified electrode is when detecting ortho-nitraniline, 0.6 ~ 20
μ g/mL detects linearly, and detection is limited to 6.625 × 10-12M；When detecting meta nitro aniline, detect in line at 0.6 ~ 20 μ g/mL
Property, detection is limited to 1.005 × 10-7M；When detecting paranitroanilinum, detecting linearly at 0.6 ~ 20 μ g/mL, detection is limited to
1.876×10-10M。
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110003363A (en) * | 2019-04-16 | 2019-07-12 | 合肥工业大学 | Electrochemical Modification composite material and preparation method thereof and electrochemical sensor |
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| CN104569122A (en) * | 2015-01-22 | 2015-04-29 | 广西师范学院 | Method for detecting concentration of copper ions in solution |
| CN104597091A (en) * | 2015-01-22 | 2015-05-06 | 广西师范学院 | Preparation method for modified electrode |
| CN105044173A (en) * | 2015-07-06 | 2015-11-11 | 常州大学 | Production method of graphene quantum dot/beta-cyclodextrin composite membrane modified electrode, and application of electrode in electrochemical identification of tryptophan enantiomers. |
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- 2016-07-04 CN CN201610515778.5A patent/CN106198697A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104569122A (en) * | 2015-01-22 | 2015-04-29 | 广西师范学院 | Method for detecting concentration of copper ions in solution |
| CN104597091A (en) * | 2015-01-22 | 2015-05-06 | 广西师范学院 | Preparation method for modified electrode |
| CN105044173A (en) * | 2015-07-06 | 2015-11-11 | 常州大学 | Production method of graphene quantum dot/beta-cyclodextrin composite membrane modified electrode, and application of electrode in electrochemical identification of tryptophan enantiomers. |
Non-Patent Citations (3)
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110003363A (en) * | 2019-04-16 | 2019-07-12 | 合肥工业大学 | Electrochemical Modification composite material and preparation method thereof and electrochemical sensor |
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