CN101706431A - Chemiluminescence method for detecting organophosphorus pesticide - Google Patents
Chemiluminescence method for detecting organophosphorus pesticide Download PDFInfo
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- CN101706431A CN101706431A CN200910062644A CN200910062644A CN101706431A CN 101706431 A CN101706431 A CN 101706431A CN 200910062644 A CN200910062644 A CN 200910062644A CN 200910062644 A CN200910062644 A CN 200910062644A CN 101706431 A CN101706431 A CN 101706431A
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Abstract
The invention discloses a chemiluminescence method for detecting an organophosphorus pesticide, and belongs to the field of pesticide residue analysis and the technical field of chemiluminescence analysis. The method comprises the following steps: 1, selecting a chemiluminescence system; 2, selecting a sensitizer; 3, performing single factor and orthogonal tests; 4, performing interference tests; 5, drawing a standard curve; 6, analyzing a sample; 7, researching a chemiluminescence mechanism; and 8, researching a relationship between a structure of the pesticide and chemiluminescence. The method has the advantages of simple and quick operation, wide linear range and low cost; an inorganic salt NaCl serves as the sensitizer of the system for the first time so as to improve the sensitivity of the system; and the method is suitable for detecting residue of organophosphorus pesticides with similar structures.
Description
Technical field
The invention belongs to pesticide residue analysis field and chemiluminescence analytical technique field, be specifically related to a kind of chemiluminescence method that detects organophosphorus pesticide.
Background technology
Organophosphorus pesticide is to contain the C-P key, or C-O-P, or C-S-P, or the organic compound of C-N-P key.After Germany found that organophosphorus had powerful insecticidal effect in 1938, begin to be widely used in agricultural.China now can produce more than 40 kind with the supply home market since development and production organophosphorus pesticide in 1956, has become one of world pesticide producing big country.After nineteen eighty-three, China began to have forbidden organo-chlorine pesticides such as benzene hexachloride and D.D.T. (dichloro-diphenyl-trichloroethane), organophosphorus pesticide became the agricultural chemicals of China's use amount maximum.At present, the pesticide species on China's agricultural chemicals market mainly contains organophosphorus pesticide, carbamate chemicals for agriculture, pyrethroid pesticide and biological pesticide.Because various factorss such as price and use habits, organophosphorus pesticide is still main pesticide species.
Because the widespread use of organophosphorus pesticide causes food that pesticide residual contamination has in various degree taken place.
Organophosphorus pesticide belongs to neural poison to people's toxicity, can pass through skin, respiratory tract and intestines and stomach and absorb poisoning, and particularly fat-soluble organophosphorus pesticide solution absorbs faster through skin.Main effect is the cholinesterase that suppresses in the body, make at neural tie point and can not be hydrolyzed to acetylcholine for realizing the acetylcholine that neurotransmission produces, thereby cause because of acetylcholine in vivo bulk deposition cause poisoning by acetylcholine.Cause the disorder of human nerve function, cause parasympathetic, sympathetic and neural inhibition and the neural excitement in parasympathetic joint back.In addition, organophosphorus pesticide tends to be oxidized to the compound bigger than original toxicity in vivo.For example pesticide metabolism such as thimet, disulfoton is first sulfone and second sulfone, and toxicity is bigger than substance thing.
So far, the method that is used to detect organophosphorus pesticide both at home and abroad mainly contains vapor-phase chromatography, liquid phase chromatography, immunoassay, enzyme and suppresses method, biology sensor method etc.
1, vapor-phase chromatography fast because of its high selectivity, high-effect, high sensitivity, speed, use wide, amount of samples is few, simultaneously the compartment analysis multicomponent mixture, be easy to characteristics such as robotization, being most widely used in the organophosphorus pesticide residual quantity analysis, the method maturation; But the agricultural chemicals for boiling point height or poor heat stability can not directly carry out separation detection, need carry out derivatization treatment.So just increase the difficulty of sample pre-treatments inevitably, be unfavorable for the flexible Application of Pesticides Testing and grasp fast; The versatility of GC in pesticide residue analysis is also poor simultaneously.
Though 2, high performance liquid chromatography has advantages such as high separating efficiency, high sensitivity.But all than relatively large, expensive, cost is higher for the same its equipment with vapor-phase chromatography.The moving phase majority is with poisonous solvent in addition, as acetonitrile, methyl alcohol etc., lab assistant and environment has also been caused certain harm.And high performance liquid chromatography is long required analysis time, need carry out pre-treatment to sample, and the pre-treatment process of sample is more complicated often, is unfavorable for fast detecting.
3, prerequisite and the key of utilizing immunoassay to detect organophosphorus pesticide is to prepare specific antibody, and organophosphorus pesticide belongs to small-molecule substance, must connect with macromolecular substances (as protein), could be used as immunogene.And immunogenic making is complicated, be difficult to obtain, so immunoassay has certain limitation in the application of mensuration organophosphorus pesticide.
Though 4, utilize the biosensor assay organophosphorus pesticide easy, quick, sensitive, but of a sort organophosphorus pesticide had same inhibiting effect with acetylcholinesterase, therefore this class sensor selectivity is not high. and enzyme is very unstable, there is deactivation phenomenom, organophosphorus pesticide is irreversible to the inhibition of enzyme, enzyme electrode can not be reused, and cost is high. and it is low that enzyme suppresses method sensitivity, generally only is applicable to qualitative and half-quantitative detection.
Art methods is because detection sensitivity is low and unfavorable factors such as analysis operation complicacy, instrument costliness are very restricted, so be badly in need of seeking a kind of quick, easy, highly sensitive, reliable, low cost method that can detect organophosphorus pesticide.
Chemiluminescence (Chemiluminescence, be called for short CL), be chemiluminescent substance after the oxidation of the catalysis of catalyzer or oxygenant, form the intermediate of an excited state, when this excited state intermediate is got back to stable ground state, launch photon simultaneously, can utilize luminous measuring instrument measuring light quantum yield.Owing to have advantages such as sensitivity, easy, quick, low cost, in recent years, the research of chemiluminometry on pesticide residue analysis is used and is received much concern.It is to carry out some special chemical reactions with luminescent substance luminol (Luminol), lucigenin (Lucigenin) etc. and organophosphorus pesticide that chemoluminescence method detects organophosphorus pesticide, the intermediate of reaction or reaction product have absorbed chemical energy that reaction discharged and the excited state that jumps, when coming back to ground state, emit photon, photon by photomultiplier and amplifier after, change electric current into, and be exaggerated, under certain condition, size of current is directly proportional with the concentration of organophosphorus pesticide.
A kind of chemiluminescent organophosphorus pesticide residual analyzer and detection method thereof are disclosed in the patented claim of Chinese invention patent publication number 1664567A.This detection method with potassium persulfate under titanium dioxide nano-particle and the ultraviolet catalytic with vegetables or fruit on organophosphorus pesticide be decomposed into phosphate, phosphate and molybdate and vanadate form phosphorus molybdenum vanadium heteropolyacid, the oxidation luminol solution, produce chemiluminescence, carry out quantitatively recording the total amount of organophosphorus pesticide on vegetables or the fruit according to chemiluminescence intensity.But there is following defective in this patent: patent is declared can be used for mensuration to organophosphorus pesticide total amount on vegetables or the fruit, but organophosphorus pesticide is of a great variety, this patent only provides the chemiluminescence detection to metrifonate, DDVP, omethoate, can not determine whether necessarily can detect the different organophosphorus pesticide of other chemical constitution structures, thinking of therefore can not taking a part for the whole can detect residual total amount.
Summary of the invention
The objective of the invention is to overcome the shortcoming and defect that prior art exists, a kind of chemiluminescence method that detects organophosphorus pesticide is provided.
The object of the present invention is achieved like this:
Adopt the sensitizer of NaCl first, choose and contain as system
The organophosphorus pesticide of group is a research object, provides a kind of to the general chemical luminescence detection method of the organophosphorus pesticide of structural similarity.
At first, phoxim, chlopyrifos, the luminous signal of fenifrothion in different chemical luminous systems are screened, to select best chemical luminous system by a large amount of experiments; After definite optimum response system luminol-hydrogen peroxide system, based on phoxim, chlopyrifos, the enhanced sensitivity signal of fenifrothion in system is fainter, in order to increase the sensitivity of reaction, investigate five kinds of inorganic ion (KBr in the experiment, NaBr, NaCl, KI, KCl) and six kinds of surfactant [three kinds of non-ionics Tween-80s, polyglycol-400, Triton X-100, a kind of cationic surfactant bromohexadecane base Trimethylamine (CTMAB), two kinds of anionic surfactant sodium dodecylbenzene sulfonate (SDBS), lauryl sodium sulfate (SDS)] to the enhanced sensitivity power of system, determine that finally NaCl is best sensitizer; Luminol concentration, H have been compared by single factor and orthogonal experiment
2O
2Concentration, NaCl concentration and pH are to phoxim, chlopyrifos, the influence of fenifrothion chemiluminescence intensity, under optimization technology, measure the range of linearity, do the selectivity of interference experiment verification method, simultaneously sample is analyzed and is done recovery experiment. in addition from the kinetic curve of system, fluorescent spectroscopy, desk study is carried out to chemiluminescence mechanism in four aspects of the experimental fact of ultraviolet spectral analysis and chemiluminescence reaction, and proposition phoxim, chlopyrifos, the possible mechanism of fenifrothion and luminol-hydroperoxidation. simultaneously, the chemical constitution of agricultural chemicals and the relation between the chemiluminescence are proposed.
Specifically, the present invention includes the following step:
1. the selection of chemical luminous system
Investigated organophosphorus pesticide at three kinds of chemical luminous system KMnO
4System, luminol-KMnO
4System and luminol-H
2O
2Chemiluminescence behavior in the system determines that best chemical luminophor is luminol-H
2O
2System;
2. the selection of sensitizer
Investigation is in the presence of sensitizer KBr, NaBr, NaCl, KI, KCl, Tween-80, polyglycol-400, Triton X-100, CTMAB, SDBS and SDS, and organophosphorus pesticide is at luminol-H
2O
2The intensity of chemiluminescence signal in the system determines that NaCl is best sensitizer;
3. experiment of single factor and orthogonal experiment
Relatively determine the optimum reaction condition of system by single factor and orthogonal experiment:
Luminol concentration is 1 * 10
-5Mol/L～1 * 10
-3Mol/L,
H
2O
2Concentration is 0.05mol/L～0.5mol/L,
NaCl concentration is 0.5mol/L～5mol/L,
PH is 11～13.5;
4. interference experiment
The ion or the compound that may exist in to actual sample under the 3. determined condition of step carry out interference experiment;
5. the drafting of typical curve
Drawing standard curve under the 3. determined condition of step is a horizontal ordinate with the concentration of organophosphorus pesticide, is the ordinate curve plotting with the chemiluminescence intensity of organophosphorus pesticide in system, and chemiluminescence intensity and agricultural chemicals are in concentration 1 * 10
-8G/mL～1 * 10
-6Present good linear relationship in the g/mL scope;
6. sample analysis
Equivalent takes by weighing two parts in sample in the beaker of 250mL, and a copy of it adding distil water soaked 1 hour and washing, got cleansing solution as sample a; The certain density organophosphorus pesticide of configuration is sprayed onto on another duplicate samples, places after 2 hours and wash, get cleansing solution as sample b, working sample a and sample b with distilled water;
The discussion of 7. chemiluminescence mechanism
Adopt RF-5301PC type fluorospectrophotometer and UV-1700 ultraviolet-visible pectrophotometer to measure the fluorescence spectrum and the ultraviolet spectrum of system respectively, desk study is carried out to chemiluminescence mechanism in four aspects of the experimental fact of the kinetic curve of system and reaction in addition, proposes organophosphorus pesticide and luminol-H
2O
2The possible mechanism of reaction;
8. the structure of agricultural chemicals and the relation between the chemiluminescence
To the Study on Chemiluminescence of organophosphorus pesticides such as phoxim, chlopyrifos, fenifrothion, Entex, DDVP, phosphamidon, parathion, Azodrin, Hostathion, parathion-methyl, malathion, discussion contains
The structure of the organophosphorus pesticide of group and the relation between the chemiluminescence.
The present invention has following advantage and good effect:
1, simple to operate, quick, the range of linearity is wide, and cost is low;
2, proposed the sensitizer as system first, increased the sensitivity of system with inorganic salts NaCl.
3, be applicable to detection to organophosphorus pesticide with analog structure.
Description of drawings
Fig. 1 is the graph of a relation between luminol concentration and the organophosphorus pesticide chemiluminescence intensity Δ I;
Fig. 2 is H
2O
2Graph of a relation between concentration and the organophosphorus pesticide chemiluminescence intensity Δ I;
Fig. 3 is the graph of a relation between NaCl concentration and the organophosphorus pesticide chemiluminescence intensity Δ I;
Fig. 4 is the graph of a relation between pH and the organophosphorus pesticide chemiluminescence intensity Δ I;
Fig. 5 is a phoxim standard colors spectrogram;
Fig. 6 is the blank chromatogram of sample pakchoi;
Fig. 7 is a sample pakchoi recovery chromatogram.
Embodiment
Describe in detail below in conjunction with drawings and Examples:
One, experiment reagent
In the following embodiments if not otherwise specified, test used reagent all from following dated information and manufacturer:
Luminol is analyzed pure sigma company
The development of phoxim standard items experiment reagent Inst. of Environment Protection ﹠ Scientific Research Monitor, Ministry of Agric
Potassium permanganate is analyzed pure Wuhan City north of the Changjiang River chemical reagent factory
Dihua worker company limited is won in the pure Tianjin of hydrogen peroxide assay
Sodium chloride is analyzed pure Jiaozhuo chemical reagent work of prosperous peace Science and Technology Co., Ltd.
Sodium bromide is analyzed pure Tianjin and is recovered fine chemistry industry research institute
Potassium iodide is analyzed pure Chemical Reagent Co., Ltd., Sinopharm Group
Potassium chloride is analyzed pure Chemical Reagent Co., Ltd., Sinopharm Group
Potassium bromide is analyzed pure Guangzhou Chemical Reagent Factory
Cobaltous sulphate is analyzed in the Hunan, pure Hunan chemical reagent and is adopted for the station
Glazier's salt is analyzed pure Shanghai Ke Chang fine chemicals company
Copper sulphate is analyzed the pure sea green source Fine Chemical Works of
Potassium nitrate is analyzed pure Shanghai Ke Chang fine chemicals company
Tertiary sodium phosphate is analyzed the rich Dihua worker company limited in pure Tianjin
Neopelex chemical pure Shanghai chemical reagent packing factory
Tween-80 is analyzed pure Amresco company
Cetyl trimethyl ammonium bromide is analyzed pure Wuhan Ya Fa Bioisystech Co., Ltd
Polyglycol-400 is analyzed chemical plant, Gansu Province, west, pure Guangdong
Lauryl sodium sulfate is analyzed Shuande, pure Guangdong chemical-biological research institute
Triton X-100 analyzes pure sigma company
Two, experimentation
In order to verify the present invention, employing this method and vapor-phase chromatography have been carried out comparison and detection to the content of organophosphorus pesticide in the vegetables.
1, the chemiluminescence reaction condition determines
As Fig. 1,2,3,4, preliminary experiment shows that phoxim is at alkaline luminol-H
2O
2Can produce faint chemiluminescence signal in the system.For improving the sensitivity of reaction, three kinds of non-ionics Triton X-100, Tween-80, PEG-400 have been investigated, a kind of cationic surfactant CTMAB, two kinds of anionic surfactant SDBS, SDS and inorganic salts KBr, NaBr, NaCl, KI, KCl etc. are to the enhancing effect of reaction luminous intensity.By discovering, in 11 kinds of sensitizers of investigation, as NaCl during as sensitizer, the background signal minimum, the luminous intensity maximum is taken all factors into consideration, and finally selects the sensitizer of NaCl as system.Compare luminol concentration (1 * 10 by single factor and orthogonal experiment
-6Mol/L～1 * 10
-3Mol/L), H
2O
2((0.5mol/L～5mol/L) and pH (pH11～13.5) are to the influence of phoxim chemiluminescence intensity, and experiment is final determines that the top condition of reaction is: luminol concentration 5 * 10 for 0.05mol/L～0.5mol/L), NaCl concentration for concentration
-4Mol/L, NaCl concentration 4mol/L, H
2O
2Concentration 0.3mol/L, pH13.
2, interference experiment
According to detection method of the present invention, tested the influence of presumable concurrent to testing in the sample.Under optimal conditions, be 5 * 10 for concentration
-7The phoxim standard solution of g/mL, being no more than level in relative error is 5% situation, can allow the existence of following concurrent: 1000 times Cl
-, K
+Interference measurement not; 500 times Na
+Interference measurement not; 100 times 5O
4 2-, NO
3 -Interference measurement not; 10 times Al
3+, CO
3 2-, PO
4 3-Interference measurement not; 5 times Pb
2+Interference measurement not; 0.1 Mg doubly
2+Interference measurement not; 0.001 Cu doubly
2+, Co
2+Interference measurement not.
3, the drafting of typical curve
Under selected top condition, phoxim is 1 * 10
-8G/mL～1 * 10
-6Linear with luminous intensity in the concentration range of g/mL, its regression equation is: y=1214.3x+95232, coefficient R is 0.9959.To concentration is 5 * 10
-7The relative standard deviation that the phoxim of g/mL carries out 11 replicate determinations continuously is 4.2%.According to IUPAC suggestion, calculate this method and detect and be limited to 5.4 * 10
-9G/mL.
4, the preparation of sample and analysis
(1) the pakchoi sample that takes by weighing 10.0g is in the beaker of 250mL, with the washing of 100mL distilled water and soaked 1 hour, gets cleansing solution as sample a; 10g pakchoi after the washing is dried, spray the phoxim of a certain amount of concentration known, place after 2 hours and wash, get cleansing solution as sample b with 100mL distilled water; Get an amount of sample a and sample b constant volume, do chemical luminescent detecting, promptly do sample experiment and recovery experiment by experimental technique.
(2) get remaining sample a and each 25mL of sample b, place the 150mL separating funnel respectively, add isopyknic dichloromethane extraction, discard water layer, with dichloromethane layer behind activated carbon decolorizing and anhydrous sodium sulfate drying, rotary evaporation concentrates near doing, and is settled to 2mL with methylene chloride, is GC by following chromatographic condition and analyzes (control experiment).
By Fig. 5,6,7 as can be known, the retention time of phoxim standard items is 6.152min, does not contain the agricultural chemicals phoxim in the gas chromatography determination pakchoi blank sample, and the retention time of the retention time of recovery sample phoxim component and phoxim standard items is coincide.
The measurement result of two kinds of methods sees Table 1.
Phoxim assay result in table 1 pakchoi
Table 1 reflects two kinds of method institute test sample product and recovery experimental result basically identical.
Verified the credibility of Novel Chemiluminescence Method thus.
Attached: GC conditions:
The attached flame luminosity of Agilent 6890N gas chromatograph (FPD) detecting device;
DB-1701 elastic quartz capillary column (30m * 0.53mm * 1.0 μ m);
Column temperature (temperature programme):
Injector temperature: 220 ℃;
Sensing chamber's temperature: 250 ℃;
N
2：5mL/min；
H
2：75mL/min；
Air: 100mL/min;
No split sampling, sample size are 1 μ L, and the peak area external standard method is quantitative.
Claims (1)
1. a chemiluminescence method that detects organophosphorus pesticide is characterized in that comprising the following steps:
1. the selection of chemical luminous system
Determine that best chemical luminophor is luminol-H
2O
2System;
2. the selection of sensitizer
Determine that NaCl is best sensitizer;
3. experiment of single factor and orthogonal experiment
Relatively determine the optimum reaction condition of system by single factor and orthogonal experiment:
Luminol concentration is 1 * 10
-5Mol/L～1 * 10
-3Mol/L,
H
2O
2Concentration is 0.05mol/L～0.5mol/L,
NaCl concentration is 0.5mol/L～5mol/L,
PH is 11～13.5;
4. interference experiment
The ion or the compound that may exist in to actual sample under the 3. determined condition of step carry out interference experiment;
5. the drafting of typical curve
Concentration with organophosphorus pesticide is horizontal ordinate, is the ordinate curve plotting with the chemiluminescence intensity of organophosphorus pesticide in system, and chemiluminescence intensity and agricultural chemicals are in concentration 1 * 10
-8G/mL～1 * 10
-6Present good linear relationship in the g/mL scope;
6. sample analysis
Equivalent takes by weighing two parts in sample in the beaker of 250mL, and a copy of it adding distil water soaked 1 hour and washing, got cleansing solution as sample a; The certain density organophosphorus pesticide of configuration is sprayed onto on another duplicate samples, places after 2 hours and wash, get cleansing solution as sample b, working sample a and sample b with distilled water;
The discussion of 7. chemiluminescence mechanism
Adopt RF-5301PC type fluorospectrophotometer and UV-1700 ultraviolet-visible pectrophotometer to measure the fluorescence spectrum and the ultraviolet spectrum of system respectively, desk study is carried out to chemiluminescence mechanism in four aspects of the experimental fact of the kinetic curve of system and reaction in addition, proposes organophosphorus pesticide and luminol-H
2O
2The possible mechanism of reaction;
8. the structure of agricultural chemicals and the relation between the chemiluminescence
To the Study on Chemiluminescence of organophosphorus pesticides such as phoxim, chlopyrifos, fenifrothion, Entex, DDVP, phosphamidon, parathion, Azodrin, Hostathion, parathion-methyl, malathion, discussion contains
The structure of the organophosphorus pesticide of group and the relation between the chemiluminescence.
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| CN102053155A (en) * | 2010-06-29 | 2011-05-11 | 华中农业大学 | Homogeneous chemiluminescence immunoassay method for measuring for organophosphorus pesticide Dursban |
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| CN102053155A (en) * | 2010-06-29 | 2011-05-11 | 华中农业大学 | Homogeneous chemiluminescence immunoassay method for measuring for organophosphorus pesticide Dursban |
| CN102175865A (en) * | 2010-12-29 | 2011-09-07 | 中国农业科学院农业质量标准与检测技术研究所 | Determination kit for triazophos chemoluminescence immunoassay and preparation method and using method thereof |
| CN102175865B (en) * | 2010-12-29 | 2013-08-21 | 中国农业科学院农业质量标准与检测技术研究所 | Preparation method of determination kit for triazophos chemoluminescence immunoassay |
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| CN102539417A (en) * | 2011-12-30 | 2012-07-04 | 宁波大学 | Device for detecting methyl parathion pesticide residue through electrochemiluminescence |
| CN102590192A (en) * | 2012-02-17 | 2012-07-18 | 中国科学院合肥物质科学研究院 | Chemical luminescence enhanced type method for detecting pesticide residues |
| CN105717089A (en) * | 2016-04-27 | 2016-06-29 | 兰州大学 | Sensor for detecting phosphorus containing pesticides and manufacture and use methods thereof |
| CN105717089B (en) * | 2016-04-27 | 2019-01-04 | 兰州大学 | Sensor and preparation and application for phosphorous Pesticides Testing |
| CN107941769A (en) * | 2017-11-29 | 2018-04-20 | 重庆大学 | A kind of detection method of parathion-methyl |
| CN107941769B (en) * | 2017-11-29 | 2020-06-02 | 重庆大学 | Method for detecting methyl parathion |
| CN109856091A (en) * | 2018-03-16 | 2019-06-07 | 北方工业大学 | Time-resolved fluorescence test strip for detecting monocrotophos and application thereof |
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