CN113588851B - Method for extracting and measuring dithiocarbamic acid ester, measuring device and application thereof - Google Patents
Method for extracting and measuring dithiocarbamic acid ester, measuring device and application thereof Download PDFInfo
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- CN113588851B CN113588851B CN202110855614.8A CN202110855614A CN113588851B CN 113588851 B CN113588851 B CN 113588851B CN 202110855614 A CN202110855614 A CN 202110855614A CN 113588851 B CN113588851 B CN 113588851B
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- dithiocarbamic acid
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- -1 dithiocarbamic acid ester Chemical class 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000002156 mixing Methods 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 16
- FKOLRODZLWCAKW-UHFFFAOYSA-N O.FC(C(C(F)(F)F)O)(F)F Chemical compound O.FC(C(C(F)(F)F)O)(F)F FKOLRODZLWCAKW-UHFFFAOYSA-N 0.000 claims abstract description 14
- WDBRXQONTNKZTB-UHFFFAOYSA-K dipotassium sodium hydrogen phosphate chloride Chemical compound P(=O)(O)([O-])[O-].[K+].[K+].[Cl-].[Na+] WDBRXQONTNKZTB-UHFFFAOYSA-K 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims abstract description 7
- 239000006228 supernatant Substances 0.000 claims abstract description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 6
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 claims abstract description 3
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims abstract description 3
- 238000002791 soaking Methods 0.000 claims abstract description 3
- 239000011780 sodium chloride Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 241000208125 Nicotiana Species 0.000 claims description 34
- 235000002637 Nicotiana tabacum Nutrition 0.000 claims description 34
- 150000004659 dithiocarbamates Chemical class 0.000 claims description 27
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 235000019505 tobacco product Nutrition 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims 2
- 238000007598 dipping method Methods 0.000 claims 1
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 16
- 238000004458 analytical method Methods 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 description 42
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 39
- 239000003638 chemical reducing agent Substances 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 25
- 239000012990 dithiocarbamate Substances 0.000 description 20
- 238000011084 recovery Methods 0.000 description 18
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 14
- 239000005823 Propineb Substances 0.000 description 13
- KKMLIVYBGSAJPM-UHFFFAOYSA-L propineb Chemical compound [Zn+2].[S-]C(=S)NC(C)CNC([S-])=S KKMLIVYBGSAJPM-UHFFFAOYSA-L 0.000 description 13
- 230000002572 peristaltic effect Effects 0.000 description 12
- 239000005802 Mancozeb Substances 0.000 description 11
- 239000002699 waste material Substances 0.000 description 11
- 238000002372 labelling Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000011261 inert gas Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000004364 calculation method Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 238000001819 mass spectrum Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 238000009616 inductively coupled plasma Methods 0.000 description 5
- YKSNLCVSTHTHJA-UHFFFAOYSA-L maneb Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S YKSNLCVSTHTHJA-UHFFFAOYSA-L 0.000 description 5
- 229920000940 maneb Polymers 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 4
- 210000001015 abdomen Anatomy 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 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 4
- 238000005119 centrifugation Methods 0.000 description 4
- 238000004811 liquid chromatography Methods 0.000 description 4
- 239000012086 standard solution Substances 0.000 description 4
- 239000001119 stannous chloride Substances 0.000 description 4
- 235000011150 stannous chloride Nutrition 0.000 description 4
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 3
- 239000005695 Ammonium acetate Substances 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 239000005843 Thiram Substances 0.000 description 3
- 239000005870 Ziram Substances 0.000 description 3
- 235000019257 ammonium acetate Nutrition 0.000 description 3
- 229940043376 ammonium acetate Drugs 0.000 description 3
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical class NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 239000000447 pesticide residue Substances 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 3
- 229960002447 thiram Drugs 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- DUBNHZYBDBBJHD-UHFFFAOYSA-L ziram Chemical compound [Zn+2].CN(C)C([S-])=S.CN(C)C([S-])=S DUBNHZYBDBBJHD-UHFFFAOYSA-L 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 2
- UDWPONKAYSRBTJ-UHFFFAOYSA-N [He].[N] Chemical compound [He].[N] UDWPONKAYSRBTJ-UHFFFAOYSA-N 0.000 description 2
- 239000011717 all-trans-retinol Substances 0.000 description 2
- 235000019169 all-trans-retinol Nutrition 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000003899 bactericide agent Substances 0.000 description 2
- 230000000711 cancerogenic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
- 235000019634 flavors Nutrition 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000005809 Metiram Substances 0.000 description 1
- 206010068319 Oropharyngeal pain Diseases 0.000 description 1
- 241000233679 Peronosporaceae Species 0.000 description 1
- 201000007100 Pharyngitis Diseases 0.000 description 1
- 208000003251 Pruritus Diseases 0.000 description 1
- 206010039509 Scab Diseases 0.000 description 1
- 208000037883 airway inflammation Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- TXSULMYZLWFIAT-UHFFFAOYSA-N carbamodithioic acid;ethene Chemical class C=C.NC(S)=S TXSULMYZLWFIAT-UHFFFAOYSA-N 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 235000010300 dimethyl dicarbonate Nutrition 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000007803 itching Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 229920000257 metiram Polymers 0.000 description 1
- 231100000219 mutagenic Toxicity 0.000 description 1
- 230000003505 mutagenic effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000926 not very toxic Toxicity 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 244000052769 pathogen Species 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000000241 respiratory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- 231100000378 teratogenic Toxicity 0.000 description 1
- 230000003390 teratogenic effect Effects 0.000 description 1
- 210000001685 thyroid gland Anatomy 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- 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
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
- G01N27/626—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode using heat to ionise a gas
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention belongs to the field of detection and analysis, and particularly relates to a method for extracting dithiocarbamic acid ester compounds in a sample, which comprises the following steps: soaking a sample in a water-hexafluoroisopropanol mixed solution, adding a sodium chloride-dipotassium hydrogen phosphate mixture, mixing, centrifuging, and separating out supernatant as an extracting solution containing dithiocarbamic acid ester compounds; wherein the volume ratio of water to hexafluoroisopropanol in the water-hexafluoroisopropanol mixed solution is (7-11) 1, and the weight ratio of sodium chloride to dipotassium hydrogen phosphate in the sodium chloride-dipotassium hydrogen phosphate mixture is (0.4-1) 1. The invention also relates to a method, a device and application for measuring the contents of various dithiocarbamic acid ester compounds in a sample. The method can accurately determine the contents of various dithiocarbamic acid ester compounds in the sample, and has good repeatability and high precision.
Description
Technical Field
The invention belongs to the field of detection and analysis, and particularly relates to a method for extracting dithiocarbamic acid ester compounds in a sample, and a method and a device for measuring the content of various dithiocarbamic acid ester compounds in the sample and application thereof.
Background
Dithiocarbamates (DTCs) are a very widely used class of bactericides in the world, which can be used to control over 400 pathogens in over 70 crops, and are the earliest and most widely used class of organic compounds in history. The bactericide has low cost and wide application, and is still widely used for preventing and treating downy mildew, spot disease, scab and the like caused by algae bacteria and fungi imperfecti in crops such as fruit trees, vegetables and the like. However, with the widespread use of dithiocarbamates, it has been found that animals and plants to which it has been applied produce a metabolite called thiohexanaphthene (ETU) during metabolism, which is carcinogenic, teratogenic and mutagenic and affects thyroid function for a long period of time, and is prescribed by the U.S. occupational safety and health agency as a carcinogen. In addition, dithiocarbamates have a moderate stimulating effect on mammalian skin and respiratory organs, and are manifested by itching, sore throat, and airway inflammation.
At present, there are various methods for analyzing the pesticide residue of dithiocarbamic acid esters internationally, including spectrophotometry, gas chromatography, liquid chromatography and the like, but the existing methods are to adopt a reducing agent to carry out the-CS in the pesticide residue of dithiocarbamic acid esters 2 The functional group is reduced into carbon disulfide, and then the content of the carbon disulfide is detected by an instrument so as to obtain the content of the dithiocarbamic acid ester pesticide residues. However, dithiocarbamates are a class of compounds that include dimethyl dithiocarbamates (DMDCs, such as sodium, iron, zinc, thiram), ethylene dithiocarbamates (EBDCs, such asCommon dithiocarbamate compounds such as mancozeb, maneb, zineb and mancozeb and propylenedithiocarbamate (PBDCs such as propineb and propineb) are not very toxic, but the toxicity of the dithiocarbamate compounds containing heavy metal ions is remarkably enhanced, so that the toxicity of different types of dithiocarbamate compounds is different, but the contents of various dithiocarbamate compounds cannot be detected by the existing method respectively, so that the residual amount of the dithiocarbamate compounds with relatively strong toxicity cannot be accurately obtained.
Thus, there is a need for a method for separately determining the amount of each dithiocarbamate compound in a sample.
Disclosure of Invention
The invention aims to provide a method for extracting dithiocarbamic acid ester compounds in a sample, which removes impurity interference through specific steps and has high extraction rate of the dithiocarbamic acid ester compounds; it is still another object of the present invention to provide an apparatus for measuring the content of various dithiocarbamate compounds in a sample; the invention also aims to provide a method for measuring the contents of various dithiocarbamic acid ester compounds in a sample by using the device, which can accurately measure the contents of various dithiocarbamic acid ester compounds in the sample, and has good repeatability and high precision.
To achieve the above object, a first aspect of the present invention relates to a method for extracting a dithiocarbamate compound from a sample, comprising the steps of:
soaking a sample in a water-hexafluoroisopropanol mixed solution, adding a sodium chloride-dipotassium hydrogen phosphate mixture, mixing, centrifuging, and separating out supernatant as an extracting solution containing dithiocarbamic acid ester compounds; wherein the volume ratio of water to hexafluoroisopropanol in the water-hexafluoroisopropanol mixture is (7-11): 1 (e.g. 8:1, 9:1, 10:1), and the weight ratio of sodium chloride to dipotassium hydrogen phosphate in the sodium chloride-dipotassium hydrogen phosphate mixture is (0.4-1): 1 (e.g. 0.5:1, 0.6:1, 0.7:1, 0.75:1, 0.8:1, 0.85:1, 0.9:1).
In some embodiments of the first aspect of the invention, the sample is a tobacco material and/or a tobacco product, preferably a tobacco material; more preferably, the sample is selected from flue-cured tobacco, burley tobacco and aromatic tobacco.
In some embodiments of the first aspect of the invention, the impregnation and/or mixing is performed under vortex shaking conditions.
In some embodiments of the first aspect of the invention, 2-10 mL of the water-hexafluoroisopropanol mixture is used per gram of sample, e.g. 3mL, 4mL, 5mL, 6mL, 7mL, 8mL, 9mL.
In some embodiments of the first aspect of the invention, 1 to 8g of the sodium chloride-dipotassium hydrogen phosphate mixture, e.g., 2g, 3g, 4g, 5g, 6g, 7g, is used per gram of sample.
In some embodiments of the first aspect of the invention, the impregnation is for 3 to 20 minutes, for example 5, 7, 8, 10, 12, 15, 17, 19 minutes.
In some embodiments of the first aspect of the invention, the mixing is for 1 to 10 minutes, for example 2, 3, 4, 5, 6, 7, 8, 9 minutes.
In some embodiments of the first aspect of the invention, the centrifugation is performed at a speed of 6000 to 16000rpm, for example 8000rpm, 10000rpm, 12000rpm, 15000rpm.
In some embodiments of the first aspect of the invention, the centrifugation is for 2 to 10 minutes, for example 3 minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes.
In some embodiments of the first aspect of the invention, the sample is immersed when the sample is immersed.
The second aspect of the invention relates to a device for measuring the content of various dithiocarbamic acid ester compounds in a sample, which comprises a liquid chromatograph, a micro-reactor, a gas-liquid separator and an inductively coupled plasma mass spectrum which are sequentially connected in series; wherein,,
the liquid chromatograph is provided with a sample inlet and a sample outlet;
the micro-reactor comprises a reducing agent storage tank, a reaction coil and a mixing coil; one end of the reaction coil is provided with a reducing agent inlet and a sample inlet, the other end of the reaction coil is provided with a reaction product outlet, the reducing agent inlet is connected with a reducing agent storage tank, and the sample inlet is connected with a sample outlet of the liquid chromatograph; one end of the mixing coil is provided with a feed liquid inlet and an inert gas inlet, the other end of the mixing coil is provided with a discharge hole, and the feed liquid inlet of the mixing coil is connected with a reaction product outlet of the reaction coil;
the gas-liquid separator comprises a fat belly type pipe with an upper end and a lower end being open, the lower end is used as a waste liquid outlet, the upper end is used as an air outlet, a feeding port is arranged on the fat belly part and is connected with a discharging port of the mixing coil, and the air outlet is connected with a sample inlet arranged on the inductively coupled plasma mass spectrometer.
In some embodiments of the second aspect of the invention, the microreactor further comprises a peristaltic pump, the reducing agent inlet of the reaction coil being connected to the reducing agent reservoir by the peristaltic pump.
In some embodiments of the second aspect of the present invention, the peristaltic pump has a dual-channel structure, the reducing agent inlet of the reaction coil is connected to the reducing agent storage tank through one channel of the peristaltic pump, and the waste liquid outlet of the gas-liquid separator discharges waste liquid through the other channel of the peristaltic pump.
In some embodiments of the second aspect of the invention, the number of turns of the reaction coil is 1.5 to 5 times, preferably 2 to 3 times, the number of turns of the hybrid coil.
In some embodiments of the second aspect of the invention, the reaction coil has 26 to 60 turns, preferably 30 to 50 turns.
In some embodiments of the second aspect of the invention, the hybrid coil has 8 to 22 turns, preferably 10 to 20 turns.
In some embodiments of the second aspect of the invention, the inner wall of the reaction coil and/or the mixing coil is distributed with a spiral.
In some embodiments of the second aspect of the invention, the inner diameter of the tube of the mixing coil is 1 to 2 times, for example 1.4 times, the inner diameter of the tube of the reaction coil.
In some embodiments of the second aspect of the invention, the inner diameter of the tube of the reaction coil is the same as the inner diameter of the reducing agent inlet.
In some embodiments of the second aspect of the invention, the internal diameter of the reductant inlet is from 1.5 to 5mm, preferably from 2 to 4mm, for example 2.5mm.
In some embodiments of the second aspect of the invention, the inner diameter of the waste outlet is equal to the inner diameter of the reductant inlet.
The third aspect of the present invention relates to a method for determining the content of various dithiocarbamate compounds in a sample, comprising the steps of:
obtaining an extract containing dithiocarbamate compounds according to the method of the first aspect of the present invention;
measuring the extracting solution by adopting the device of the second aspect of the invention to obtain a liquid chromatogram and a mass chromatogram;
calculating the carbon disulfide content generated by various dithiocarbamic acid ester compounds in the extracting solution according to the liquid chromatogram and ion peaks with the mass number of 75.8-77.3 in the mass chromatogram, and then calculating the content of various dithiocarbamic acid ester compounds in the sample;
wherein, in the device, the device comprises a plurality of control units,
the operating conditions of liquid chromatography include: the chromatographic column is an FTFF chromatographic column; the column temperature is 3 ℃ -10 ℃ (preferably 5 ℃ -8 ℃); the mobile phase is an aqueous ammonium acetate solution with a concentration of 400-500 mmol/L (for example 450 mmol/L), and the aqueous ammonium acetate solution contains 0.01-0.07 mol/L sodium hydroxide (for example 0.05 mol/L);
the operating conditions of inductively coupled plasma mass spectrometry include: a detection mode of full scanning integration is adopted; the flow rate of the plasma gas is 14-18L/min (for example, 16L/min); the auxiliary air flow is 0.5-3L/min (for example, 1L/min); the sample lifting rate is 0.5-1 mL/min (e.g., 0.8 mL/min).
In some embodiments of the third aspect of the present invention, the carbon disulfide content generated by each dithiocarbamate compound in the extract is quantitatively calculated by combining the ionic peaks with the mass number of 75.8-77.3 in the mass spectrum according to the qualitative type of the dithiocarbamate compound in the retention time of different chromatographic peaks in the liquid chromatogram.
In some embodiments of the third aspect of the present invention, the content of carbon disulfide generated by each dithiocarbamate compound in the extract is calculated by an external standard method according to ion peaks with mass numbers of 75.8-77.3 in the mass spectrogram; preferably, the external standard is carbon disulphide.
In some embodiments of the third aspect of the invention, the mobile phase flow rate of the liquid chromatograph is in the range of 0.1 to 0.3mL/min, preferably in the range of 0.2 to 0.25mL/min.
In some embodiments of the third aspect of the present invention, the sample injection amount of the liquid chromatograph is 10 μl.
In some embodiments of the third aspect of the invention, the sample flow rate of the liquid chromatograph is equal to the mobile phase flow rate.
In some embodiments of the third aspect of the invention, the forward power of the inductively coupled plasma mass spectrometry is 1100 to 1300W, for example 1200W;
in some embodiments of the third aspect of the invention, the inductively coupled plasma mass spectrometry has a sampling depth of 6 to 7mm, for example 6.5mm.
In some embodiments of the third aspect of the invention, the sampling cone aperture of the inductively coupled plasma mass spectrometry is in the range 0.7 to 1.4mm, for example 1.0mm.
In some embodiments of the third aspect of the invention, the skimmer cone aperture of the inductively coupled plasma mass spectrometry is 0.5 to 1mm, for example 0.8mm.
In some embodiments of the third aspect of the present invention, the data acquisition mode of the inductively coupled plasma mass spectrometry is a peak-jump mode.
In some embodiments of the third aspect of the invention, the residence time of the inductively coupled plasma mass spectrometry is 20 to 40ms, for example 30ms.
In some embodiments of the third aspect of the present invention, the number of acquisition points per unit mass of the inductively coupled plasma mass spectrometry is 3.
In some embodiments of the third aspect of the present invention, the number of data acquisition repetitions of the inductively coupled plasma mass spectrometry is three.
In some embodiments of the third aspect of the invention, the integration time of the inductively coupled plasma mass spectrometry is 0.100s.
In some embodiments of the third aspect of the invention, the temperature of the reaction coil in the apparatus is in the range of 35 ℃ to 50 ℃, preferably 40 ℃ to 45 ℃.
In some embodiments of the third aspect of the invention, the temperature of the mixing coil in the apparatus is 60 ℃ to 75 ℃, preferably 65 ℃ to 70 ℃.
In some embodiments of the third aspect of the invention, the apparatus wherein the gas-liquid separator is maintained at 20 ℃ to 40 ℃.
In some embodiments of the third aspect of the invention, the flow rates of the reductant inlet and the waste outlet are equal in the device.
In some embodiments of the third aspect of the present invention, in the apparatus, the reducing agent in the reducing agent tank is an acidic stannous chloride aqueous solution, preferably 8 to 10mol/L acidic stannous chloride aqueous solution; more preferably, the pH of the acidic stannous chloride aqueous solution is between 6.6 and 6.8.
In some embodiments of the third aspect of the invention, the flow rate of the reductant inlet in the device is 9 to 10mL/min, preferably 9.75 to 9.8mL/min.
In some embodiments of the third aspect of the invention, in the device, the flow rate of the sample inlet of the reaction coil is equal to the flow rate of the sample outlet of the liquid chromatograph.
In some embodiments of the third aspect of the invention, the flow rate of the inert gas inlet in the apparatus is 9.2 to 11mL/min, preferably 9.9 to 10.1mL/min.
In some embodiments of the third aspect of the invention, the inert gas is a nitrogen-helium mixture, preferably having a nitrogen to helium volume ratio of 1 (5-10), for example 1:8.
In some embodiments of the third aspect of the invention, the mode of analysis of inductively coupled plasma mass spectrometry is quantitative analysis.
A fourth aspect of the invention relates to a method for determining the toxic dithiocarbamate compound content in a sample, comprising the steps of:
determining the content of each dithiocarbamate compound in the sample according to the method of the third aspect of the invention;
the content of toxic dithiocarbamate compounds is summed.
In some embodiments of the fourth aspect of the invention, the sample is a tobacco material and/or a tobacco product, preferably a tobacco material, more preferably selected from flue-cured tobacco, burley tobacco and aromatic tobacco.
A fifth aspect of the invention relates to the use of the device according to the second aspect of the invention for determining the content of various dithiocarbamate compounds in a sample.
In some embodiments of the fifth aspect of the invention, the sample is a tobacco material and/or a tobacco product, preferably a tobacco material, more preferably selected from flue-cured tobacco, burley tobacco and aromatic tobacco.
In some embodiments of the invention, the dithiocarbamate is selected from one or more of mancozeb, maneb, metiram, maneb, zineb, thiram, ziram, propineb, thiram and ziram.
The invention has the beneficial effects that:
1. the method for extracting the dithiocarbamic acid ester compound in the sample can remove impurity interference and improve the extraction rate of the dithiocarbamic acid ester compound.
2. The method and the device for measuring the contents of various dithiocarbamic acid ester compounds in the sample can accurately measure the contents of various dithiocarbamic acid ester compounds in the sample, and have good repeatability and high precision.
Drawings
In order that the invention may be more readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings, in which:
FIG. 1 is a schematic view of one embodiment of the apparatus for measuring the content of various dithiocarbamate compounds in a sample according to the present invention;
FIG. 2 is a liquid chromatogram of the sample to be tested in example 2;
wherein: a is liquid chromatography, B is a micro-reactor, C is a gas-liquid separator, D is an inductively coupled plasma mass spectrum, 1 is a reducing agent storage tank, 2 is a peristaltic pump, 3 is a reaction coil, 4 is a mixing coil, 5 is a reducing agent inlet, 6 is a sample inlet, 7 is a reaction product outlet, 8 is a feed liquid inlet, 9 is an inert gas inlet, 10 is a discharge port, 11 is a fat portion, 12 is a waste liquid outlet, 13 is an air outlet, and 14 is a feed inlet.
Detailed Description
Embodiments of the present invention will now be described more fully hereinafter with reference to the accompanying examples, in which it is shown, however, that the examples are shown, and in which the invention is practiced. The following description of at least one exemplary embodiment is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
FIG. 1 is a schematic view of one embodiment of the apparatus for measuring the content of various dithiocarbamate compounds in a sample according to the present invention;
the device comprises a liquid chromatograph A, a micro-reactor B, a gas-liquid separator C and an inductively coupled plasma mass spectrum D which are sequentially connected in series, wherein the liquid chromatograph A and the micro-reactor B can be horizontally placed, and the gas-liquid separator C is vertically placed; wherein,,
the liquid chromatograph A is provided with a sample inlet and a sample outlet;
the micro-reactor B comprises a reducing agent storage tank 1, a peristaltic pump 2, a reaction coil 3 and a mixing coil 4; one end of the reaction coil 3 is provided with a reducing agent inlet 5 and a sample inlet 6 in parallel, the other end is provided with a reaction product outlet 7, the reducing agent inlet 5 is connected with the reducing agent storage tank 1 through the peristaltic pump 2, and the sample inlet 6 is connected with a sample outlet of the liquid chromatograph A; one end of the mixing coil 4 is provided with a feed liquid inlet 8 and an inert gas inlet 9 in parallel, the other end of the mixing coil is provided with a discharge hole 10, and the feed liquid inlet 8 of the mixing coil 4 is connected with a reaction product outlet 7 of the reaction coil 3;
the gas-liquid separator C comprises a fat belly pipe with an upper end and a lower end being open, the lower end is used as a waste liquid outlet 12, the upper end is used as an air outlet 13, the fat belly part 11 is provided with a feed inlet 14 which is connected with a discharge port 10 of the mixing coil, and the air outlet 13 is connected with a sample inlet of the inductively coupled plasma mass spectrum D; the peristaltic pump 2 is a double-channel device, the waste liquid outlet 12 is connected with the other channel of the peristaltic pump 2 through a hose with the same diameter as the waste liquid outlet 12, and the flow rates of the waste liquid outlet 12 and the reducing agent inlet 5 are controlled to be the same through the peristaltic pump 2;
in the embodiment, the reaction coil is 30-50 turns;
in the embodiment, the mixed coil has 10-20 turns;
in the embodiment, the inner walls of the reaction coil and the mixing coil are distributed with spiral lines;
in this embodiment, the inner diameter of the pipeline of the hybrid coil is 1.4 times that of the reaction coil;
in this embodiment, the inner diameter of the pipeline of the reaction coil is the same as the inner diameter of the reducing agent inlet;
in this example, the inside diameter of the reductant inlet is 2.5mm;
in this embodiment, the inner diameter of the waste liquid outlet is equal to the inner diameter of the reducing agent inlet.
The invention also relates to a system for measuring the content of various dithiocarbamic acid ester compounds in a sample, which comprises an impregnating device, a mixing device, a sedimentation separation device and a device shown in figure 1; wherein,,
the impregnating equipment is provided with a feed inlet and a discharge outlet, wherein the feed inlet is used for adding a sample and water-hexafluoroisopropanol mixed solution;
the mixing equipment is provided with a feed inlet, an auxiliary agent inlet and a discharge outlet, the feed inlet of the mixing equipment is connected with the discharge outlet of the impregnating equipment, and the auxiliary agent inlet is used for adding a sodium chloride-dipotassium hydrogen phosphate mixture;
the sedimentation separator is provided with a feed inlet which is connected with a discharge port of the mixing equipment, the upper part of the sedimentation separator is provided with a supernatant outlet which is connected with a sample inlet of the liquid chromatograph in the device;
in this embodiment, the system further comprises a vortex oscillator in which the impregnating device and the mixing device are located.
Example 1
(1) 2g of flue-cured tobacco sample is weighed into a 50mL centrifuge tube, 10mL of water-hexafluoroisopropanol mixed solution (volume ratio is 10:1) is added, vortex shaking is carried out for 8min, then 4g of sodium chloride-dipotassium hydrogen phosphate mixed powder (weight ratio is 0.75:1) is added, vortex shaking is carried out for 2min, centrifugation is carried out for 5min at 10000rpm, and supernatant fluid is taken as a sample to be detected.
(2) The device shown in fig. 1 is used for detecting the sample to be detected, and the operating conditions of the device are as follows:
(1) operating conditions of liquid chromatography a: the chromatographic column is an FTFF chromatographic column (specification 4.6mm x 150 mm); column temperature is 5-8 ℃; the mobile phase is 450mmol/L ammonium acetate aqueous solution (containing 0.05mol/L sodium hydroxide); the flow rate of the mobile phase is 0.2-0.25 mL/min; the sample injection amount is 10 mu L; the sample flow rate of the liquid chromatograph A is equal to the flow rate of the mobile phase;
(2) operating conditions of microreactor B: the reducer is 8-10 mol/L acidic stannous chloride aqueous solution (pH value is 6.6-6.8); the flow rate (double channels) of the peristaltic pump 2 is 9.8-9.75 mL/min; the pipeline of the reaction coil 3 is kept at 40-45 ℃; the flow rate of the sample inlet 6 of the reaction coil 3 is equal to the sample outlet flow rate of the liquid chromatograph A; the pipeline of the mixing coil 4 is kept at 65-70 ℃; the inert gas is nitrogen-helium mixed gas (volume ratio is 1:8); the flow rate of the inert gas inlet 9 is 9.9-10.1 mL/min;
(3) operating conditions of the gas-liquid separator C: the gas-liquid separator C is placed under the constant temperature condition of 20-40 ℃ (precision 2 ℃);
(4) operating parameters of inductively coupled plasma mass spectrometry D:
table 1 operating parameters of inductively coupled plasma mass spectrometry
And (3) determining the types of the dithiocarbamic acid ester compounds in the sample to be detected according to the retention time of different chromatographic peaks in the chromatogram, and obtaining the peak area of the ion peak with the mass number of 75.8-77.3 in the mass spectrum corresponding to each dithiocarbamic acid ester compound.
(3) Calculation and results
Preparing a carbon disulfide series standard solution: diluting a carbon disulfide standard with isooctane to obtain a carbon disulfide stock solution with the concentration of 10 mug/mL; accurately transferring 0.05mL, 0.1mL, 0.2mL, 0.5mL, 1mL, 2mL and 5mL of carbon disulfide stock solution into different 25mL volumetric flasks respectively, and fixing the volume by isooctane to obtain a carbon disulfide series standard solution. The concentration range of the carbon disulphide series standard solution should cover the content that is expected to be detected.
And (3) detecting the carbon disulfide series standard solution by adopting the inductively coupled plasma mass spectrometry in the (2), wherein the operation parameters are as in (4) in the (2), and a standard working curve is manufactured according to the concentration of the carbon disulfide and the ion peak-to-peak area of the mass number of 75.8-77.3 in the mass spectrogram.
Substituting the peak area of the ion peak with the mass number of 75.8-77.3 in the mass spectrogram corresponding to each dithiocarbamic acid ester compound in the sample to be detected into a standard working curve for calculation to obtain the carbon disulfide content generated by each dithiocarbamic acid ester compound in the sample to be detected, and then calculating the dithiocarbamic acid ester compound content in the flue-cured tobacco sample according to the following formula.
In the formula:
x represents the content of dithio-carbamate compound in the tobacco sample, and the unit is mg/kg;
c represents the content of carbon disulfide generated by each dithiocarbamic acid ester compound in the sample to be detected, and the unit is mug/mL;
v represents the volume of the sample to be measured, and the unit is mL;
s represents the conversion coefficient of carbon disulfide to each dithiocarbamate compound, as shown in table 2;
m represents the mass of the tobacco sample, and the unit is g;
w represents the moisture mass content of the tobacco sample,% W/W.
TABLE 2 conversion coefficients of various dithiocarbamate compounds
The contents of the various dithiocarbamate compounds in the flue-cured tobacco samples of this example are shown in Table 3.
TABLE 3 content of various dithiocarbamate Compounds in flue-cured tobacco samples
| Dithiocarbamate compound | Content (mg/kg) |
| Propineb (zinc propineb) | 0.056 |
| Fumei iron | 0.063 |
| Mancozeb | 0.031 |
(4) Average mark recovery and precision
Adding 50mg of propineb standard substance, 50mg of Fumei standard substance and 50mg of mancozeb standard substance into 2g of flue-cured tobacco sample to obtain a standard-added sample; the contents of various dithiocarbamate compounds in the labeled sample were detected according to the methods in (1) to (3), and then the labeled recovery was calculated.
The detection was repeated 6 times to calculate the average addition recovery and RSD.
The results are shown in Table 4.
TABLE 4 Table 4
As can be seen from Table 1, the method has high labeling recovery rate, meets the actual detection requirement, and has high accuracy; in addition, the method has good repeatability of detection.
Example 2
(1) 3.5g of burley tobacco sample is weighed into a 50mL centrifuge tube, 15mL of water-hexafluoroisopropanol mixed solution (volume ratio is 9:1) is added, vortex shaking is carried out for 10min, then 5g of sodium chloride-dipotassium hydrogen phosphate mixed powder (weight ratio is 0.8:1) is added, vortex shaking is carried out for 3min, centrifugation is carried out for 7.5min at 10000rpm, and supernatant fluid is taken as a sample to be detected.
(2) Detecting a sample to be detected by using a detection device, wherein the structure and the operation conditions of the detection device are the same as those of the (2) in the embodiment 1; the chromatogram of the sample to be tested in this example is shown in fig. 2, and each of the peaks of the chromatogram sequentially represents mancozeb, propineb and maneb from left to right.
(3) Calculation and results
The calculation method is the same as in item (3) of example 1. The contents of the various dithiocarbamate compounds in the burley tobacco samples are calculated as shown in table 5.
TABLE 5 content of various dithiocarbamate Compounds in burley tobacco samples
| Dithiocarbamate compound | Content (mg/kg) |
| Propineb (zinc propineb) | 0.124 |
| Mancozeb | 0.239 |
| Mancozeb sodium | 0.096 |
(4) Average mark recovery and precision
Adding 10mg of propineb standard substance, 10mg of mancozeb standard substance and 10mg of maneb sodium standard substance into 3.5g of burley tobacco sample to obtain a standard-added sample; the contents of various dithiocarbamate compounds in the labeled test sample were measured according to the items (1) to (3) in example 1, and then the labeled recovery was calculated.
The above detection was repeated 6 times to calculate the average labeled recovery and RSD.
The results are shown in Table 6.
TABLE 6
As can be seen from Table 6, the method has high labeling recovery rate, meets the actual detection requirement, and has high accuracy; in addition, the method has good repeatability of detection.
Example 3
(1) Weighing 5g of aromatic tobacco sample into a 50mL centrifuge tube, adding 20mL of water-hexafluoroisopropanol mixed solution with the volume ratio of 10:1, vortex-shaking for 10min, then adding 6g of sodium chloride-dipotassium hydrogen phosphate mixed powder (weight ratio of 0.85:1), vortex-shaking for 4min, centrifuging at 10000rpm for 9min, and taking supernatant as a sample to be tested.
(2) The sample to be tested is detected by using a detection device, and the structure and the operation conditions of the detection device are the same as those of the (2) in the embodiment 1.
(3) Calculation and results
The calculation method is the same as in item (3) of example 1. The contents of the various dithiocarbamate compounds in the flavor smoke samples were calculated as shown in table 7.
Table 7 content of various dithiocarbamate compounds in the flavor smoke samples
| Dithiocarbamate compound | Content (mg/kg) |
| Fumei zinc | 0.387 |
| Mancozeb magnesium | 0.166 |
| Propineb (zinc propineb) | 0.028 |
(4) Average mark recovery and precision
Adding 25mg of a ziram standard substance, 25mg of a mancozeb standard substance and 25mg of a propineb standard substance into 5g of a aromatic tobacco sample to obtain a standard-added sample; the contents of various dithiocarbamate compounds in the labeled test sample were measured according to the items (1) to (3) in example 1, and then the labeled recovery was calculated.
The above detection was repeated 6 times to calculate the average labeled recovery and RSD.
The results are shown in Table 8.
TABLE 8
As can be seen from Table 8, the method has high labeling recovery rate, meets the actual detection requirement, and has high accuracy; in addition, the method has good repeatability of detection.
Comparative example
The water-hexafluoroisopropanol mixture in example 1 was replaced with an equal volume of the water-methanol mixture (volume ratio 10:1), the rest was the same as in example 1, and a labeling recovery experiment was performed according to item (4) in example 1 (labeling amount was the same as in example 1), and the resulting average labeling recovery was shown in table 9.
The water-hexafluoroisopropanol mixture in example 1 was replaced with an equal volume of the water-ethanol mixture (volume ratio 10:1), the rest was the same as in example 1, and the labeling recovery experiment was performed according to item (4) in example 1 (labeling amount was the same as in example 1), and the resulting average labeling recovery was shown in table 9.
TABLE 9 average addition of the results for recovery
As can be seen from the combination of tables 4 and 9, the method of the present invention has higher recovery rate and higher accuracy compared with the comparative example method.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (3)
1. A method for extracting dithiocarbamate compounds from a sample, comprising the steps of:
soaking a sample in a water-hexafluoroisopropanol mixed solution, adding a sodium chloride-dipotassium hydrogen phosphate mixture, mixing, centrifuging, and separating out supernatant as an extracting solution containing dithiocarbamic acid ester compounds; wherein the sample is tobacco raw material and/or tobacco product, the volume ratio of water and hexafluoroisopropanol in the water-hexafluoroisopropanol mixed solution is (7-11): 1, and the weight ratio of sodium chloride and dipotassium hydrogen phosphate in the sodium chloride-dipotassium hydrogen phosphate mixture is (0.4-1): 1.
2. The method of claim 1, characterized by one or more of the following:
A. the sample is a tobacco raw material;
B. impregnating and/or mixing under vortex shaking conditions;
C. 2-10 mL of water-hexafluoroisopropanol mixed solution is adopted for each gram of sample;
D. 1-8 g of sodium chloride-dipotassium hydrogen phosphate mixture is adopted for each gram of sample;
E. dipping for 3-20 minutes;
F. mixing for 1-10 minutes;
G. centrifugal treatment is carried out at the rotating speed of 6000-16000 rpm;
H. and centrifuging for 2-10 minutes.
3. The method of claim 2, wherein in item a, the sample is selected from flue-cured tobacco, burley tobacco, and aromatic tobacco.
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