CN104634851A - Electrochemical method for rapidly screening polychlorinated biphenyl - Google Patents
Electrochemical method for rapidly screening polychlorinated biphenyl Download PDFInfo
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- CN104634851A CN104634851A CN201510022750.3A CN201510022750A CN104634851A CN 104634851 A CN104634851 A CN 104634851A CN 201510022750 A CN201510022750 A CN 201510022750A CN 104634851 A CN104634851 A CN 104634851A
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Abstract
The invention relates to the technical field of rapid screening of polychlorinated biphenyl, and particularly relates to an electrochemical method for rapidly screening polychlorinated biphenyl in a water system. According to the method, pyrrole is adopted as a conducting polymer, beta-cyclodextrin functional graphene modified pyrolytic graphite electrode is prepared by a constant-potential polymerization method, and polychlorinated biphenyl in the water system is rapidly screened by virtue of different recognition capacities of probe molecular ferrocene and polychlorinated biphenyl and the subjective-objective body of cyclodextrin. The modified electrode is simple to produce, good in stability and non-toxic; moreover, by adopting the determination method, the interference of co-existing substances can be effectively alleviated, and the selectivity and sensitivity for the polychlorinated biphenyl are high.
Description
Technical field
The present invention relates to polychlorinated biphenyl Rapid screening techniques field, particularly relating to a kind of is conducting polymer with pyrroles, utilize constant potential polymerization to prepare poly-beta-schardinger dextrin-(β-CDP) functionalization graphene (Grp) and modify pyrolytic graphite electrode (PGE), different by probe molecule ferrocene and polychlorinated biphenyl and cyclodextrin Host-guest Recognition ability, realize the electrochemical method of the rapid screening of polychlorinated biphenyl in aqueous systems.
Background technology
Polychlorinated biphenyl is typical aromatic halide, and be not easily decomposed or biodegradation, chemical stability is high, is insoluble in water, easily by food chain enrichment in the grease of biosome.Even if also can there is teratogenesis, carcinogenic, mutagenic threat to human health in these materials in trace level.At present chromatography, spectroscopic methodology, catalysis method etc. are mainly concentrated on to the detection means of polychlorinated biphenyl, wherein chromatography because having fast, the advantage such as high resolving power, high selectivity, become the major technique analyzed and measure in Trace Polychlorinated Biphenyls measuring technology gradually.Although these detection meanss have higher sensitivity and selectivity, mostly need complicated pretreatment process and complex operation, cost is high, and experimental facilities is too heavy, cannot realize rapid screening and the detection of contaminated samples.It is a class easier in various detection method that electrochemical method detects, there is higher sensitivity and selectivity, be particularly suitable for in-situ enrichment and mensuration, by the modification to electrode interface, be suitable for the analysis requirement in complex matrices, thus quick detection and the judgement of sample can be realized.But the electrochemical sensor of development is at present confined to the aspect such as biology sensor, electrical catalyze reduction, and the building process of its reappearance and sensor affects sensor further developing in environment measuring always.Therefore, need badly and set up a kind of simple and convenient, high selectivity, highly sensitive electrochemical methods rapid screening is carried out to polychlorinated biphenyl.This all has important scientific meaning and application prospect at aspects such as environmental monitoring, Emergent detection, epistemic context process, environmental pollution early warning and improvement.
Graphene is because having large surface area, and the electro catalytic activity of good electric conductivity, thermal conductivity, structural stability and excellence, is widely used in electrochemical sensor.But in actual applications, usually its surface is carried out functionalization to meet the use of some particular demands.The present invention is by modifying the rapid screening of β-CDP realize target thing at graphenic surface.The structure of cyclodextrin molecular presents a kind of tubbiness of hollow, the outside that hydroxyls all in its structure is all seated bucket defines the hydrophilic outer wall of cyclodextrin molecular, and the oxygen atom of the carbon atom and hydrogen atom and glucosides that are positioned at inner side constitutes cyclodextrin molecular hydrophobic interior cavities, thus the characteristic of " outer hydrophilic, interior hydrophobic " is shown.The most characteristic feature that cyclodextrin special construction presents is exactly optionally in conjunction with multiple guest molecule, can form the inclusion complex having different degree of stability in aqueous.Cyclodextrin can as the suitable guest molecule of host molecule inclusion size, and guest molecule size is applicable to its cave size, as long as polarity is less than water, just can replace hydrone and the cavity that enters cyclodextrin forms inclusion complex.
Polychlorinated biphenyl self does not have electrochemical activity, but competition mechanism can be there is with electroactive material ferrocene when forming host-guest complex with cyclodextrin in its pair of benzene ring structure, when making electrochemically to study, after add polychlorinated biphenyl in the solution containing probe molecule ferrocene, different due to ferrocene and polychlorinated biphenyl and cyclodextrin Host-guest Recognition ability, polychlorinated biphenyl, by the position of ferrocene in substituted cyclodextrin cavity, makes ferrocene reduce at the peak current of electrode surface.A kind of electrochemical method can be set up accordingly to study the competitive relation of polychlorinated biphenyl and ferrocene, thus realize the rapid screening of polychlorinated biphenyl.
Summary of the invention
Object of the present invention is exactly provide for the shortcoming in above-mentioned polychlorinated biphenyl mensuration.A kind of is conducting polymer with pyrroles, utilize constant potential polymerization to prepare β-CDP functionalization Grp and modify PGE, different by probe molecule ferrocene and polychlorinated biphenyl and cyclodextrin Host-guest Recognition ability, realize the electrochemical method of the rapid screening of polychlorinated biphenyl in aqueous systems.This modified electrode makes easier, and good stability is nontoxic, and this assay method effectively reduces the interference of coexisting substances, has high selectivity to polychlorinated biphenyl, high sensitivity.
Technical scheme of the present invention is: a kind of electrochemical method for rapid screening polychlorinated biphenyl, take pyrroles as conducting polymer, utilize constant potential polymerization to prepare β-CDP functionalization Grp and modify PGE, different by probe molecule ferrocene and polychlorinated biphenyl and cyclodextrin Host-guest Recognition ability, realize the electrochemical method of the rapid screening of polychlorinated biphenyl in aqueous systems.
This take pyrroles as conducting polymer, utilize constant potential polymerization to prepare β-CDP functionalization Grp and modify PGE, its concrete making step is: take 5.0 g beta-schardinger dextrin-s in 8 mL massfractions be in the NaOH solution of 33%, under room temperature, mechanical raking is spent the night, mixed solution is heated to 30 DEG C and adds rapidly 2.4 mL epichlorokydrin, acetone cessation reaction is added, with 12 mol × L after keeping 30 DEG C to stir 4 h
-1hCl regulate pH to 6.0, dries at 50 DEG C and spends the night, cooling, with HCl neutralize, suction filtration, revolves steaming and obtains β-CDP; Get the graphene oxide water solution of 20 mL 0.5 mg/mL, add dense NH successively
3(300 μ L), hydrazine hydrate (20 μ L) and β-CDP (80 mg), then obtain the β-CDP-Grp of 0.25 mg/mL at 60 DEG C of stirring in water bath 4 h; Pipette above-mentioned solution 5 mL and 6.9 μ L pyrroles, added 5.0 mL 0.5 mol/L H
2sO
4in solution, heating for dissolving; Solution after dissolving was led to high pure nitrogen after 15 minutes, and take PGE as working electrode, Ag/AgCl electrode is contrast electrode, platinum electrode is to electrode, adopt constant potential 0.7 V polymerization, take out electrode ultrapure water after polymerase 17 0 s and fully wash, obtained modified electrode β-CDP-Grp/Ppy/PGE.With β-CDP-Grp/Ppy/PGE for working electrode, Ag/AgCl electrode is contrast electrode, and platinum electrode is to electrode, utilizes differential pulse voltammetry to carry out electrochemical measurement to polychlorinated biphenyl.
For an electrochemical method for rapid screening polychlorinated biphenyl, concrete steps are:
(1) 10 are being contained
-4mol × L
-110 mL 0.1 mol × L of ferrocene
-1in the electrolytic cell of KCl solution, with β-CDP-Grp/Ppy/PGE for working electrode, Ag/AgCl electrode is contrast electrode, and platinum electrode is to electrode; Experiment is carried out on CHI625B Electrochemical Comprehensive Tester, and its attached computer software is made for the acquisition and processing of experimental data; In-0.2 ~ 0.6 V potential range, carry out differential pulse scanning, record differential pulse voltammetry voltammogram, measures peak point current, is blank peak point current
i p0;
(2) getting a certain amount of polychlorinated biphenyl solution with microsyringe joins in electrolytic cell, carries out differential pulse scanning, and record differential pulse voltammetry voltammogram, measures peak point current
i p1, calculate the difference DELTA adding peak current after polychlorinated biphenyl
i p1(
i p1-
i p0); According to said method, add the polychlorinated biphenyl standard solution of variable concentrations, the difference DELTA of corresponding peak current can be obtained
i p, peak point current difference DELTA
i pgood linear relationship is presented with the logarithm of polychlorinated biphenyl concentration;
The range of linearity of polychlorinated biphenyl 1016 is 1.0 × 10
-13~ 1.0 × 10
-5mol × L
-1, linear equation is Δ
i p=-0.6779lg
c-9.4093,
cbe concentration, unit is mol × L
-1, peak current
i punit is μ A, linearly dependent coefficient R
2=0.9976, detect and be limited to 5.0 × 10
-14mol × L
-1;
The range of linearity of polychlorinated biphenyl 1232 is 1.0 × 10
-13~ 1.0 × 10
-5mol × L
-1, linear equation is Δ
i p=-0.2729lg
c-3.8541,
cbe concentration, unit is mol × L
-1, peak current
i punit is μ A, linearly dependent coefficient R
2=0.9991, detect and be limited to 1.0 × 10
-14mol × L
-1;
The range of linearity of PCB126 0 is 1.0 × 10
-11~ 1.0 × 10
-5mol × L
-1, linear equation is Δ
i p=-0.2221lg
c-2.6469,
cbe concentration, unit is mol × L
-1, peak current
i punit is μ A, linearly dependent coefficient R
2=0.9858, detect and be limited to 1.0 × 10
-12mol × L
-1;
The range of linearity of polychlorinated biphenyl 1248 is 1.0 × 10
-11~ 1.0 × 10
-5mol × L
-1, linear equation is Δ
i p=-0.4241lg
c-5.1723,
cbe concentration, unit is mol × L
-1, peak current
i punit is μ A, linearly dependent coefficient R
2=0.9990, detect and be limited to 1.0 × 10
-12mol × L
-1;
The range of linearity of polychlorinated biphenyl 1254 is 1.0 × 10
-11~ 1.0 × 10
-5mol × L
-1, linear equation is Δ
i p=-0.4534lg
c-5.280,
cbe concentration, unit is mol × L
-1, peak current
i punit is μ A, linearly dependent coefficient R
2=0.9992, detect and be limited to 3.0 × 10
-12mol × L
-1;
The range of linearity of polychlorinated biphenyl 1221 is 1.0 × 10
-13~ 1.0 × 10
-5mol × L
-1, linear equation is Δ
i p=-0.3000lg
c-4.1439,
cbe concentration, unit is mol × L
-1, peak current
i punit is μ A, linearly dependent coefficient R
2=0.9985, detect and be limited to 1.0 × 10
-14mol × L
-1;
The range of linearity of polychlorinated biphenyl 1242 is 1.0 × 10
-12~ 1.0 × 10
-5mol × L
-1, linear equation is Δ
i p=-0.5046lg
c-6.2219,
cbe concentration, unit is mol × L
-1, peak current
i punit is μ A, linearly dependent coefficient R
2=0.9989, detect and be limited to 2.0 × 10
-13mol × L
-1;
The range of linearity containing the standard model of 7 kinds of polychlorinated biphenyl is 7.0 × 10
-13~ 7.0 × 10
-6mol × L
-1, linear equation is Δ
i p=-0.3976lgc-5.6116,
cbe concentration, unit is mol × L
-1, peak current
i punit is μ A, linearly dependent coefficient R
2=0.9948, detect and be limited to 1.0 × 10
-13mol × L
-1;
(3) in conjunction with the above-mentioned linear relationship containing the standard model of 7 kinds of polychlorinated biphenyl, testing sample is measured: containing 10
-4mol × L
-110 mL 0.1 mol × L of ferrocene
-1in the electrolytic cell of KCl solution, with β-CDP-Grp/Ppy/PGE for working electrode, Ag/AgCl electrode is contrast electrode, and platinum electrode is to electrode; Experiment is carried out on CHI625B Electrochemical Comprehensive Tester, and its attached computer software is made for the acquisition and processing of experimental data; Differential pulse scanning is carried out, record differential pulse voltammetry voltammogram in-0.2 ~ 0.6 V potential range; Then add a certain amount of solution to be measured, in-0.2 ~ 0.6 V potential range, carry out differential pulse scanning, record differential pulse voltammetry voltammogram, obtains the difference DELTA of peak current
i p, by Δ
i pbring above-mentioned equation into, the concentration calculating polychlorinated biphenyl in liquid to be measured can be asked.
Beneficial effect of the present invention is: a kind of electrochemical method for rapid screening polychlorinated biphenyl, polychlorinated biphenyl and ferrocene is utilized to there is competition mechanism when forming host-guest complex with cyclodextrin, when making electrochemically to study, after add polychlorinated biphenyl in the solution containing probe molecule ferrocene, different due to ferrocene and polychlorinated biphenyl and cyclodextrin Host-guest Recognition ability, polychlorinated biphenyl, by the position of ferrocene in substituted cyclodextrin cavity, makes ferrocene reduce at the peak current of electrode surface.A kind of electrochemical method can be set up accordingly to study the competitive relation of polychlorinated biphenyl and ferrocene, thus realize the rapid screening of polychlorinated biphenyl.
A kind of electrochemical method for rapid screening polychlorinated biphenyl, the ferrocene that there is competition mechanism between tested polychlorinated biphenyl is adopted to detect polychlorinated biphenyl as probe molecule, change according to the electrochemical signals of ferrocene at electrode surface, by measuring the content of polychlorinated biphenyl in solution to the detection of intensity of variation.This modified electrode makes easier, and good stability is nontoxic, and this assay method effectively reduces the interference of coexisting substances, has high selectivity to polychlorinated biphenyl, high sensitivity.
accompanying drawing illustrates:
Figure 1 shows that the cyclic voltammogram of naked PGE and β-CDP-Grp/Ppy/PGE.
Figure 2 shows that the DPV oxidation peak figure that the standard model containing 7 kinds of polychlorinated biphenyl affects modified electrode electrochemical signals.
Figure 3 shows that peak current difference of the present invention and lg
clinear relationship chart.
Figure 4 shows that Δ
i pwith the log-linear graph of a relation of polychlorinated biphenyl 1016, polychlorinated biphenyl 1232, PCB126 0, polychlorinated biphenyl 1248, polychlorinated biphenyl 1254, polychlorinated biphenyl 1221, polychlorinated biphenyl 1242 concentration, containing 10
-4mol × L
-110 mL 0.1 mol × L of ferrocene
-1kCl solution is end liquid.
Wherein, polychlorinated biphenyl concentration 0,7.0 × 10 is represented respectively by the oxidation peak figure of a to i in Fig. 2
-13, 7.0 × 10
-12, 7.0 × 10
-11, 7.0 × 10
-10, 7.0 × 10
-9, 7.0 × 10
-8, 7.0 × 10
-7, 7.0 × 10
-6mol/L;
1-PGE, 2-β-CDP-Grp/Ppy/PGE, 3-polychlorinated biphenyl 1016,4-polychlorinated biphenyl 1232,5-PCB126 0,6-polychlorinated biphenyl 1248,7-polychlorinated biphenyl 1254,8-polychlorinated biphenyl 1221,9-polychlorinated biphenyl 1242.
embodiment:
In order to understand the present invention better, describe technical scheme of the present invention in detail with instantiation below, but the present invention is not limited thereto.
Embodiment 1
A kind of electrochemical method for rapid screening polychlorinated biphenyl, take pyrroles as conducting polymer, utilize constant potential polymerization to prepare β-CDP functionalization Grp and modify PGE, different by probe molecule ferrocene and polychlorinated biphenyl and cyclodextrin Host-guest Recognition ability, realize the electrochemical method of the rapid screening of polychlorinated biphenyl in aqueous systems.
1 pyrroles and β-CDP functionalization Grp make modified electrode, the steps include: to take 5.0 g beta-schardinger dextrin-s in 8 mL massfractions be in the NaOH solution of 33%, under room temperature, mechanical raking is spent the night, mixed solution is heated to 30 DEG C and adds rapidly 2.4 mL epichlorokydrin, acetone cessation reaction is added, with 12 mol × L after keeping 30 DEG C to stir 4 h
-1hCl regulate pH to 6.0, dries at 50 DEG C and spends the night, cooling, with HCl neutralize, suction filtration, revolves steaming and obtains β-CDP; Get the graphene oxide water solution of 20 mL 0.5 mg/mL, add dense NH successively
3(300 μ L), hydrazine hydrate (20 μ L) and β-CDP (80 mg), then obtain the β-CDP-Grp of 0.25 mg/mL at 60 DEG C of stirring in water bath 4 h; Pipette above-mentioned solution 5 mL and 6.9 μ L pyrroles, added 5.0 mL 0.5 mol/L H
2sO
4in solution, heating for dissolving; Solution after dissolving was led to high pure nitrogen after 15 minutes, and take PGE as working electrode, Ag/AgCl electrode is contrast electrode, platinum electrode is to electrode, adopt constant potential 0.7 V polymerization, take out electrode ultrapure water after polymerase 17 0 s and fully wash, obtained modified electrode β-CDP-Grp/Ppy/PGE.
2 utilize above-mentioned β-CDP-Grp/Ppy/PGE rapid screening polychlorinated biphenyl, and concrete steps are:
(1) 10 are being contained
-4mol × L
-110 mL 0.1 mol × L of ferrocene
-1in the electrolytic cell of KCl solution, with β-CDP-Grp/Ppy/PGE for working electrode, Ag/AgCl electrode is contrast electrode, and platinum electrode is to electrode; Experiment is carried out on CHI625B Electrochemical Comprehensive Tester, and its attached computer software is made for the acquisition and processing of experimental data; In-0.2 ~ 0.6 V potential range, carry out differential pulse scanning, record differential pulse voltammetry voltammogram, measures peak point current, is blank peak point current
i p0;
(2) getting a certain amount of polychlorinated biphenyl solution with microsyringe joins in electrolytic cell, carries out differential pulse scanning, and record differential pulse voltammetry voltammogram, measures peak point current
i p1, calculate the difference DELTA adding peak current after polychlorinated biphenyl
i p1(
i p1-
i p0); According to said method, add the polychlorinated biphenyl standard solution of variable concentrations, the difference DELTA of corresponding peak current can be obtained
i p, peak point current difference DELTA
i pgood linear relationship is presented with the logarithm of polychlorinated biphenyl concentration;
The range of linearity of polychlorinated biphenyl 1016 is 1.0 × 10
-13~ 1.0 × 10
-5mol × L
-1, linear equation is Δ
i p=-0.6779lg
c-9.4093,
cbe concentration, unit is mol × L
-1, peak current
i punit is μ A, linearly dependent coefficient R
2=0.9976, detect and be limited to 5.0 × 10
-14mol × L
-1;
The range of linearity of polychlorinated biphenyl 1232 is 1.0 × 10
-13~ 1.0 × 10
-5mol × L
-1, linear equation is Δ
i p=-0.2729lg
c-3.8541,
cbe concentration, unit is mol × L
-1, peak current
i punit is μ A, linearly dependent coefficient R
2=0.9991, detect and be limited to 1.0 × 10
-14mol × L
-1;
The range of linearity of PCB126 0 is 1.0 × 10
-11~ 1.0 × 10
-5mol × L
-1, linear equation is Δ
i p=-0.2221lg
c-2.6469,
cbe concentration, unit is mol × L
-1, peak current
i punit is μ A, linearly dependent coefficient R
2=0.9858, detect and be limited to 1.0 × 10
-12mol × L
-1;
The range of linearity of polychlorinated biphenyl 1248 is 1.0 × 10
-11~ 1.0 × 10
-5mol × L
-1, linear equation is Δ
i p=-0.4241lg
c-5.1723,
cbe concentration, unit is mol × L
-1, peak current
i punit is μ A, linearly dependent coefficient R
2=0.9990, detect and be limited to 1.0 × 10
-12mol × L
-1;
The range of linearity of polychlorinated biphenyl 1254 is 1.0 × 10
-11~ 1.0 × 10
-5mol × L
-1, linear equation is Δ
i p=-0.4534lg
c-5.280,
cbe concentration, unit is mol × L
-1, peak current
i punit is μ A, linearly dependent coefficient R
2=0.9992, detect and be limited to 3.0 × 10
-12mol × L
-1;
The range of linearity of polychlorinated biphenyl 1221 is 1.0 × 10
-13~ 1.0 × 10
-5mol × L
-1, linear equation is Δ
i p=-0.3000lg
c-4.1439,
cbe concentration, unit is mol × L
-1, peak current
i punit is μ A, linearly dependent coefficient R
2=0.9985, detect and be limited to 1.0 × 10
-14mol × L
-1;
The range of linearity of polychlorinated biphenyl 1242 is 1.0 × 10
-12~ 1.0 × 10
-5mol × L
-1, linear equation is Δ
i p=-0.5046lg
c-6.2219,
cbe concentration, unit is mol × L
-1, peak current
i punit is μ A, linearly dependent coefficient R
2=0.9989, detect and be limited to 2.0 × 10
-13mol × L
-1;
The range of linearity containing the standard model of 7 kinds of polychlorinated biphenyl is 7.0 × 10
-13~ 7.0 × 10
-6mol × L
-1, linear equation is Δ
i p=-0.3976lgc-5.6116,
cbe concentration, unit is mol × L
-1, peak current
i punit is μ A, linearly dependent coefficient R
2=0.9948, detect and be limited to 1.0 × 10
-13mol × L
-1;
(3) in conjunction with the above-mentioned linear relationship containing the standard model of 7 kinds of polychlorinated biphenyl, testing sample is measured: containing 10
-4mol × L
-110 mL 0.1 mol × L of ferrocene
-1in the electrolytic cell of KCl solution, with β-CDP-Grp/Ppy/PGE for working electrode, Ag/AgCl electrode is contrast electrode, and platinum electrode is to electrode; Experiment is carried out on CHI625B Electrochemical Comprehensive Tester, and its attached computer software is made for the acquisition and processing of experimental data; Differential pulse scanning is carried out, record differential pulse voltammetry voltammogram in-0.2 ~ 0.6 V potential range; Then add a certain amount of solution to be measured, in-0.2 ~ 0.6 V potential range, carry out differential pulse scanning, record differential pulse voltammetry voltammogram, obtains the difference DELTA of peak current
i p, by Δ
i pbring above-mentioned equation into, the concentration calculating polychlorinated biphenyl in liquid to be measured can be asked.
Because polychlorinated biphenyl seldom separately exists in environment, therefore must consider the impact of other materials in the rapid screening of polychlorinated biphenyl, the present invention has investigated inorganic ions common in environment and organism Na
+, Zn
2+, Mg
2+, NH
4 +, Na
+, NO
3 ?, SO
4 2, nitrophenols, amino phenol, chlorophenol is to the response condition of modified electrode, and result shows that the mensuration of these materials to polychlorinated biphenyl is not disturbed, and visible prepared β-CDP-Grp/Ppy/PGE has high selectivity to polychlorinated biphenyl.This modified electrode system overcomes the defect that general sensor cannot realize the rapid screening of electrically inactive contaminated samples, the rapid screening that can realize sample according to the change of probe molecule peak current, for the work such as ambient scene detection, the screening of pollutant sample provide new method support.
Claims (4)
1. the electrochemical method for rapid screening polychlorinated biphenyl, it is characterized in that taking pyrroles as conducting polymer, utilize constant potential polymerization to prepare poly-beta-schardinger dextrin-(β-CDP) functionalization graphene (Grp) and modify pyrolytic graphite electrode (PGE), different by probe molecule ferrocene and polychlorinated biphenyl and cyclodextrin Host-guest Recognition ability, realize the rapid screening of polychlorinated biphenyl in aqueous systems.
2. a kind of electrochemical method for rapid screening polychlorinated biphenyl according to claim 1, it is characterized in that, utilize pyrroles and β-CDP functionalization Grp make modified electrode the steps include: to take 5.0 g beta-schardinger dextrin-s in 8 mL massfractions be in the NaOH solution of 33%, under room temperature, mechanical raking is spent the night, mixed solution is heated to 30 DEG C and adds rapidly 2.4 mL epichlorokydrin, acetone cessation reaction is added, with 12 mol × L after keeping 30 DEG C to stir 4 h
-1hCl regulate pH to 6.0, dries at 50 DEG C and spends the night, cooling, with HCl neutralize, suction filtration, revolves steaming and obtains β-CDP; Get the graphene oxide water solution of 20 mL 0.5 mg/mL, add dense NH successively
3(300 μ L), hydrazine hydrate (20 μ L) and β-CDP (80 mg), then obtain the β-CDP-Grp of 0.25 mg/mL at 60 DEG C of stirring in water bath 4 h; Pipette above-mentioned solution 5 mL and 6.9 μ L pyrroles, added 5.0 mL 0.5 mol/L H
2sO
4in solution, heating for dissolving; Solution after dissolving was led to high pure nitrogen after 15 minutes, and take PGE as working electrode, Ag/AgCl electrode is contrast electrode, platinum electrode is to electrode, adopt constant potential 0.7 V polymerization, take out electrode ultrapure water after polymerase 17 0 s and fully wash, obtained modified electrode β-CDP-Grp/Ppy/PGE.
3. a kind of electrochemical method for rapid screening polychlorinated biphenyl according to claim 1, it is characterized in that, with β-CDP-Grp/Ppy/PGE for working electrode, Ag/AgCl electrode is contrast electrode, platinum electrode is to electrode, ferrocene is electrochemical probe, utilizes differential pulse voltammetry to carry out electrochemical measurement to polychlorinated biphenyl.
4. a kind of electrochemical method for rapid screening polychlorinated biphenyl according to the arbitrary claim of claim 1-3, it is characterized in that, concrete steps are:
(1) 10 are being contained
-4mol × L
-110 mL 0.1 mol × L of ferrocene
-1in the electrolytic cell of KCl solution, with β-CDP-Grp/Ppy/PGE for working electrode, Ag/AgCl electrode is contrast electrode, and platinum electrode is to electrode; Experiment is carried out on CHI625B Electrochemical Comprehensive Tester, and its attached computer software is made for the acquisition and processing of experimental data; In-0.2 ~ 0.6 V potential range, carry out differential pulse scanning, record differential pulse voltammetry voltammogram, measures peak point current, is blank peak point current
i p0;
(2) getting a certain amount of polychlorinated biphenyl solution with microsyringe joins in electrolytic cell, carries out differential pulse scanning, and record differential pulse voltammetry voltammogram, measures peak point current
i p1, calculate the difference DELTA adding peak current after polychlorinated biphenyl
i p1(
i p1-
i p0); According to said method, add the polychlorinated biphenyl standard solution of variable concentrations, the difference DELTA of corresponding peak current can be obtained
i p, peak point current difference DELTA
i pgood linear relationship is presented with the logarithm of polychlorinated biphenyl concentration;
The range of linearity of polychlorinated biphenyl 1016 is 1.0 × 10
-13~ 1.0 × 10
-5mol × L
-1, linear equation is Δ
i p=-0.6779lg
c-9.4093,
cbe concentration, unit is mol × L
-1, peak current
i punit is μ A, linearly dependent coefficient R
2=0.9976, detect and be limited to 5.0 × 10
-14mol × L
-1;
The range of linearity of polychlorinated biphenyl 1232 is 1.0 × 10
-13~ 1.0 × 10
-5mol × L
-1, linear equation is Δ
i p=-0.2729lg
c-3.8541,
cbe concentration, unit is mol × L
-1, peak current
i punit is μ A, linearly dependent coefficient R
2=0.9991, detect and be limited to 1.0 × 10
-14mol × L
-1;
The range of linearity of PCB126 0 is 1.0 × 10
-11~ 1.0 × 10
-5mol × L
-1, linear equation is Δ
i p=-0.2221lg
c-2.6469,
cbe concentration, unit is mol × L
-1, peak current
i punit is μ A, linearly dependent coefficient R
2=0.9858, detect and be limited to 1.0 × 10
-12mol × L
-1;
The range of linearity of polychlorinated biphenyl 1248 is 1.0 × 10
-11~ 1.0 × 10
-5mol × L
-1, linear equation is Δ
i p=-0.4241lg
c-5.1723,
cbe concentration, unit is mol × L
-1, peak current
i punit is μ A, linearly dependent coefficient R
2=0.9990, detect and be limited to 1.0 × 10
-12mol × L
-1;
The range of linearity of polychlorinated biphenyl 1254 is 1.0 × 10
-11~ 1.0 × 10
-5mol × L
-1, linear equation is Δ
i p=-0.4534lg
c-5.280,
cbe concentration, unit is mol × L
-1, peak current
i punit is μ A, linearly dependent coefficient R
2=0.9992, detect and be limited to 3.0 × 10
-12mol × L
-1;
The range of linearity of polychlorinated biphenyl 1221 is 1.0 × 10
-13~ 1.0 × 10
-5mol × L
-1, linear equation is Δ
i p=-0.3000lg
c-4.1439,
cbe concentration, unit is mol × L
-1, peak current
i punit is μ A, linearly dependent coefficient R
2=0.9985, detect and be limited to 1.0 × 10
-14mol × L
-1;
The range of linearity of polychlorinated biphenyl 1242 is 1.0 × 10
-12~ 1.0 × 10
-5mol × L
-1, linear equation is Δ
i p=-0.5046lg
c-6.2219,
cbe concentration, unit is mol × L
-1, peak current
i punit is μ A, linearly dependent coefficient R
2=0.9989, detect and be limited to 2.0 × 10
-13mol × L
-1;
The range of linearity containing the standard model of 7 kinds of polychlorinated biphenyl is 7.0 × 10
-13~ 7.0 × 10
-6mol × L
-1, linear equation is Δ
i p=-0.3976lgc-5.6116,
cbe concentration, unit is mol × L
-1, peak current
i punit is μ A, linearly dependent coefficient R
2=0.9948, detect and be limited to 1.0 × 10
-13mol × L
-1;
(3) in conjunction with the above-mentioned linear relationship containing the standard model of 7 kinds of polychlorinated biphenyl, testing sample is measured: containing 10
-4mol × L
-110 mL 0.1 mol × L of ferrocene
-1in the electrolytic cell of KCl solution, with β-CDP-Grp/Ppy/PGE for working electrode, Ag/AgCl electrode is contrast electrode, and platinum electrode is to electrode; Experiment is carried out on CHI625B Electrochemical Comprehensive Tester, and its attached computer software is made for the acquisition and processing of experimental data; Differential pulse scanning is carried out, record differential pulse voltammetry voltammogram in-0.2 ~ 0.6 V potential range; Then add a certain amount of solution to be measured, in-0.2 ~ 0.6 V potential range, carry out differential pulse scanning, record differential pulse voltammetry voltammogram, obtains the difference DELTA of peak current
i p, by Δ
i pbring above-mentioned equation into, the concentration calculating polychlorinated biphenyl in liquid to be measured can be asked.
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| CN107121484A (en) * | 2017-05-19 | 2017-09-01 | 济南大学 | A kind of electrochemical method of Sensitive Detection glyphosate |
| CN114166917A (en) * | 2020-08-24 | 2022-03-11 | 南开大学 | Method for electrochemically separating, detecting and releasing exosomes |
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