CN102590192A - Chemical luminescence enhanced type method for detecting pesticide residues - Google Patents
Chemical luminescence enhanced type method for detecting pesticide residues Download PDFInfo
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- CN102590192A CN102590192A CN2012100373366A CN201210037336A CN102590192A CN 102590192 A CN102590192 A CN 102590192A CN 2012100373366 A CN2012100373366 A CN 2012100373366A CN 201210037336 A CN201210037336 A CN 201210037336A CN 102590192 A CN102590192 A CN 102590192A
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Abstract
The invention discloses a chemical luminescence enhanced type method for detecting pesticide residues, comprising the following steps of: preparing zymoid active particles and establishing a luminol chemical luminescence system, wherein the chemical luminescence enhancement is realized by adding organic phosphorus pesticide sample containing at least one phosphorus-sulfur single bond and having a series of concentrations and a free-radical scavenger into a zymoid active particle solution; then, adding a chemical illuminant, namely a luminol solution, wherein the chemical luminescence intensity of the obtained mixture is obviously enhanced compared with that of a blank in which the equal amount of the free-radical scavenger is added only at the moment; and accordingly, determining a linear relation between a sample concentration and the chemical luminescence intensity. According to the method disclosed by the invention, a principle of inhibiting the removing of free radicals by surface coordination is firstly utilized to design a chemical luminescence enhanced type sensor, which can be used for sensitive detection of a special pesticide component. Taking organic phosphorus pesticide ethoprophos as an example, the linear range is 0.1-1000 nmol/L and 1-100 micromoles/liter and the detection limit is 0.1 nmol/L.
Description
One, technical field
The present invention relates to a kind of analytical approach of agricultural chemicals; Be particularly related to a kind of chemiluminescence analysis detection method of trace agricultural chemicals, specifically a kind of method of utilizing surface coordination to suppress the chemiluminescence enhanced detection residues of pesticides of radicals scavenging principle development.
Two, background technology
Agricultural chemicals at control crop disease, worm, crop smothering, guarantees agricultural foison as a kind of important agricultural material, promotes aspects such as high yield, high-quality, efficient modernized agricultural development bringing into play irreplaceable effect.Yet immoderate agricultural chemicals uses and bad border of ecology, food security and health has been constituted serious threat, also becomes one of focus of international trade dispute simultaneously.Because agricultural chemicals residual component content is often very little in the actual sample; The coexistence component is complicated; Therefore set up analytical approach quick, highly sensitive, high selectivity and in the residual detection of farming, seem particularly urgent, this for preserve the ecological environment, ensure human health, reduce agricultural losses, promoting economic development is of great significance.The Analytical Techniques of Pesticide Residues of China starts from the 1950's, has occurred many effective discriminatings and analyzing detecting method in recent years.At present, the lab analysis of residues of pesticides mainly depends on large-scale instrument and accomplishes with detecting in the agricultural product, for example, and vapor-phase chromatography, liquid phase chromatography, gas-matter coupling analytic approach etc.These methods are highly sensitive, but required instrument is expensive, and sample pre-treatments complicacy, length consuming time and the scene of can't accomplishing are detected.Following agricultural residual detection requires to quick scene, cheapness, minimizing solvent, reduces environmental pollution, microminiaturization and automation direction development, and this is a national challenge difficult problem that needs to be resolved hurrily with society.
Chemiluminescence analysis is highly sensitive with it, instrument and equipment simple, analyze advantages such as realizing robotization fast and easily, is bringing into play important effect in fields such as biochemical analysis, environmental monitoring and food securities.In recent years, utilize chemiluminescence method to detect residues of pesticides and also receive people's attention.People such as Roda utilize agricultural chemicals to suppress the active principle of enzyme acetylcholine (AchE), adopt the portable injection chemiluminescence method to detect organophosphorus pesticides such as paraoxon, Aldicarb, and the detectability of paraoxon and Aldicarb is respectively 0.75 μ gL
-1With 4 μ gL
-1Compare with other detection system, this method is simple, quick, and higher sensitivity and reappearance are arranged.Ayyagari etc. have reported based on alkaline phosphatase catalytic chemistry luminous detection Rogor.Alkaline phosphatase can the phosphorous acid esters generation of catalysis dephosphorylation, and Rogor suppresses the behavior of phosphate, produces faint luminous signal, and detection is limited to 500ppb.Gao etc. are fixed on the fibre tip catalytic reaction with enzyme, the luminous signal of generation through same fiber collecting, be delivered to the CCD detecting device and detect.In addition, Pande etc. utilize bioabsorbable copolymer fixedly alkaline phosphatase at a glass capillary inwall parathion-methyl etc. is detected, detectability reaches 500-700ppb.These chemical luminous systems that detect residues of pesticides all utilize enzyme to improve detection sensitivity and selectivity, so lack serviceable life, cost an arm and a leg, and are unfavorable for promoting the use of.In addition, the someone reports that utilizing the stronger peroxidating phosphate of organophosphorus pesticide formation oxidability to develop the residual detecting sensor of chemiluminescence enhancement mode farming, yet this enhancing detection method susceptibility and selectivity are all relatively poor.At present, utilize surface coordination to suppress the chemiluminescence enhanced sensor that the radicals scavenging principle constitutes and still do not have bibliographical information, nobody relates to especially to the detection of residues of pesticides for it.
Three, summary of the invention
The present invention is directed to the above-mentioned deficiency of prior art; Aim to provide the method that a kind of fast detecting phonamiphos, Profenofos etc. contain organophosphorus pesticide (thiol formula thiophosphate or the phosphorodithioate) residual quantity of at least one sulphur phosphorus singly-bound, technical matters to be solved is to utilize agricultural chemicals to disinthibite radicals scavenging to realize the chemiluminescence enhancing detection in the coordination on fermentoid active particle surface.
Described chemiluminescence signal is that oxidation chemistry luminous agent luminol produces chemiluminescence then because the dissolved oxygen DO in the fermentoid active particle catalysis water produced negative oxygen ion; At this moment if add free radical scavenger, because the free radical that produces is consumed (also claiming radicals scavenging), so chemiluminescence signal weakens until disappear (quencher).Luminous signal weakens between quencher and radicals scavenging agent content and has certain linear.
The coordination of organophosphorus pesticide on fermentoid active particle surface that contains at least one phosphorus sulphur singly-bound has the effect that free radical scavenger is removed free radical that suppresses; Therefore compare with the blank that only adds free radical scavenger; Chemiluminescence intensity obviously strengthens, and can establish the linear relationship between sample concentration and the chemiluminescence intensity in view of the above.
The present invention utilizes fermentoid active particle catalysis dissolved oxygen DO to form negative oxygen ion just and surface coordination suppresses character such as radicals scavenging, and its Combined application in chemiluminescence detection, is developed a kind of chemiluminescence enhanced detection method.
Described chemiluminescence enhancing is meant that the luminol chemiluminescence system (blank) only to add free radical scavenger is reference; After agricultural chemicals and free radical scavenger joined fermentoid active particle solution together; Add the luminous agent luminol solution again, at this moment the system chemiluminescence intensity is compared obvious enhancing with blank, when the content one of the content of free radical scavenger and luminol regularly; Along with the increase of pesticide concentration, chemiluminescence intensity grows from weak to strong gradually.The process that the corresponding chemiluminescence intensity of testing sample change in concentration scope changes.Set up the linear relationship between testing sample concentration and the chemiluminescence intensity through the chemiluminescence enhancement mode in other words, thereby realize the detection by quantitative of testing sample.
Linear relationship between the variation that to be the increase of establishing testing sample concentration grow from weak to strong with chemiluminescence intensity of the key of technical scheme of the present invention, change of luminous intensity serves as that reference relatively obtains with blank system.
Technical scheme of the present invention comprises the preparation of fermentoid active particle and the foundation of luminol chemiluminescence system; Difference with the prior art is that described chemiluminescence enhancing is that the series concentration organophosphorus pesticide sample that contains at least one phosphorus sulphur singly-bound is added in the fermentoid active particle solution with free radical scavenger; Add chemiluminescence agent luminol solution then; Compare with the blank that only adds the equivalent free radical scavenger this moment; Chemiluminescence intensity obviously strengthens, and establishes the linear relationship between sample concentration and the chemiluminescence intensity in view of the above.
Described luminol chemiluminescence system is to be made up of the luminol WS (dissolved oxygen DO is arranged in the water) and fermentoid active particle.Then constitute blank system if in this system, add free radical scavenger.
Described fermentoid active particle is to have the active nano particle of quasi-enzyme catalytic, is selected from magnetic Fe
3O
4, CoFe
2O
4Semiconductor particle such as particle or ZnO, ZnS or noble metal and various composite structures such as Au, Pb.
Described free radical scavenger is selected from ethanol or methyl alcohol.
Because chemiluminescence is derived from the mixing of two kinds of solution, for obtaining maximum chemiluminescence intensity, every kind of solution has a best working concentration in the present invention, and the best working concentration of luminol solution is 1 * 10
-4M is to magnetic Fe
3O
4The best working concentration of nano particle is 25 μ g/mL.
When selecting magnetic Fe
3O
4When nano particle and mass percentage concentration 99% ethanol are free radical scavenger, can be dissolved in that to add concentration behind 99% ethanol be the magnetic Fe of 25 μ g/mL, pH=2 with containing at least one phosphorus sulphur singly-bound organophosphorus pesticide sample
3O
4In the nano-particle solution, add concentration 1 * 10 then
-4The luminol solution of M is compared with the blank that only adds equivalent 99% ethanol, and luminous intensity obviously strengthens, and establishes the linear relationship between sample concentration and the luminous intensity in view of the above.
, linear relationship just can carry out the detection of residues of pesticides to full pattern after establishing by routine operation.
Advantage of the present invention and good effect:
The present invention utilizes surface coordination to suppress the principle of radicals scavenging first, designs the chemiluminescence enhanced sensor, and the sensitivity that can be used for specific farm chemical ingredients detects.With the organophosphorus pesticide phonamiphos is example, and its range of linearity is 0.1～1000nmol/L and 1～100 μ mol/L, detects and is limited to 0.1nmol/L.
The inventive method has all advantages of chemiluminescence sensor, as need not large-scale instrument, and fast convenient, highly sensitive, effect is remarkable.
The chemiluminescence poor anti jamming capability is because therefore complicated component can seriously disturb chemiluminescence signal in the full pattern.In the method, can overcome the interference of full pattern composition through the method for magnetic resolution.Therefore do not need complicated pre-treatment processes such as enrichment, operate simplyr, cost is lower.
Four, description of drawings
Fig. 1 utilizes surface coordination to suppress the chemiluminescence enhanced sensor synoptic diagram that the radicals scavenging principle is constructed.
Fig. 2 is to the chemiluminescence enhancing detection of phonamiphos and corresponding linear relationship chart.
Fig. 3 is the chemiluminescence enhanced sensor to adding the detection principle of agricultural chemicals and figure as a result in fruit juice, the green tea.
Fig. 4 is the selectivity test figure of chemiluminescence enhanced sensor.
Five, embodiment
Existing is free radical scavenger and magnetic Fe with mass percentage concentration 99% ethanol
3O
4Nano particle is narrated as follows for the example non-limiting examples:
1, magnetic Fe
3O
4The preparation of nano particle
List of references L.Z.Gao et al, Nat.Nanotech., the coprecipitation method of 2007,2,577 reports.
The HCl of 10 μ L is added in the 20mL deionized water, and letting nitrogen in and deoxidizing added the FeCl of 2.4g after 30 minutes
24H
2The FeCl of O and 4.6g
36H
2O, ultrasonic dissolution after filter transfer in the deionized water that the 80mL letting nitrogen in and deoxidizing crosses, and keep nitrogen atmosphere.Subsequently, the ammoniacal liquor of 10mL dropwise is added in the above-mentioned solution, the rapid flavescence of solution, and color deepens gradually, and then blackening.Dropwise, system is warming up to 40 ℃, reacted 0.5 hour, be warmed up to 85 ℃ of reactions 2 hours again.Behind centrifuge washing, be distributed to again in the deionized water, subsequent use.Can find out that from the XRD style particle that obtains is a cube phase Fe
3O
4, crystallite dimension 10nm.Before using magnetic particle is diluted in the deionized water of pH=2, concentration is 25 μ g/mL.
2, the confirming of linear relationship between phonamiphos concentration and the luminous intensity
Phonamiphos is dissolved in the ethanolic solution, is made into the solution of series concentration (1-60 μ M).The magnetic particle dilution of 30 μ L being added in the hole of Chemiluminescence Apparatus 96 orifice plates, add the phonamiphos ethanolic solution of 30 μ L again, behind the vibration 10s, add the chemiluminescence in this hole of 90 μ L luminol solutions test, is standard with the highest peak.For confirming the chemiluminescence detection signal, needing luminous with the system of simple adding 30 μ L ethanol is reference, can find out that through contrast phonamiphos has strengthened chemiluminescence, and along with the increase chemiluminescence intensity of phonamiphos concentration increases gradually, shown in Fig. 2 A.Therefore the concentration that can come the quantitative test phonamiphos through the luminous enhancing amount of chemistry, shown in Fig. 2 B, its range of linearity has two parts to constitute, and is respectively 0.1～1000nmol/L and 1～100 μ mol/L, detects and is limited to 0.1nmol/L.
3, to adding the detection of agricultural chemicals in grape juice and the green tea
If directly detect the pesticide molecule in the grape juice, because the interference of internal component can not obtain chemiluminescence signal.And in the method, the process (Fig. 3) of the absorption-separation through magnetic particle-disperse again can effectively overcome the interference of full pattern composition, thereby realize the detection to actual sample.Typically; The ethanolic solution that contains finite concentration agricultural chemicals phonamiphos is added in the grape juice, stir and add magnetic particle after 5 minutes, continue to stir and made the agricultural chemicals coordination be attached to particle surface in 10 minutes; Then; Through externally-applied magnetic field magnetic particle is separated, discard fruit juice solution and add a certain amount of deionized water (pH=2) again, the control particle concentration is 25 μ g/mL.According to same step, in grape juice, add the ethanolic solution that does not contain agricultural chemicals and obtain reference particle solution.Carry out chemiluminescent assay and detection according to step 2, because pesticide molecule coordination is attached on the magnetic particle, the ethanol that therefore only needs to add 30 μ L gets final product.Same process also is used in the green tea to add the detection of agricultural chemicals, but because complicated more composition, need carry out the process of twice separation-disperse again.
4, magnetic Fe
3O
4The selectivity test of nano particle
Chemiluminescence susceptibility is high, but poor selectivity.The present invention is to magnetic Fe
3O
4Nano particle is selected phonamiphos EP, Profenofos PF, metrifonate DL, chlopyrifos CP, parathion-methyl PM, 2,4-dichlorphenoxyacetic acid 2, and 4-D tests.As shown in Figure 4, be 1 * 10 in concentration
-4Under the condition of M, phonamiphos causes the enhancing of 18 times of chemiluminescence intensities, and the intensification factor of Profenofos is 10, and other agricultural chemicals does not have influence basically to chemiluminescence.Contrast above-mentioned several kinds of Pesticide Molecule structures, can find out that this system can selectivity detects the farm chemical ingredients that contains sulphur phosphorus singly-bound such as phonamiphos, Profenofos.
Claims (4)
1. the method for chemiluminescence enhanced detection residues of pesticides; Comprise the preparation of fermentoid active particle and the foundation of luminol chemiluminescence system; It is characterized in that: it is that the series concentration organophosphorus pesticide sample that contains at least one phosphorus sulphur singly-bound is added in the fermentoid active particle solution with free radical scavenger that described chemiluminescence strengthens; Add chemiluminescence agent luminol solution then; Compare with the blank that only adds the equivalent free radical scavenger this moment, and chemiluminescence intensity obviously strengthens, and establishes the linear relationship between sample concentration and the chemiluminescence intensity in view of the above.
2. method according to claim 1 is characterized in that: described fermentoid active particle is to have the active nano particle of quasi-enzyme catalytic, is selected from magnetic Fe
3O
4, CoFe
2O
4Particle or ZnO, ZnS semiconductor particle or Au, Pb noble metal and various composite structure.
3. method according to claim 1 is characterized in that: described free radical scavenger is selected from ethanol or methyl alcohol.
4. method according to claim 1 is characterized in that: the series concentration organophosphorus pesticide sample that will contain at least one phosphorus sulphur singly-bound is dissolved in that to add concentration behind 99% ethanol be the magnetic Fe of 25 μ g/mL, pH=2
3O
4In the nano-particle solution, add concentration 1 * 10 then
-4The luminol solution of M is compared with the blank that only adds equivalent 99% ethanol, and luminous intensity obviously strengthens, and establishes the linear relationship between sample concentration and the luminous intensity in view of the above.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103389301A (en) * | 2013-08-01 | 2013-11-13 | 辛焕发 | Method for fast detecting pesticide residue |
| CN110186912A (en) * | 2019-05-20 | 2019-08-30 | 济南大学 | A method of based on thiocholine coreaction promotor electrogenerated chemiluminescence aptamer sensor and measurement chlopyrifos |
| CN113791064A (en) * | 2021-09-08 | 2021-12-14 | 武汉谱信环保科技有限公司 | Rapid detection method of quinalphos pesticide residue |
| CN115308180A (en) * | 2022-08-08 | 2022-11-08 | 青岛农业大学 | Fluorescent zinc oxide quantum dot, and preparation method and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993023756A1 (en) * | 1992-05-08 | 1993-11-25 | Monitor Diagnostics, Inc. | Use of nonmetallic tetrapyrrole molecules and novel signal solutions in chemiluminescent reactions and assays |
| WO2002022861A1 (en) * | 2000-09-13 | 2002-03-21 | California Institute Of Technology | Oxygenase enzymes and screening method |
| CN1664567A (en) * | 2005-03-14 | 2005-09-07 | 陕西师范大学 | Chemiluminescent organophosphorus pesticide residual analyzer and detecting method thereof |
| CN101148584A (en) * | 2007-11-15 | 2008-03-26 | 上海交通大学 | Method for catalyzing and enhancing chemical luminescence by nano particles |
| CN101706431A (en) * | 2009-06-09 | 2010-05-12 | 华中农业大学 | Chemiluminescence method for detecting organophosphorus pesticide |
| CN102053085A (en) * | 2009-10-28 | 2011-05-11 | 中国科学院高能物理研究所 | Method for detecting glucose by ferroferric oxide nano particle catalytic chemiluminescence |
| CN102191034A (en) * | 2010-03-03 | 2011-09-21 | 中国科学技术大学 | N-(4-aminobutyl)-N-ethylisoluminol luminescence functionalized nanogold, and preparation method and application thereof |
| CN102221529A (en) * | 2011-03-31 | 2011-10-19 | 吉林大学 | Method for rapidly detecting residuals of organophosphorus pesticides in vegetables by utilizing Au nano-particle colorimetric method |
-
2012
- 2012-02-17 CN CN201210037336.6A patent/CN102590192B/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993023756A1 (en) * | 1992-05-08 | 1993-11-25 | Monitor Diagnostics, Inc. | Use of nonmetallic tetrapyrrole molecules and novel signal solutions in chemiluminescent reactions and assays |
| WO2002022861A1 (en) * | 2000-09-13 | 2002-03-21 | California Institute Of Technology | Oxygenase enzymes and screening method |
| CN1664567A (en) * | 2005-03-14 | 2005-09-07 | 陕西师范大学 | Chemiluminescent organophosphorus pesticide residual analyzer and detecting method thereof |
| CN101148584A (en) * | 2007-11-15 | 2008-03-26 | 上海交通大学 | Method for catalyzing and enhancing chemical luminescence by nano particles |
| CN101706431A (en) * | 2009-06-09 | 2010-05-12 | 华中农业大学 | Chemiluminescence method for detecting organophosphorus pesticide |
| CN102053085A (en) * | 2009-10-28 | 2011-05-11 | 中国科学院高能物理研究所 | Method for detecting glucose by ferroferric oxide nano particle catalytic chemiluminescence |
| CN102191034A (en) * | 2010-03-03 | 2011-09-21 | 中国科学技术大学 | N-(4-aminobutyl)-N-ethylisoluminol luminescence functionalized nanogold, and preparation method and application thereof |
| CN102221529A (en) * | 2011-03-31 | 2011-10-19 | 吉林大学 | Method for rapidly detecting residuals of organophosphorus pesticides in vegetables by utilizing Au nano-particle colorimetric method |
Non-Patent Citations (6)
| Title |
|---|
| ANDREW L. ROSE AND T. DAVID WAITE: "Chemiluminescence of Luminol in the Presence of Iron(II) and Oxygen:Oxidation Mechanism and Implications for Its Analytical Use", 《ANAL.CHEM.》 * |
| HUI WEI AND ERKANG WANG: "Fe3O4 Magnetic nanoparticles as peroxidase mimetics and their applications in H2O and Glucose detection", 《ANAL.CHEM.》 * |
| 刘晓宇等: "蔬菜中有机磷农药辛硫磷的化学发光分析研究", 《分析化学》 * |
| 林洁华等: "基于固定化纳米金增强化学发光双酶传感器测定葡萄糖", 《中国科学(B辑:化学)》 * |
| 熊志刚等: "磁性纳米粒子固定葡萄糖氧化酶修饰电极电致化学发光葡萄糖传感器", 《分析化学》 * |
| 饶志明等: "流动注射化学发光测定甲基对硫磷", 《分析化学》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103389301A (en) * | 2013-08-01 | 2013-11-13 | 辛焕发 | Method for fast detecting pesticide residue |
| CN110186912A (en) * | 2019-05-20 | 2019-08-30 | 济南大学 | A method of based on thiocholine coreaction promotor electrogenerated chemiluminescence aptamer sensor and measurement chlopyrifos |
| CN110186912B (en) * | 2019-05-20 | 2021-07-06 | 济南大学 | Electrochemiluminescence aptamer sensor based on thiocholine co-reaction accelerator and method for determining chlorpyrifos |
| CN113791064A (en) * | 2021-09-08 | 2021-12-14 | 武汉谱信环保科技有限公司 | Rapid detection method of quinalphos pesticide residue |
| CN113791064B (en) * | 2021-09-08 | 2024-03-12 | 武汉谱信环保科技有限公司 | Rapid detection method for quinfos pesticide residue |
| CN115308180A (en) * | 2022-08-08 | 2022-11-08 | 青岛农业大学 | Fluorescent zinc oxide quantum dot, and preparation method and application thereof |
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