CN106370708A - Electrochemistry sensor for measuring organophosphorus pesticide residues and measurement method thereof - Google Patents
Electrochemistry sensor for measuring organophosphorus pesticide residues and measurement method thereof Download PDFInfo
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- CN106370708A CN106370708A CN201610754304.6A CN201610754304A CN106370708A CN 106370708 A CN106370708 A CN 106370708A CN 201610754304 A CN201610754304 A CN 201610754304A CN 106370708 A CN106370708 A CN 106370708A
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- organophosphorus pesticide
- detection
- electrochemical
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- residual quantity
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- 239000003987 organophosphate pesticide Substances 0.000 title claims abstract description 42
- 230000005518 electrochemistry Effects 0.000 title abstract description 7
- 238000000691 measurement method Methods 0.000 title abstract 2
- 238000000034 method Methods 0.000 claims abstract description 37
- 108010022752 Acetylcholinesterase Proteins 0.000 claims abstract description 10
- 229940022698 acetylcholinesterase Drugs 0.000 claims abstract description 8
- -1 methylacetamide phosphoramide Chemical compound 0.000 claims abstract description 7
- 102000012440 Acetylcholinesterase Human genes 0.000 claims abstract 3
- 238000001514 detection method Methods 0.000 claims description 53
- 230000004044 response Effects 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 28
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 20
- MCWXGJITAZMZEV-UHFFFAOYSA-N dimethoate Chemical compound CNC(=O)CSP(=S)(OC)OC MCWXGJITAZMZEV-UHFFFAOYSA-N 0.000 claims description 16
- 238000012417 linear regression Methods 0.000 claims description 16
- 239000007853 buffer solution Substances 0.000 claims description 15
- OEBRKCOSUFCWJD-UHFFFAOYSA-N dichlorvos Chemical compound COP(=O)(OC)OC=C(Cl)Cl OEBRKCOSUFCWJD-UHFFFAOYSA-N 0.000 claims description 15
- 229950001327 dichlorvos Drugs 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 13
- 238000012360 testing method Methods 0.000 claims description 13
- 229960001952 metrifonate Drugs 0.000 claims description 12
- NFACJZMKEDPNKN-UHFFFAOYSA-N trichlorfon Chemical compound COP(=O)(OC)C(O)C(Cl)(Cl)Cl NFACJZMKEDPNKN-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 10
- 238000005498 polishing Methods 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 239000012086 standard solution Substances 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 230000000694 effects Effects 0.000 claims description 9
- 238000000840 electrochemical analysis Methods 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 239000011574 phosphorus Substances 0.000 claims description 9
- ATROHALUCMTWTB-OWBHPGMISA-N phoxim Chemical compound CCOP(=S)(OCC)O\N=C(\C#N)C1=CC=CC=C1 ATROHALUCMTWTB-OWBHPGMISA-N 0.000 claims description 8
- 229950001664 phoxim Drugs 0.000 claims description 8
- PNVJTZOFSHSLTO-UHFFFAOYSA-N Fenthion Chemical compound COP(=S)(OC)OC1=CC=C(SC)C(C)=C1 PNVJTZOFSHSLTO-UHFFFAOYSA-N 0.000 claims description 7
- LCCNCVORNKJIRZ-UHFFFAOYSA-N parathion Chemical compound CCOP(=S)(OCC)OC1=CC=C([N+]([O-])=O)C=C1 LCCNCVORNKJIRZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000575 pesticide Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 6
- 230000008021 deposition Effects 0.000 claims description 6
- 238000000835 electrochemical detection Methods 0.000 claims description 6
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 6
- 239000005924 Pirimiphos-methyl Substances 0.000 claims description 5
- 238000001548 drop coating Methods 0.000 claims description 5
- PZXOQEXFMJCDPG-UHFFFAOYSA-N omethoate Chemical compound CNC(=O)CSP(=O)(OC)OC PZXOQEXFMJCDPG-UHFFFAOYSA-N 0.000 claims description 5
- QHOQHJPRIBSPCY-UHFFFAOYSA-N pirimiphos-methyl Chemical group CCN(CC)C1=NC(C)=CC(OP(=S)(OC)OC)=N1 QHOQHJPRIBSPCY-UHFFFAOYSA-N 0.000 claims description 5
- 238000004365 square wave voltammetry Methods 0.000 claims description 5
- SJUCACGNNJFHLB-UHFFFAOYSA-N O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical compound O=C1N[ClH](=O)NC2=C1NC(=O)N2 SJUCACGNNJFHLB-UHFFFAOYSA-N 0.000 claims description 4
- OIPILFWXSMYKGL-UHFFFAOYSA-N acetylcholine Chemical compound CC(=O)OCC[N+](C)(C)C OIPILFWXSMYKGL-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- FHIVAFMUCKRCQO-UHFFFAOYSA-N diazinon Chemical compound CCOP(=S)(OCC)OC1=CC(C)=NC(C(C)C)=N1 FHIVAFMUCKRCQO-UHFFFAOYSA-N 0.000 claims description 4
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 4
- 230000002829 reductive effect Effects 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 229960004373 acetylcholine Drugs 0.000 claims description 3
- 239000008055 phosphate buffer solution Substances 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 108090000371 Esterases Proteins 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 239000002917 insecticide Substances 0.000 claims description 2
- 150000002903 organophosphorus compounds Chemical class 0.000 claims description 2
- 238000001338 self-assembly Methods 0.000 claims description 2
- 238000004832 voltammetry Methods 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 229910021505 gold(III) hydroxide Inorganic materials 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract description 5
- 239000010931 gold Substances 0.000 abstract description 5
- 229910052737 gold Inorganic materials 0.000 abstract description 5
- 102000004190 Enzymes Human genes 0.000 abstract description 4
- 108090000790 Enzymes Proteins 0.000 abstract description 4
- 229940088598 enzyme Drugs 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 230000003993 interaction Effects 0.000 abstract description 2
- 238000005259 measurement Methods 0.000 abstract 2
- 239000002105 nanoparticle Substances 0.000 abstract 2
- 239000000523 sample Substances 0.000 description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 102100033639 Acetylcholinesterase Human genes 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 235000013311 vegetables Nutrition 0.000 description 4
- 208000007964 Organophosphate Poisoning Diseases 0.000 description 3
- 208000005374 Poisoning Diseases 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000006911 enzymatic reaction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 238000011534 incubation Methods 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 231100000570 acute poisoning Toxicity 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000012496 blank sample Substances 0.000 description 2
- 230000003139 buffering effect Effects 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 239000002027 dichloromethane extract Substances 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000003986 organophosphate insecticide Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000857 drug effect Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007830 nerve conduction Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 244000045947 parasite Species 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- BULVZWIRKLYCBC-UHFFFAOYSA-N phorate Chemical compound CCOP(=S)(OCC)SCSCC BULVZWIRKLYCBC-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- SEEPANYCNGTZFQ-UHFFFAOYSA-N sulfadiazine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CC=N1 SEEPANYCNGTZFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses an electrochemistry sensor for measuring organophosphorus pesticide residues and measurement method thereof. The surface of the electrochemistry sensor is decorated with gold nanoparticles, the sulfydryl methylacetamide phosphoramide molecules are automatically assembled and connected with the gold nanoparticle surface through an Au-S key. Based on the principle that acetylcholin esterase can have strong interactions with organophosphorus, the electrochemistry sensor provides an electrochemistry measuring method that requires no enzyme catalysis. The sensor uses short measurement time, can be used for single and gross measurements of organophosphorus.
Description
Technical field
The invention belongs to food safety detection and analysis technical field, it is related to one kind and can be used for organophosphorus pesticide residual quantity inspection
The electrochemical test sensors surveyed and its detection method.
Background technology
Shi Ge populous nation of China, large agricultural country, the annual agricultural output imported and exported occupies first place in the world, organophosphorus pesticide
Have that insecticidal spectrum is wider, parasite killing mode is diversified, wide in variety, drug effect is high, degradable, the residence time is short, with strong points the features such as,
Become the insecticides that China's range is the widest, usage amount is maximum, bring huge economic benefit to China.But
On the other hand, also bring huge harm to food safety, ecosystem etc..Several organophosphate poisonings according to nearest report
Event, Zhong County occurs organophosphate poisoning event to lead to 3 people dead, and 11 people are admitted to hospital；The thimet severe overweight that Qingdao occurs
Malicious Folium Allii tuberosi event, leads to 11 people's poisonings；Wuhan 5.23 organophosphors event leads to multidigit patient acute poisoning；The first of Jiangmen city
Amine phosphorus acute poisoning event；During 18 students in Qimen County, Anhui Province middle school are because of the edible green vegetable containing organophosphorus pesticide
Poison.Organophosphate poisoning event frequently occurs in recent years, brings serious social influence, and country uses to organophosphorus pesticide
Supervision and require increasingly stringent.
Country all defines its MRL (mrl) to every kind of pesticide, and this is that inspection and quarantine departments at different levels judge agriculture
The whether qualified most basic standard of product, but it is widely present " cocktail " method during Pesticide use, make simultaneously
Reach same purpose with the close pesticide of multiple effects.This method both can reach preferable practical function, simultaneously again permissible
Avoiding using a kind of single pesticide makes its content be judged to substandard product more than mrl.But, act on close multiple agricultures
Although each of which is not exceeded for medicine, its total amount is likely to be exceeded, from the point of view of the impact effect to human body and environment, still
So have and necessarily endanger and need to draw attention.
The hazardness of organophosphorus insecticide acetylcholinesterase (ache) easily and in human body mainly due to organophosphors
Active center combine, the catalysis activity of suppression ache, lose catalysis acetylcholine (ach) ability that hydrolyzes, so that choline
Assemble in human body, cause the wadding of Nerve conduction disorderly, a series of poisoning symptoms occur.Multiple have if existed in crops
The Phosphorus pesticide of machine although the content of each of which is below the mrl value of national regulation, but due to the inhibitory action of ache being
Sum can be added, therefore still suffer from causing the danger of poisoning.
Method currently used for organophosphorus residue detection mainly has GC-MS, liquid phase chromatogram-mass spectrometry combination
Usage, high performance liquid chromatography and inhibiting AChE etc..Chromatograph alanysis method needs large-sized analytic instrument, and process operation is numerous
Trivial it is impossible to realize Site Detection；Enzyme level rule is because the advantage such as instrument miniaturization, detection time be short is in organophosphors quick detection
Field occupies a tiny space.However, the enzyme source by being used is various, its selectivity and activity are all variant greatly, to reality
The repeatability of detection and reliability bring detrimental effect.
Content of the invention
It is an object of the invention to provide a kind of electrochemical test sensors of organophosphorus pesticide residual quantity.Described sensing
Device can be used for independent detection and the total amount detection of organophosphorus pesticide residual quantity.
Another object of the present invention is to providing a kind of electrochemical method of organophosphorus pesticide residual quantity detection.Described detection
Method is quick, efficient, sensitivity is high, good stability.
For achieving the above object, the technical solution adopted in the present invention is as follows:
A kind of electrochemical sensor of organophosphorus pesticide residual quantity detection, including basal electrode it is characterised in that described electricity
The basal electrode surface deposition of chemical sensor has nanogold particle, and sulfydryl second methylamine phosphamide is modified in substrate electricity by au-s
On the nanogold particle of pole surface deposition.
Preferably, described basal electrode is glass-carbon electrode.
Described electrochemical sensor is adopted and is prepared with the following method: first by through polishing, polishing and the substrate being cleaned by ultrasonic
In electrode immersion chlorauric acid solution, using potentiostatic method gold chloride electrochemical reduction is nanogold particle, and is deposited on substrate
Electrode surface；Again by sulfydryl second methylamine phosphamide (tma) solution drop coating on basal electrode surface, dry, by self assembly sulfydryl
Second methylamine phosphamide is modified on the nanogold particle of electrode surface deposition with au-s key；Finally received with the closing of sulfydryl hexanol solution
The residual activity site on rice gold grain surface.
Described sulfydryl second methylamine phosphamide (tma) structure is shown below,
Following methods are adopted to prepare in the embodiment of the present invention: by n- bromo-succinimide (nhs) and 1- (3- dimethylamino
Propyl group) -3- ethyl-carbodiimide hydrochloride (edc) is dissolved in phosphate buffer solution (pbs) and is stirred at room temperature, and is then added to sulfydryl second
Stir in acid solution, finally add stirring reaction in the hydrochloric acid solution of Bayer 71628；Separate out solid after revolving solvent, that is, institute is obtained
The tma stating.
A kind of electrochemical detection method of organophosphorus pesticide residual quantity, comprises the following steps:
(1) preparation of electrochemical sensor:
First the glass-carbon electrode through polishing, polishing and ultrasonic cleaning is immersed in chlorauric acid solution, with constant potential electrochemistry
Gold chloride is reduced to nanogold particle by reducing process, and is deposited on glassy carbon electrode surface, using pbs buffer solution cleaning glass carbon electricity
Pole is simultaneously dried；Again by sulfydryl second methylamine phosphamide (tma) solution drop coating in glassy carbon electrode surface, dry；Finally use sulfydryl hexanol
Solution closes the residual activity site on glassy carbon electrode surface nanogold particle surface；Prepared electrochemical sensor；
(2) preparation of standard solution:
The pbs buffering preparing one group of organophosphorus pesticide sample containing different concentration known including blank standard specimen is molten
Liquid is standard solution, the wherein acetylcholinesterase containing same concentrations (ache)；
(3) foundation of working curve:
The electrochemical test sensors of preparation in step (1) are immersed in the standard solution prepared in step (2) respectively and incubates
Educate, use pbs buffer solution to rinse electrochemical test sensors after incubation, then the electrochemical test sensors after rinsing are placed in and contain
There is k3[fe(cn)6] pbs buffer solution in carry out square wave voltammetry (swv) scanning, recording responses electric current；The sound of blank standard specimen
Induced current is i0, the response current containing organophosphors standard sample is ix, the value added δ i of response current is equal to ixWith i0Difference
Absolute value；The concentration c of described δ i and organophosphorus pesticide in standard solution is depicted as δ i-c working curve, is returned using linear
Method is returned to obtain δ i-c equation of linear regression；
(4) detection of organophosphorus pesticide residual quantity:
Testing sample is formulated as containing molten with the pbs buffering of the acetylcholinesterase (ache) of step (2) same concentrations
Liquid, according to step (3) identical method, described electrochemical sensor is incubated and square wave voltammetry (swv) scanning, note
Record response current；Value added δ i according to response current and δ i-c equation of linear regression, are calculated organic phosphorus compound residual
Allowance.
Described organophosphorus pesticide residual quantity electrochemical detection method, can also examine to the total amount of organophosphorus residue amount
Survey, further include steps of
(5) organophosphorus pesticide total amount detection:
The different organophosphors obtaining in step (3) are detected corresponding δ i-c equation of linear regression traveling matching (to step
(3) slope of different organophosphors corresponding δ i-c equation of linear regression obtaining in, intercept distinguish averaged), had
The working curve of machine phosphorus residual quantity total amount detection；Testing sample is formulated as containing the acetylcholine with step (2) same concentrations
The pbs buffer solution of esterase (ache), according to step (3) identical method, described electrochemical sensor is incubated and side
Ripple voltammetry (swv) scans, recording responses electric current；Work between value added according to response current and organophosphorus residue total amount
Curve, is calculated organophosphorus pesticide total amount.
Described organophosphorus pesticide includes but is not limited to fenthion, metrifonate, dichlorvos, chlopyrifos, parathion, diazine
Phosphorus, Bayer 71628, pirimiphos-methyl, Rogor, phoxim and omethoate.
The present invention is based on acetylcholinesterase (ache) and organophosphorus pesticide occurs the principle of strong interaction, is tied
Closing on described electrochemical sensor, thus changing the electrochemical response signal of electrochemical sensor, realizing organophosphorus residue
Detection.The electrochemical sensor of the present invention and its detection method, short without enzymatic reaction, detection time, can be used for organophosphors
Individually detection and total amount detection.
Electrochemical sensor of the present invention and detection method can be used for plant-derived food such as veterinary antibiotics, and
The independent detection of the organophosphorus residue amount in environment and total amount detection.
The electrochemical sensor that the present invention provides individually detect detection during a kind of organophosphorus pesticide be limited to 0.19～
0.77ng/ml, the range of linearity is 1～1500ng/ml；When detecting for variety classes organophosphorus pesticide total amount, the range of linearity exists
In the range of 50～1000ng/ml, the relative error of total amount testing result is less than 10%.
Beneficial effect: the present invention utilizes acetylcholinesterase with organophosphorus insecticide, the former of strong combination can occur
Reason, there is provided a kind of without enzymatic reaction, detection time is short, the electrochemistry of the individually detection that can be used for organophosphors and total amount detection passes
Sensor and its detection method.Electrochemical sensor of the present invention adopts chemical modification method to prepare, and greatly strengthen sensor
Stability and repeatability are so that working curve when variety classes organophosphorus pesticide individually detects is very close to, thus reduce
Total amount detects the error brought during working curve matching, improves reliability and the accuracy of total amount testing result；Meanwhile, this
Bright with other using inhibiting AChE carry out organophosphors quick detection method except that, the present invention provide electrochemical sensing
Device and detection method need not carry out enzymatic reaction, greatly save detection time, it also avoid because adopting separate sources simultaneously
Enzyme led to testing result poor repeatability problem.
Describe the present invention with reference to specific embodiment.Protection scope of the present invention is not to be embodied as
Mode is limited, but is defined in the claims.
Brief description
Fig. 1 be sulfydryl second methylamine phosphamide (tma) hydrogen nuclear magnetic resonance spectrum (1h-nmr).
Fig. 2 a)-Fig. 2 d) is followed successively by electrochemical sensor and carries out list to fenthion, metrifonate, dichlorvos and chlopyrifos respectively
The solely swv curve chart of detection, concentration is followed successively by 0ng/ml, 1ng/ml, 10ng/ml, 50ng/ to wherein every width in figure from top to bottom
Ml, 100ng/ml, 200ng/ml, 400ng/ml, 600ng/ml, 800ng/ml, 1200ng/ml and 1500ng/ml.
Fig. 3 a)-Fig. 3 d) is followed successively by electrochemical sensor and respectively parathion, diazinon, Bayer 71628 and pirimiphos-methyl entered
The swv curve chart that row individually detects；Wherein every width in figure from top to bottom concentration be followed successively by 0ng/ml, 1ng/ml, 10ng/ml,
50ng/ml, 100ng/ml, 200ng/ml, 400ng/ml, 600ng/ml, 800ng/ml, 1200ng/ml and 1500ng/ml.
Fig. 4 a)-Fig. 4 c) is followed successively by electrochemical sensor and respectively Rogor, phoxim and omethoate individually detected
Swv curve chart；Wherein every width in figure from top to bottom concentration be followed successively by 0ng/ml, 1ng/ml, 10ng/ml, 50ng/ml,
100ng/ml, 200ng/ml, 400ng/ml, 600ng/ml, 800ng/ml, 1200ng/ml and 1500ng/ml.
Fig. 5 is the δ i-c working curve to the independent detection of fenthion.
Specific embodiment
Below by specific embodiment, technical solutions according to the invention are further described in detail, but are necessary
Point out that following examples are served only for the description to content of the invention, do not constitute limiting the scope of the invention.
The preparation of embodiment 1 organophosphorus pesticide residual quantity electrochemical test sensors
(1) preparation of sulfydryl second methylamine phosphamide (tma)
Bayer 71628 (0.1g) is dissolved in 10ml hydrochloric acid (0.1mol/l), under condition of ice bath, stirs 1h, prepare Bayer 71628
Hydrochloric acid solution；By n- bromo-succinimide (nhs, 0.542g) and 1- (3- dimethylamino-propyl) -3- ethyl carbodiimide
Hydrochlorate (edc, 0.254g) is dissolved in during phosphate-buffered is dissolved in and being stirred at room temperature 3 hours, is slow added into TGA and (uses
Sodium bicarbonate solution adjusts ph to neutral) in solution, continue to stir 2 hours, gained reactant is added to the hydrochloric acid of Bayer 71628
After continuing in solution to stir 10 hours under room temperature, rotation under room temperature evaporates most of solvent, separates out a large amount of white solids.Decompression
Sucking filtration, is washed with a small amount of frozen water, prepared tma.Its hydrogen nuclear magnetic resonance spectrum (1H-nmr) see Fig. 1.
(2) preparation of sensor: by the glass-carbon electrode of a diameter of 3mm successively with the al of a diameter of 0.3 μm and 0.05 μm2o3
Polishing powder is polishing to minute surface, uses dehydrated alcohol-distilled water, distilled water to be cleaned by ultrasonic 5min successively, cleaner with distilled water flushing；
The glass-carbon electrode handled well is immersed in chlorauric acid solution (mass percent concentration is 1%), with constant potential (- 0.2v) electrification
Learn deposition nanometer gold (persistent period is 60s)；Above-mentioned electrode is rinsed well with pbs buffer solution, by sulfydryl second first after drying
Amine phosphinylidyne amine aqueous solution (10 μ l, 0.1mol/l) drop coating, on electrode, is placed in 37 DEG C of vacuum drying ovens and dries；By covalent modification
Incubation 30min in the sulfydryl hexanol aqueous solution (mass percent concentration is 1%) that electrode after tma is placed in, in order to close nanometer
The residual activity site of gold surface, finally uses pbs buffer solution that electrode washing is totally standby.
The independent detection of embodiment 2 organophosphors standard sample
The present embodiment is individually detected to organophosphors standard sample respectively, and organophosphorus pesticide sample is selected from fenthion, enemy
Hundred worms, dichlorvos, chlopyrifos, parathion, diazinon, Bayer 71628, pirimiphos-methyl, Rogor, phoxim and omethoate.
By in embodiment 1 preparation electrochemical sensor immerse respectively organic phosphorus concentration be followed successively by 0ng/ml, 1ng/ml,
10ng/ml, 50ng/ml, 100ng/ml, 200ng/ml, 400ng/ml, 600ng/ml, 800ng/ml, 1200ng/ml and
It is incubated in the pbs buffer solution (ache being all wherein 10 μ g/ml containing concentration) of 1500ng/ml, used pbs buffer solution
It is placed in containing k after rinsing well3[fe(cn)6] pbs buffer solution in carry out square wave voltammetry (swv) scanning, recording responses electricity
Stream；The response current of blank standard specimen is i0, the response current containing organophosphors standard specimen is ix, the value added δ i of response current is equal to
ixWith i0Difference；The concentration c of δ i and organophosphors in Incubating Solution is depicted as δ i-c working curve, is obtained using linear regression method
To δ i-c equation of linear regression.
Testing sample is incubated to described electrochemical sensor using same procedure under similarity condition and swv is swept
Retouch, recording responses electric current；The value added δ i of response current is substituted into δ i-c equation of linear regression, you can obtain in testing sample
The residual quantity of corresponding organophosphors.
Accompanying drawing 2a) -2d), Fig. 3 a) -3d), Fig. 4 a) -4c) be followed successively by fenthion, metrifonate, dichlorvos, chlopyrifos, to sulfur
The swv curve that phosphorus, diazinon, Bayer 71628, pirimiphos-methyl, Rogor, phoxim and omethoate individually detect.Accompanying drawing 5 is right
The δ i-c working curve that fenthion individually detects.The above-mentioned organophosphors individually δ i-c equation of linear regression of detection, linear correlation
Coefficient (r), the range of linearity and lowest detectable limit are shown in Table 1.
The independent testing result of table 1 organophosphorus residue amount
The mark-on detection of dichlorvos in embodiment 3 Fructus Mali pumilae
Weigh the Fructus Mali pumilae sample (three parts of parallel sample, every part of quality is 50 ± 0.005g) cleaning up and put in beaker,
Add dichlorvos standard solution, be subsequently adding 50ml water and 100ml acetone, rubbed with pulverizer and extract 3min.Take after filtration
100ml filtrate is placed in separatory funnel, adds 15g sodium chloride, acutely stands after vibration 3min, uses 50ml bis- after solution layering
Chloromethanes aqueous phase extracted, acetone and dichloromethane extract are merged.Wherein moisture is removed with anhydrous sodium sulfate drying, revolving is dense
It is reduced to about 2ml, with nitrogen, remaining liq is dried up, be eventually adding 10ml ethanol-water solution (v:v=1:1), shake to dissolving,
Low temperature shading preserves stand-by.
Prepare the blank sample being added without dichlorvos according to the method described above, the mark-on with 3 different dichlorvos concentration of addition
Sample (standard addition method), and with method described in embodiment 2, described electrochemical sensor is incubated and swv scanning, note
Record response current；δ between value added δ i according to the corresponding response current of the dichlorvos obtaining in embodiment 2 and concentration c
I-c equation of linear regression, obtains the residual quantity of dichlorvos.The detection response rate the results are shown in Table 2.
The mark-on testing result of dichlorvos in table 2 Fructus Mali pumilae
The mark-on detection of metrifonate in embodiment 4 green vegetable
Weigh the green vegetable sample (three parts of parallel sample, every part of quality is 50 ± 0.005g) cleaning up and put in beaker,
Add metrifonate standard solution, be subsequently adding 50ml water and 100ml acetone, rubbed with pulverizer and extract 3min.Take after filtration
100ml filtrate is placed in separatory funnel, adds 15g sodium chloride, acutely stands after vibration 3min, uses 50ml bis- after solution layering
Chloromethanes aqueous phase extracted, acetone and dichloromethane extract are merged.Wherein moisture is removed with anhydrous sodium sulfate drying, revolving is dense
It is reduced to about 2ml, with nitrogen, remaining liq is dried up, be eventually adding 10ml ethanol-water solution (v:v=1:1), shake to dissolving,
Low temperature shading preserves stand-by.
Prepare the blank sample being added without metrifonate according to the method described above, the mark-on with 3 different metrifonate concentration of addition
Sample (standard addition method), and with method described in embodiment 2, described electrochemical sensor is incubated and swv scanning, note
Record response current；Value added δ i according to the corresponding response current of the metrifonate obtaining in embodiment 2 and metrifonate concentration c it
Between δ i-c equation of linear regression, obtain the residual quantity of metrifonate.The detection response rate the results are shown in Table 3.
The mark-on testing result of metrifonate in table 3 green vegetable
The total amount detection of embodiment 5 organophosphors standard sample
(1) organophosphors total amount detects the foundation of linear equation: is individually detected by a kind of organophosphors of gained ten in embodiment 2
Working curve understand, when different organophosphors individually detect, the expression formula of working curve is very close to, wherein the meansigma methodss of slope be-
0.022458, its relative standard deviation is 8.44%；The meansigma methodss of intercept are -6.188, therefore by organophosphorus pesticide total amount and sound
The linear equation model of detection between the value added δ i of induced current is δ i=-0.022458c-6.188；
(2) the total amount detection of organophosphors standard sample: by chlopyrifos: dichlorvos: phoxim: parathion presses different mol ratio
Mixing is dissolved in pbs buffer solution, is configured to a series of different testing sample of total concentrations.Entered with method described in embodiment 2
Row incubation and swv scanning, recording responses electric current；The value added δ i of response current is substituted into the linear equation of matching in step (1)
In, obtain organophosphors total amount measured value.Measured value is relatively shown in Table 4 and table 5 with add value.
Table 4 organophosphorus pesticide total amount detects (chlopyrifos: dichlorvos: phoxim: parathion mol ratio=1:1:1:1)
| Add concentration (ng/ml) | 800 | 600 | 400 | 300 | 200 | 100 | 50 | 1 |
| Detectable concentration (ng/ml) | 822.27 | 577.82 | 385.90 | 316.21 | 196.22 | 106.7 | 54.13 | 10.91 |
| The response rate (%) | 102.8 | 96.3 | 96.4 | 105.4 | 98.1 | 106.7 | 108.3 | 1090 |
| Relative error (%) | +2.8 | -3.7 | -3.5 | +5.4 | -1.9 | +6.7 | +8.3 | +990 |
Table 5 organophosphors total amount detects (chlopyrifos: dichlorvos: phoxim: parathion mol ratio=1:2:3:4)
| Add concentration (ng/ml) | 1000 | 800 | 600 | 400 | 200 | 100 | 50 | 1 |
| Detectable concentration (ng/ml) | 986.2 | 814.8 | 631.8 | 418.5 | 195.1 | 94.4 | 53.9 | 8.54 |
| The response rate (%) | 98.6 | 101.9 | 105.3 | 104.6 | 97.5 | 94.4 | 107.8 | 854 |
| Relative error (%) | -1.4 | +1.9 | +5.3 | +4.6 | -2.5 | -5.6 | +7.8 | +854 |
Claims (7)
1. the electrochemical sensor of a kind of organophosphorus pesticide residual quantity detection, including substrate glass-carbon electrode it is characterised in that described
The basal electrode surface deposition of electrochemical sensor has nanogold particle, and sulfydryl second methylamine phosphamide passes through au-s key and modifies in institute
The nanogold particle surface stated.
2. a kind of electrochemical sensor of organophosphorus pesticide residual quantity detection according to claim 1 is it is characterised in that institute
State electrochemical sensor and adopt and prepare with the following method: first by the glass-carbon electrode immersion chlorine through polishing, polishing and ultrasonic cleaning
In auric acid solution, using potentiostatic method gold chloride electrochemical reduction is nanogold particle, and is deposited on basal electrode surface；Again
By sulfydryl second Bayer 71628 amide solution drop coating on basal electrode surface, dry, by self assembly by sulfydryl second methylamine phosphamide with
Au-s key is modified on the nanogold particle of electrode surface deposition；Sulfydryl hexanol solution is finally used to close nanogold particle surface
Residual activity site.
3. the electrochemical sensor of a kind of organophosphorus pesticide residual quantity detection according to claim 1 and 2, its feature exists
In described sulfydryl second methylamine phosphamide adopts following methods to prepare: by n- bromo-succinimide and 1- (3- dimethylamino third
Base) -3- ethyl-carbodiimide hydrochloride is dissolved in phosphate buffer solution and is stirred at room temperature, be then added to stir in mercaptoacetic acid solution
Mix, finally add stirring reaction in the hydrochloric acid solution of Bayer 71628；Separate out solid after revolving solvent, that is, described sulfydryl second first is obtained
Amine phosphamide.
4. a kind of electrochemical detection method of organophosphorus pesticide residual quantity is it is characterised in that described detection method includes following step
Rapid:
(1) preparation of electrochemical sensor:
First the glass-carbon electrode through polishing, polishing and ultrasonic cleaning is immersed in chlorauric acid solution, with constant potential electrochemical reduction
Gold chloride is reduced to nanogold particle by method, and is deposited on glassy carbon electrode surface, cleans glass carbon using phosphate buffer solution (pbs)
Electrode simultaneously dries；Again by sulfydryl second Bayer 71628 amide solution drop coating in glassy carbon electrode surface, dry；Finally use sulfydryl hexanol solution
The residual activity site on closing glassy carbon electrode surface nanogold particle surface, prepared electrochemical sensor；
(2) preparation of standard solution:
The pbs buffer solution preparing one group of organophosphorus pesticide sample containing different concentration known including blank standard specimen is
Standard solution, the wherein acetylcholinesterase containing same concentrations；
(3) foundation of working curve:
The electrochemical test sensors of preparation in step (1) are immersed in the standard solution prepared in step (2) respectively and is incubated, incubate
Use pbs buffer solution to rinse electrochemical test sensors after educating, then the electrochemical test sensors after rinsing are placed in containing k3
[fe(cn)6] pbs buffer solution in carry out square wave voltammetry scanning, recording responses electric current；The response current of blank standard specimen is
i0, the response current containing organophosphorus pesticide standard sample is ix, the value added δ i of response current is equal to ixWith i0Difference exhausted
To value；The concentration c of described δ i and organophosphorus pesticide in standard solution is depicted as δ i-c working curve, using linear regression method
Obtain δ i-c equation of linear regression；
(4) detection of organophosphorus pesticide residual quantity:
Testing sample is formulated as containing the pbs buffer solution with the acetylcholinesterase of step (2) same concentrations, according to step
Suddenly (3) identical method is incubated to described electrochemical sensor and square wave voltammetry scanning, recording responses electric current；According to sound
The value added δ i of induced current and δ i-c equation of linear regression, are calculated organic phosphorus compound residual quantity.
5. organophosphorus pesticide residual quantity according to claim 4 electrochemical detection method it is characterised in that also include with
Lower step:
(5) organophosphorus pesticide total amount detection:
By the different detection of organic phosphorus pesticide obtaining in step (3) corresponding δ i-c equation of linear regression traveling matching, had
The working curve of machine phosphorus insecticide residual quantity total amount detection；Testing sample is formulated as containing the acetyl with step (2) same concentrations
The pbs buffer solution of acetylcholine esterase, is incubated and square wave to described electrochemical sensor according to step (3) identical method
Voltammetry scans, recording responses electric current；Linear regression side between value added according to response current and organophosphorus residue total amount
Journey, is calculated organophosphorus pesticide total amount.
6. the electrochemical detection method of organophosphorus pesticide residual quantity according to claim 5 is it is characterised in that described matching
Obtain in the slope of working curve of organophosphorus pesticide residual quantity total amount detection and intercept respectively step (3) afterwards is difference organic
The slope meansigma methodss of phosphorus pesticide corresponding δ i-c equation of linear regression, intercept meansigma methodss.
7. the electrochemical detection method of the organophosphorus pesticide residual quantity according to claim 4 or 5 is it is characterised in that described
Organophosphorus pesticide be selected from fenthion, metrifonate, dichlorvos, chlopyrifos, parathion, diazinon, Bayer 71628, pirimiphos-methyl,
One or more of Rogor, phoxim and omethoate.
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