CN109827948A - A kind of rapid detection method of dithiocarbamate pesticide - Google Patents
A kind of rapid detection method of dithiocarbamate pesticide Download PDFInfo
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- CN109827948A CN109827948A CN201910214552.5A CN201910214552A CN109827948A CN 109827948 A CN109827948 A CN 109827948A CN 201910214552 A CN201910214552 A CN 201910214552A CN 109827948 A CN109827948 A CN 109827948A
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- CN
- China
- Prior art keywords
- agricultural product
- detection method
- dithiocarbamate pesticide
- detection
- sers substrate
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- 238000001514 detection method Methods 0.000 title claims abstract description 57
- 239000000575 pesticide Substances 0.000 title claims abstract description 41
- 239000012990 dithiocarbamate Substances 0.000 title claims abstract description 40
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000000758 substrate Substances 0.000 claims abstract description 62
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 claims abstract description 52
- 150000003839 salts Chemical class 0.000 claims abstract description 29
- 238000001069 Raman spectroscopy Methods 0.000 claims abstract description 14
- 238000012360 testing method Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000012530 fluid Substances 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 238000000605 extraction Methods 0.000 claims abstract description 4
- 238000005119 centrifugation Methods 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 36
- 239000007788 liquid Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 16
- 229910000510 noble metal Inorganic materials 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 235000019441 ethanol Nutrition 0.000 claims description 11
- 239000000945 filler Substances 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000002082 metal nanoparticle Substances 0.000 claims description 9
- 239000002798 polar solvent Substances 0.000 claims description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002105 nanoparticle Substances 0.000 claims description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- 238000001338 self-assembly Methods 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- 150000002170 ethers Chemical class 0.000 claims description 4
- 238000007689 inspection Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 229940113088 dimethylacetamide Drugs 0.000 claims description 2
- -1 halide salt Chemical class 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
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- 239000002184 metal Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims 2
- CXBDYQVECUFKRK-UHFFFAOYSA-N 1-methoxybutane Chemical compound CCCCOC CXBDYQVECUFKRK-UHFFFAOYSA-N 0.000 claims 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 8
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- 239000000243 solution Substances 0.000 description 17
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- 229960002447 thiram Drugs 0.000 description 17
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- 239000003599 detergent Substances 0.000 description 4
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- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 239000010970 precious metal Substances 0.000 description 4
- 238000004445 quantitative analysis Methods 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 239000001509 sodium citrate Substances 0.000 description 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 4
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- 235000018481 Hylocereus undatus Nutrition 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 241001264786 Ceanothus spinosus Species 0.000 description 2
- 235000005979 Citrus limon Nutrition 0.000 description 2
- 244000131522 Citrus pyriformis Species 0.000 description 2
- 240000008067 Cucumis sativus Species 0.000 description 2
- 235000010799 Cucumis sativus var sativus Nutrition 0.000 description 2
- 244000068988 Glycine max Species 0.000 description 2
- 235000010469 Glycine max Nutrition 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
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- 241000220225 Malus Species 0.000 description 2
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- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 240000003768 Solanum lycopersicum Species 0.000 description 2
- 240000008042 Zea mays Species 0.000 description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 239000005870 Ziram Substances 0.000 description 2
- FPIPGXGPPPQFEQ-OVSJKPMPSA-N all-trans-retinol Chemical compound OC\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-OVSJKPMPSA-N 0.000 description 2
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- 229940088710 antibiotic agent Drugs 0.000 description 2
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- 238000004817 gas chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
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- 239000000447 pesticide residue Substances 0.000 description 2
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- DUBNHZYBDBBJHD-UHFFFAOYSA-L ziram Chemical compound [Zn+2].CN(C)C([S-])=S.CN(C)C([S-])=S DUBNHZYBDBBJHD-UHFFFAOYSA-L 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- GSFSVEDCYBDIGW-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)-6-chlorophenol Chemical compound OC1=C(Cl)C=CC=C1C1=NC2=CC=CC=C2S1 GSFSVEDCYBDIGW-UHFFFAOYSA-N 0.000 description 1
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- 239000005802 Mancozeb Substances 0.000 description 1
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- 235000004347 Perilla Nutrition 0.000 description 1
- 244000124853 Perilla frutescens Species 0.000 description 1
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- GAMFEMAXLMWCRG-UHFFFAOYSA-N bis(dimethylcarbamothioylsulfanyl)arsanyl n,n-dimethylcarbamodithioate Chemical compound CN(C)C(=S)S[As](SC(=S)N(C)C)SC(=S)N(C)C GAMFEMAXLMWCRG-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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Landscapes
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention discloses a kind of detection methods of dithiocarbamate pesticide in agricultural product, it include: 1) to mix agricultural product to be measured with organic solvent, the first salt packet, the second salt packet, so that dithiocarbamate pesticide enters in organic solvent, by extraction, filtering or centrifugation, obtain clear fluid test sample, first salt packet is used to absorb the moisture in agricultural product for destroying agricultural product eucaryotic cell structure, the second salt packet；2) active region of SERS substrate is dipped in the predetermined time in fluid test sample, dithiocarbamate pesticide molecule is made to be adsorbed or grab SERS substrate surface；3) Raman detection will be carried out after SERS substrate drying obtained by step (2)；Advantage easy to operate, at low cost can be had both under the premise of the present invention is high in accuracy in detection and detection sensitivity is high, detection lower limit is low.
Description
Technical field
The invention belongs to Pesticides Testing technical fields, and in particular to a kind of quick inspection of dithiocarbamate pesticide
The detection of the dithiocarbamate pesticide contained in survey method more particularly to water fruits and vegetables, crop.
Background technique
Dithiocarbamate pesticide is a kind of insecticide for being widely used in crops, can with containing sulfydryl (-
SH the coenzyme of enzyme and mushroom cell) interacts and then achievees the purpose that desinsection.Although the toxicity of the compound is lower,
But potential problem of environmental pollution is remained using such compound in fruit and vegetable and influences the health of the mankind, such as
Can stimulate human skin and mucous membrane, derivative products have it is carcinogenic and a possibility that cause human body lopsided, therefore, at present all can be to agriculture
Remaining dithiocarbamate pesticide is detected to judge whether to meet country or international standard in crop.
Detecting the method for dithiocarbamate pesticide in the prior art includes: colorimetric method, high performance liquid chromatography side
Method etc.；
Such as (such as SN/T0157-1992 imports and exports dithiocarbamate pesticide in fruit to headspace sampling-gas chromatography
Remaining detection) and (agricultures such as such as University Of Agriculture and Forestry In Fujian's Food Science institute Wang Jiaying, the red tealeaves of wangdan of ultraviolet spectrometry colorimetric method
The research of quick detection method for dithiocarbamate pesticide residue in product), however instrument needed for gas chromatography compared with
Valuableness, the principle of ultraviolet spectrometry colorimetric method are all that dithiocarbamate pesticide is resolved into carbon disulfide, pass through two sulphur
Change carbon is reacted with color developing agent carrys out qualitative and quantitative analysis, but discovery the method has false positive appearance during atual detection, separately
The outer deeper food of some colors can take color in reception pipe in preceding processing, disturb normal assay.
For another example Chinese invention CN102269696A, it discloses a kind of detections of dithiocarbamate pesticide residue
Method, comprising: for crop in cruciferae such as Chinese cabbage, radish, 50-100g sample is taken to add slightly boiled 15-25 minutes of water heating；It is right
Distillation extraction is carried out in the deeper sample of the colors such as purple perilla；Working curve is prepared simultaneously carries out colorimetric analysis.Although this patent exists
It solves the problems, such as that false positive occurs in colorimetric method to a certain extent, but practical operation is still cumbersome, detects result speed
Slowly, higher cost, the dithiocarbamate pesticide for being unfavorable for containing fruit and vegetable are used for quickly detecting.
Therefore, those skilled in the art urgently seeks a kind of sensitive technology and goes quickly to detect to be present in water fruits and vegetables
The dithiocarbamate pesticide of remaining.
Summary of the invention
The technical problem to be solved by the present invention is to overcome deficiency in the prior art, a kind of new quick detection two is provided
The method of thiocarbamates pesticide, under the premise of and detection sensitivity high in accuracy in detection is high, detection lower limit is low
Advantage easy to operate, at low cost can be had both.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows:
The detection method of dithiocarbamate pesticide in a kind of agricultural product, described detection method includes the following steps:
1) agricultural product to be measured are mixed with organic solvent, the first salt packet, the second salt packet, so that dithiocarbamate pesticide
Into in the organic solvent, by extraction, filtering or centrifugation, clear fluid test sample, the first salt packet are obtained
For destroying agricultural product eucaryotic cell structure, the second salt packet is used to absorb the moisture in agricultural product；
2) active region of SERS substrate is dipped in the predetermined time in the resulting fluid test sample of step (1), makes two sulphur
SERS substrate surface is adsorbed or grabbed for carbamate chemicals for agriculture molecule；
3) Raman detection will be carried out after SERS substrate drying obtained by step (2).
Some preferred aspects according to the present invention, the agricultural product are veterinary antibiotics, crop, are specifically as follows banana, fire
Long Guo, mango, apple, pears, cucumber, tomato, fresh corn, soybean etc..
In the present invention, " the dithiocarbamate pesticide " includes Dithane A40, zineb, ambam, Dai Sen
Manganese, Polycarbamate, Mancozeb, Carbatene, Propineb, thiram, Sodium Dimethyldithiocarbamate, good fortune U.S. potassium, ziram, bis methylarsine, good fortune
U.S. iron, asomate etc..
More according to the present invention specific and preferred aspect, the first salt packet includes nitrate, carbonate, silicic acid
One of salt, acetate, phosphate, halide salt or any combination thereof.
More according to the present invention specific and preferred aspect, the second salt packet includes sodium sulphate, calcium chloride, magnesium chloride
One of or any combination thereof.
More according to the present invention specific and preferred aspect, it is sub- that the organic solvent is selected from ethyl acetate, acetonitrile, diformazan
One of sulfone, dimethylformamide and dimethyl acetamide or any combination thereof.
Some preferred aspects according to the present invention, in step (1), the first salt packet feeds intake with the agricultural product to be measured
Mass ratio is 0.004-40: 1, it is preferable that the mass ratio that feeds intake of the first salt packet and the agricultural product to be measured is 0.01-30:
1, it is highly preferred that the mass ratio that feeds intake of the first salt packet and the agricultural product to be measured is 0.1-20: 1, it is further preferred that institute
The mass ratio that feeds intake for stating the first salt packet and the agricultural product to be measured is 0.1-10: 1.
Some preferred aspects according to the present invention, in step (1), the second salt packet feeds intake with the agricultural product to be measured
Mass ratio is 0.008-80: 1, it is preferable that the mass ratio that feeds intake of the second salt packet and the agricultural product to be measured is 0.01-50:
1, it is highly preferred that the mass ratio that feeds intake of the second salt packet and the agricultural product to be measured is 0.1-30: 1, it is further preferred that institute
The mass ratio that feeds intake for stating the second salt packet and the agricultural product to be measured is 0.2-10: 1.
Some preferred aspects according to the present invention, the detection method further include purifying the fluid test sample
The step of, the purifying includes that the fluid test sample is dried and/or is adsorbed using filler, and alcohol is then added
Class polar solvent and/or ethers polar solvent, are made the sample for Raman detection.
More according to the present invention specific and preferred aspect, the alcohols polar solvent are methanol and/or ethyl alcohol.
More according to the present invention specific and preferred aspect, the ethers polar solvent include glycol monoethyl ether and/
Or tert-butyl monomethyl ether.
More according to the present invention specific and preferred aspect, the filler are selected from C18 filler, PSA filler, graphitization
One of carbon, aluminium oxide and PEP filler or any combination thereof.
More according to the present invention specific and preferred aspect, the detection method further include not of the same race in drafting agricultural product
Standard curve between the feature peak intensity and spiked levels of class dithiocarbamate pesticide.
A specific aspect according to the present invention, the thiram, ziram Surface enhanced Raman spectroscopy characteristic peak be
933cm-1, 1138cm-1, 1370cm-1, 1497cm-1, the thiram of mark-on various concentration in fruit and vegetable, feature peak intensity with
Spiked levels are directly proportional, can be used for the quantitative analysis of thiram in fruit and vegetable after drafting standard curve.
A specific aspect according to the present invention, the characteristic peak of the Carbatene Surface enhanced Raman spectroscopy are 491cm-1, 1228cm-1, 1280cm-1, 1316m-1, 1442cm-1, 1529cm-1, the Carbatene of mark-on various concentration in fruit and vegetable,
Feature peak intensity is directly proportional to spiked levels, can be used for the quantitative analysis of Carbatene in fruit and vegetable after drafting standard curve.
A specific aspect according to the present invention, the characteristic peak of the Propineb Surface enhanced Raman spectroscopy are 471cm-1, 1472cm-1, the Propineb of mark-on various concentration in fruit and vegetable, feature peak intensity is directly proportional to spiked levels, draws mark
It can be used for the quantitative analysis of Propineb in fruit and vegetable after directrix curve.
Some preferred aspects according to the present invention, the SERS substrate are made of the drying of noble metal colloidal sol.
Some preferred aspects according to the present invention, the SERS substrate include your gold of substrate and setting on the substrate
Belong to nanoparticle or layer of precious metal.
Some preferred aspects according to the present invention, the SERS substrate include that there is the substrate of multiple pits and self assembly to exist
Noble metal nano particles cluster in the pit.Nano impression, plasma etching, ultraviolet etching, chemical etching, laser can be used
Etching, machine drilling, mechanical stamping or electrochemical process produce pit.
Lemon can be added by the solution containing precious metal salt in some specific aspects according to the present invention, the noble metal colloidal sol
It is made in lemon acid salt solution, precious metal salt includes silver nitrate, gold chloride etc..
Some specific aspects according to the present invention, noble metal include gold, silver etc.；Noble metal nano particles cluster is by your multiple gold
Belong to nanoparticle composition；Noble metal nano particles, that is, noble metal material nanoparticle；Layer of precious metal passes through coating by noble metal
Or the modes such as infiltration are formed.
Some specific aspects according to the present invention, citrate can be sodium citrate etc..
Some specific aspects according to the present invention, the method for the self assembly includes will be containing the dispersant liquid drop of nanoparticle
Add, spin coating, printing, inject or spray to the substrate surface, alternatively, the substrate surface to be immersed to the nanoparticle
In the dispersion liquid of son, pass through the solvent of the volatilization removal dispersion liquid.
There are many modes of above-mentioned immersion, for example, substrate is totally immersed into dispersion liquid, takes out substrate, carries out solvent
Volatilization；Alternatively, the surface of substrate is immersed in dispersion liquid, the volatilization that substrate carries out solvent is taken out；Alternatively, being added dropwise in substrate surface
Then one layer of dispersion liquid carries out the volatilization of solvent.Above-mentioned spin coating, which refers to, is applied to the substrate for dispersion liquid rotation by equipment
Surface.
Some preferred aspects according to the present invention, multiple pits on substrate size possessed by respective,
Spacing between shape and the pit, there are at least one differences in the arrangement mode of multiple pits.
Some preferred aspects according to the present invention, multiple pits on substrate size possessed by respective,
One or more of spacing and the arrangement mode of multiple pits between shape, the two neighboring pit are upper in rule
The variation of rule property.
The size of some preferred aspects according to the present invention, pit described in any two on the substrate is differed in 0-
1000nm, shape is identical, and the spacing between two pits of arbitrary neighborhood is differed in 0-500nm；Wherein, the ruler of the pit
The depth of the very little diameter including pit, pit.
Some preferred aspects according to the present invention, the diameter of the pit are 50nm ~ 500nm, between the pit between
Away from for 5nm ~ 50nm, noble metal nano particles number is 3 ~ 15 in the noble metal nano particles cluster, each noble metal nano
The partial size of particle is 30nm ~ 120nm.
Some preferred aspects according to the present invention, the depth of the pit are 90-10000nm.
Some preferred aspects according to the present invention, the top surface area of the substrate are 4-400mm2；It is highly preferred that the base
The top surface area of piece is 16-100mm2；It is further preferred that the top surface area of the substrate is 16-36mm2。
Some specific aspects according to the present invention, the substrate be silicon, glass, PDMS, PMMA, Al, aluminium oxide or other
Substrate.
In the present invention, the spacing between the pit refers to the minimum separation distances between adjacent two pits, more specifically
It refers to existing multiple between the arbitrary point on the arbitrary point and an adjacent pit top edge on a pit top edge
The smallest distance in distance；The diameter of pit refers to the maximum in multiple distances between any two points on pit top edge
Distance.
Some preferred aspects according to the present invention, the SERS substrate are hydrophobic type SERS substrate.In the present invention, hydrophobic type
The hydrophobic modification method used in SERS substrate can use hydrophobic modification method commonly used in the art.
In the present invention, SERS substrate (surface enhanced Raman scattering substrate) can provide molecule on a molecular scale
Therefore structural information can identify compound concentration in metal surface vibration information according to Molecular Adsorption.
Due to the use of above technical scheme, the invention has the following advantages over the prior art:
The present invention extracts and deficiency present in detection method, wound for dithiocarbamate pesticide in existing agricultural product
It newly proposes to detect using Surface enhanced Raman spectroscopy, while the detection for surface-enhanced Raman in the prior art is wanted again
It asks, designs corresponding quick pretreatment step, be the one of practical application to form a quickly and effectively SERS solution
The problem of a difficult point, innovatively proposes solve agricultural production using the first salt packet, the second salt packet rapidly extracting test sample
The interference of complex matrices in product especially fruit and vegetable, without the influence of agricultural product normal Raman, when there is simple step, analysis
Between it is short, selectivity is good, do not need large-scale instrument, meet national standard limitation requirement, dithiocarbamates first in live food can be achieved
It the advantages that quick and precisely detection of esters of gallic acid pesticide, can and detection sensitivity high in accuracy in detection be high, detection lower limit is low
Under the premise of have both advantage easy to operate, at low cost, especially detection lower limit can be down to 0.01mg/kg.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention without any creative labor, may be used also for those of ordinary skill in the art
To obtain other attached drawings according to these attached drawings；
Fig. 1 is the standard items of thiram in detection method proposed by the present invention, and the standard items surface enhanced of Carbatene, Propineb is drawn
Graceful spectrogram；★: thiram；☆: Carbatene；▲: Propineb.
Fig. 2 is the surface-enhanced Raman of red heart dragon fruit mark-on 0.5mg/L thiram in detection method proposed by the present invention
Spectrogram；
Fig. 3 is the Surface enhanced Raman spectroscopy figure of banana mark-on 1mg/L Carbatene in detection method proposed by the present invention；
Fig. 4 is pears mark-on bi-component pesticide wherein thiram 0.25ppm, the generation of various concentration in detection method proposed by the present invention
Gloomy (A 5ppm), (B 2.5ppm), (C 0.5ppm).★: thiram；☆: the Surface enhanced Raman spectroscopy figure of Carbatene；
Fig. 5 is different thiram concentration and 1370cm in detection method mango proposed by the present invention-1Peak intensity relational graph；
Fig. 6 is that the SEM of SERS substrate I prepared by the present invention schemes；
Fig. 7 is that the SEM of SERS substrate II prepared by the present invention schemes；
The SEM that Fig. 8 is SERS substrate II I prepared by the present invention schemes；
Fig. 9 is the structural schematic diagram of SERS substrate IV prepared by the present invention.
Specific embodiment
Above scheme is described further below in conjunction with specific embodiment；It should be understood that these embodiments are for illustrating
The basic principles, principal features and advantages of the present invention, and the present invention is not by the scope limitation of following embodiment；It is used in embodiment
Implementation condition further adjustment can be done according to specific requirement, the implementation condition being not specified is usually the item in routine experiment
Part.
In following embodiments, unless otherwise specified, all raw materials are both from routine that is commercially available or passing through this field
Method is prepared.
The preparation of nano silver colloidal sol:
Mass concentration is added in 100 mL three-neck flasks to be 1% silver nitrate aqueous solution 1mL and be diluted to 100ml；This is molten
Liquid is heated to boiling, and is constantly flowing back and be vigorously stirred the sodium citrate solution that lower addition concentration is 1%.Solution is gradually by colourless turn
Become light blue.Start timing after discoloration, keeps 15 min of system fluidized state under stirring condition, then naturally cool to room
Temperature obtains silver sol.
The preparation of nano gold sol:
The aqueous solution of chloraurate 1mL that mass concentration is 1% is added in 100 mL three-neck flasks and is diluted to 100ml；This is molten
Liquid is heated to boiling, and is constantly flowing back and be vigorously stirred the sodium citrate solution that lower addition concentration is 1%.Solution is gradually by yellowish turn
Become claret.Start timing after discoloration, keeps 15 min of system fluidized state under stirring condition, then naturally cool to room
Temperature obtains aurosol, adjusts the partial size that the adjustable Au of amount of sodium citrate is added.
Nano sol self assembly:
Glass slide is cut into the rectangular chip of 2cm*2cm, is cleaned up with detergent, N2Drying.O is used later2Plasma
Cleaning machine handles 5min.After impregnating 1min in the aqueous solution of 5% 3- aminopropyl triethoxysilane later, rushed with ultrapure water
2 times are washed, N2Drying.It is placed in 3h in silver sol, a large amount of water cleanings, obtain SERS substrate I, as shown in Figure 6 after taking-up.
Nano sol self assembly:
By the rectangular chip of the chip 0.4cm*0.4cm of the regular hole of nano impression band, aperture 100nm, hole depth is
60nm, spacing 90nm.It is cleaned up with detergent, N2Drying.O is used later2Plasma washing machine handles 5min.It soaks later
Bubble 3h in aurosol, a large amount of water cleanings, obtain SERS substrate II, as shown in Figure 7 after taking-up.
By the rectangular chip of the chip 0.4cm*0.4cm of the regular hole of nano impression band, aperture 500nm, hole depth
For 200nm, spacing 450nm.It is cleaned up with detergent, N2Drying.O is used later2Plasma washing machine handles 5min.It
After be immersed in 3h in aurosol, the cleaning of a large amount of water, obtains SERS substrate II I, as shown in Figure 8 after taking-up.
Embodiment 1
The detection method of dithiocarbamate pesticide in a kind of agricultural product that this example proposes, comprising the following steps:
1, it weighs 10g red heart dragon fruit and crushes (thiram, 0.5mg/L), 10ml acetonitrile solution is added, the sodium chloride of 2.5g is added
Solid shakes 2min, 5g anhydrous sodium sulfate is added, sample 3min fullys shake, 5000rpm is centrifuged 5min；
2, it takes upper solution (i.e. acetonitrile solvent phase) in test tube, is dried with nitrogen；
3, take 200 μ L methanol in above-mentioned test tube, oscillation is used as prepare liquid for several times；
4, SERS substrate I is immersed in above-mentioned 150 μ L prepare liquid, after impregnating 10min, taking-up is dried after being cleaned with ethyl alcohol, is used
Raman spectrometer is tested.Obtain the Surface enhanced Raman spectroscopy such as Fig. 2.
Embodiment 2
The detection method of dithiocarbamate pesticide in a kind of agricultural product that this example proposes, comprising the following steps:
1, it weighs 10g banana and crushes (Carbatene, 1mg/L), 10ml acetonitrile solution is added, the solid potassium chloride of 2.0g is added, shake
2min is swung, 4g anhydrous magnesium sulfate is added, sample 3min fullys shake again, 5000rpm is centrifuged 5min；
2, after taking upper solution (i.e. acetonitrile solvent phase) 2mL to filter, as prepare liquid；
3, SERS substrate II is immersed in above-mentioned 200 μ L prepare liquid, after impregnating 10min, taking-up is dried after being cleaned with ethyl alcohol, is used
Raman spectrometer is tested.Obtain the Surface enhanced Raman spectroscopy such as Fig. 3.
Embodiment 3
The detection method of dithiocarbamate pesticide in a kind of agricultural product that this example proposes, comprising the following steps:
1, it weighs each 10g of three portions of bananas and crushes (wherein A: thiram 0.25mg/L, Carbatene 5mg/L；B: thiram 0.25mg/
L, Carbatene 2.5mg/L；C: thiram 0.25mg/L, Carbatene 0.5mg/L), 10ml acetonitrile solution is added, the nitre of 2.0g is added
Sour potassium solid shakes 2min, 4g anhydrous calcium chloride is added, sample 3min fullys shake again, 5000rpm is centrifuged 5min；
2, after taking upper solution (i.e. acetonitrile solvent phase) 2mL to filter, as prepare liquid；
3, SERS substrate II I is immersed in above-mentioned 200 μ L prepare liquid, after impregnating 10min, taking-up is dried after being cleaned with ethyl alcohol,
It is tested with Raman spectrometer.The Surface enhanced Raman spectroscopy such as Fig. 4 is obtained, is apparent that the drawing of the two mixture
Graceful spectrum.
Embodiment 4
The detection method of dithiocarbamate pesticide in a kind of agricultural product that this example proposes, comprising the following steps:
1,10g mango (mark-on 0mg/L, 0.5mg/L, 1mg/L, 5mg/L, 10mg/L respectively) is weighed in centrifuge tube, is added
The potassium nitrate solid of 2.0g, concussion 2min or so is added in 10ml acetonitrile solution, 4g anhydrous calcium chloride is added, sample fullys shake again
Product 3min or so, 5000rpm are centrifuged 5min.
2, after taking upper solution (i.e. acetonitrile solvent phase) 3mL to filter, as prepare liquid；
3, SERS substrate II is immersed in above-mentioned 180 μ L prepare liquid, after impregnating 10min, taking-up is dried after being cleaned with ethyl alcohol, is used
Raman spectrometer is tested；
4, choose 1370cm-1The spectral strength at place is made linearly, and such as attached drawing 5, fit equation is y=28123-3950x, is fitted excellent
Spend R2=0.97811。
Embodiment 5
The preparation of SERS substrate: preparing pit with chemical etching method, and 1: using means such as electron beam lithographies, in silicon or other linings
Structure required for processing on bottom is as template；2: the transfer of pattern coats photoresist in material surface to be processed, then
Template is pressed in its surface, is transferred to pattern on photoresist by the way of pressurization；3: the processing of substrate makes light with ultraviolet light
Photoresist solidification, after removing template, is etched away with the photoresist that etching liquid does not completely remove previous step, exposes material table to be processed
Then face is processed using the method for chemical etching, remove whole photoresists after the completion, finally obtain high-precision have it is recessed
The substrate in hole, is cleaned up with detergent, N2Drying, uses O later2Plasma washing machine handles 5min, then is immersed according to upper
2h in aurosol made of the preparation method of nano gold sol is stated, a large amount of water cleanings, obtain SERS substrate IV, obtain after taking-up
Structure is as shown in Figure 9.This SERS substrate IV SERS with higher activity, can be used for SERS trace detection.
The SERS substrate IV of above-mentioned preparation avoids homogeneity SERS substrate in the prior art and is only capable of making for single substance
Defect such as specially can not be used for quickly detecting under unknown materials type and micro content, be catalyzed at the operation；Using having
The SERS substrate of variation, imparting this example SERS substrate has the advantages that matching range is wide, universality is strong, can have simultaneously
Have and the functions such as be catalyzed, detected, degraded to many kinds of substance, significantly reduces workload and cost.It is particularly suitable for not
Know concentration and in the detection of dithiocarbamate pesticide that can contain in the very low agricultural product of energy content, agricultural product can be with
It is veterinary antibiotics, crop, is specifically as follows banana, dragon fruit, mango, apple, pears, cucumber, tomato, fresh corn, soybean etc..
It specifically can be as follows: the detection method of dithiocarbamate pesticide in a kind of agricultural product that this example proposes, including following step
It is rapid:
1, it weighs each 10g of three portions of bananas and crushes (wherein A: thiram 0.25mg/L, Carbatene 5mg/L；B: thiram 0.25mg/
L, Carbatene 2.5mg/L；C: thiram 0.25mg/L, Carbatene 0.5mg/L), 10ml acetonitrile solution is added, the nitre of 2.0g is added
Sour potassium solid shakes 2min, 4g anhydrous calcium chloride is added, sample 3min fullys shake again, 5000rpm is centrifuged 5min；
2, after taking upper solution (i.e. acetonitrile solvent phase) 2mL to filter, as prepare liquid；
3, the SERS substrate IV of above-mentioned preparation is immersed in above-mentioned 200 μ L prepare liquid, after impregnating 10min, taking-up ethyl alcohol is clear
It dries after washing, is tested with Raman spectrometer.It is apparent that the Raman spectrum of the two mixture, detection as the result is shown
Speed is fast, adaptable.
The above method utilizes Surface enhanced Raman spectroscopy, solves the dry of complex matrices in agricultural product especially fruit and vegetable
It disturbs, without the influence of agricultural product normal Raman, with step is simple, analysis time is short, selectivity is good, does not need large-scale instrument
Device, meet national standard limitation requirement, that quick and precisely detection of dithiocarbamate pesticide etc. in live food can be achieved is excellent
Point can have both easy to operate, at low cost under the premise of accuracy in detection height and low detection sensitivity height, detection lower limit
Advantage.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention, it is all according to the present invention
Equivalent change or modification made by Spirit Essence, should be covered by the protection scope of the present invention.
Claims (10)
1. the detection method of dithiocarbamate pesticide in a kind of agricultural product, which is characterized in that the detection method packet
Include following steps:
1) agricultural product to be measured are mixed with organic solvent, the first salt packet, the second salt packet, so that dithiocarbamate pesticide
Into in the organic solvent, by extraction, filtering or centrifugation, clear fluid test sample, the first salt packet are obtained
For destroying agricultural product eucaryotic cell structure, the second salt packet is used to absorb the moisture in agricultural product；
2) active region of SERS substrate is dipped in the predetermined time in the resulting fluid test sample of step (1), makes two sulphur
SERS substrate surface is adsorbed or grabbed for carbamate chemicals for agriculture molecule；
3) Raman detection will be carried out after SERS substrate drying obtained by step (2).
2. the detection method of dithiocarbamate pesticide in agricultural product according to claim 1, which is characterized in that
The first salt packet includes one of nitrate, carbonate, silicate, acetate, phosphate, halide salt or its any group
It closes.
3. the detection method of dithiocarbamate pesticide in agricultural product according to claim 2, which is characterized in that
The second salt packet includes one of sodium sulphate, calcium chloride, magnesium chloride or any combination thereof.
4. the detection method of dithiocarbamate pesticide in agricultural product according to claim 3, which is characterized in that
The organic solvent be selected from one of ethyl acetate, acetonitrile, dimethyl sulfoxide, dimethylformamide and dimethyl acetamide or its
Any combination.
5. the detection method of dithiocarbamate pesticide in agricultural product according to claim 1, which is characterized in that
The detection method further includes the steps that purifying the fluid test sample, and the purifying includes by the liquid detecting
Sample is dried and/or is adsorbed using filler, and alcohols polar solvent and/or ethers polar solvent is then added, is made
Sample for Raman detection.
6. the detection method of dithiocarbamate pesticide in agricultural product according to claim 5, which is characterized in that
The alcohols polar solvent is methanol and/or ethyl alcohol；And/or the ethers polar solvent includes glycol monoethyl ether and/or uncle
Butyl monomethyl ether；And/or the filler is one in C18 filler, PSA filler, graphitized carbon, aluminium oxide and PEP filler
Kind or any combination thereof.
7. according to claim 1 in agricultural product described in any one of -6 claims dithiocarbamate pesticide inspection
Survey method, which is characterized in that the SERS substrate is made of the drying of noble metal colloidal sol.
8. according to claim 1 in agricultural product described in any one of -6 claims dithiocarbamate pesticide inspection
Survey method, which is characterized in that the SERS substrate includes the noble metal nano particles or expensive of substrate and setting on the substrate
Metal layer.
9. according to claim 1 in agricultural product described in any one of -6 claims dithiocarbamate pesticide inspection
Survey method, which is characterized in that the SERS substrate includes having the substrate of multiple pits and self assembly expensive in the pit
Metallic nanoparticle submanifold.
10. the detection method of dithiocarbamate pesticide, feature exist in agricultural product according to claim 9
In the diameter of the pit is 50nm ~ 500nm, and the spacing between the pit is 5nm ~ 50nm, the noble metal nano particles
Noble metal nano particles number is 3 ~ 15 in cluster, and the partial size of each noble metal nano particles is 30nm ~ 120nm.
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