CN117214332A - Method for detecting dithiocarbamic acid ester compound - Google Patents
Method for detecting dithiocarbamic acid ester compound Download PDFInfo
- Publication number
- CN117214332A CN117214332A CN202311197091.8A CN202311197091A CN117214332A CN 117214332 A CN117214332 A CN 117214332A CN 202311197091 A CN202311197091 A CN 202311197091A CN 117214332 A CN117214332 A CN 117214332A
- Authority
- CN
- China
- Prior art keywords
- carbon disulfide
- extraction
- detecting
- dithiocarbamate
- sample
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 34
- -1 dithiocarbamic acid ester compound Chemical class 0.000 title claims abstract description 33
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims abstract description 177
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000001514 detection method Methods 0.000 claims abstract description 30
- 238000001785 headspace extraction Methods 0.000 claims abstract description 28
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 26
- 239000012086 standard solution Substances 0.000 claims abstract description 20
- 239000000243 solution Substances 0.000 claims abstract description 19
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 16
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 16
- 238000004458 analytical method Methods 0.000 claims abstract description 14
- 239000012990 dithiocarbamate Substances 0.000 claims abstract description 14
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 13
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 13
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 13
- 238000012545 processing Methods 0.000 claims abstract description 6
- 238000000605 extraction Methods 0.000 claims description 29
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 25
- 239000000835 fiber Substances 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 235000013399 edible fruits Nutrition 0.000 claims description 10
- 239000002808 molecular sieve Substances 0.000 claims description 10
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 10
- 235000007164 Oryza sativa Nutrition 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 235000009566 rice Nutrition 0.000 claims description 8
- 244000269722 Thea sinensis Species 0.000 claims description 6
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 6
- 238000001819 mass spectrum Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims description 5
- 239000012159 carrier gas Substances 0.000 claims description 4
- 238000007405 data analysis Methods 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 238000010926 purge Methods 0.000 claims description 4
- 238000011002 quantification Methods 0.000 claims description 4
- 244000061176 Nicotiana tabacum Species 0.000 claims description 3
- 235000002637 Nicotiana tabacum Nutrition 0.000 claims description 3
- 241000209140 Triticum Species 0.000 claims description 3
- 235000021307 Triticum Nutrition 0.000 claims description 3
- 240000008042 Zea mays Species 0.000 claims description 3
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 3
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 3
- TXSULMYZLWFIAT-UHFFFAOYSA-N carbamodithioic acid;ethene Chemical compound C=C.NC(S)=S TXSULMYZLWFIAT-UHFFFAOYSA-N 0.000 claims description 3
- TYUWIWBZXGOFHY-UHFFFAOYSA-N carbamodithioic acid;prop-1-ene Chemical compound CC=C.NC(S)=S TYUWIWBZXGOFHY-UHFFFAOYSA-N 0.000 claims description 3
- 235000005822 corn Nutrition 0.000 claims description 3
- 238000003795 desorption Methods 0.000 claims description 3
- MZGNSEAPZQGJRB-UHFFFAOYSA-N dimethyldithiocarbamic acid Chemical compound CN(C)C(S)=S MZGNSEAPZQGJRB-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims 1
- 239000000575 pesticide Substances 0.000 abstract description 21
- 235000013870 dimethyl polysiloxane Nutrition 0.000 abstract description 14
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 abstract description 6
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 abstract description 6
- 230000035945 sensitivity Effects 0.000 abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- 239000005416 organic matter Substances 0.000 abstract description 2
- 238000002470 solid-phase micro-extraction Methods 0.000 abstract 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 24
- 238000011084 recovery Methods 0.000 description 18
- 239000005823 Propineb Substances 0.000 description 14
- KKMLIVYBGSAJPM-UHFFFAOYSA-L propineb Chemical compound [Zn+2].[S-]C(=S)NC(C)CNC([S-])=S KKMLIVYBGSAJPM-UHFFFAOYSA-L 0.000 description 14
- 239000011717 all-trans-retinol Substances 0.000 description 12
- 235000019169 all-trans-retinol Nutrition 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 241000209094 Oryza Species 0.000 description 7
- 239000000447 pesticide residue Substances 0.000 description 6
- 235000013616 tea Nutrition 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 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
- 230000032683 aging Effects 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 235000013339 cereals Nutrition 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 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
- 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 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000003899 bactericide agent Substances 0.000 description 2
- 150000004659 dithiocarbamates Chemical class 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 230000002431 foraging effect Effects 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- 239000001119 stannous chloride Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- NVHNGVXBCWYLFA-UHFFFAOYSA-N 1,3-diazinane-2-thione Chemical compound S=C1NCCCN1 NVHNGVXBCWYLFA-UHFFFAOYSA-N 0.000 description 1
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 208000031888 Mycoses Diseases 0.000 description 1
- 206010043275 Teratogenicity Diseases 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 230000000172 allergic effect Effects 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 208000006673 asthma Diseases 0.000 description 1
- 208000010668 atopic eczema Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007665 chronic toxicity Effects 0.000 description 1
- 231100000160 chronic toxicity Toxicity 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 231100000584 environmental toxicity Toxicity 0.000 description 1
- 210000004907 gland Anatomy 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 231100000211 teratogenicity Toxicity 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Landscapes
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention belongs to the technical field of organic matter detection, and particularly discloses a detection method of dithiocarbamic acid ester compounds. Firstly, preparing water, stannous chloride-hydrochloric acid solution, ascorbic acid and carbon disulfide into carbon disulfide standard solutions with different gradient concentrations, then performing headspace extraction by using PDMS/CAR/DVB, introducing a GC-QTOF instrument for analysis after completion, and drawing a standard curve; and finally, detecting the detected sample by adopting the same method, and obtaining the concentration of the dithiocarbamate compound in the detected sample through result processing. The detection method disclosed by the invention is a green, automatic and high-sensitivity detection method for the dithiocarbamic acid ester pesticides. The invention adopts solid phase microextraction, reduces the use of organic reagents, combines with GC-QTOF instrument analysis, and greatly improves the sensitivity and detection precision of the analysis method.
Description
Technical Field
The invention relates to the technical field of organic matter detection, in particular to a detection method of dithiocarbamic acid ester compounds.
Background
In order to ensure the grain yield, a large amount of pesticides are used in pest control of grain crops every year worldwide, most of the pesticides are degraded under natural conditions, and a small part of the pesticides can remain on the surface of agricultural products to flow into the consumer market, so that potential food safety problems are caused.
The dithiocarbamic acid ester (DTC) compound pesticide is one of the bactericides with the largest consumption in the world, and is widely used in crops such as vegetables, fruits, grains and the like because of the advantages of broad-spectrum bioactivity, low production cost, low environmental toxicity, good prevention and control effects on fungal diseases and the like. The dithiocarbamic acid ester pesticide mainly comprises dimethyl dithiocarbamic acid ester (such as sodium thiram, ferrous thiram, zinc thiram, etc.), ethylene dithiocarbamic acid ester (such as sodium zineb, manganese zineb, etc.), and propylene dithiocarbamic acid ester (such as sodium propineb, zinc propineb). The metabolites of dithiocarbamic acid pesticides in plants and animals, namely ethylene thiourea and propylene thiourea, have the harm of carcinogenesis, induced organism mutation, teratogenicity and the like, and meanwhile, the bactericides have chronic toxicity and can cause skin allergic infection and asthma. The residual amount of DTC pesticides is clearly required in most countries, wherein the maximum residual amount of propineb in rice is limited to 2mg/kg in food safety standards. Therefore, quantitative analysis of dithiocarbamates is necessary. Although there is a method for detecting a dithiocarbamate pesticide using GC-FPD, the method has a problem of low sensitivity and high detection limit.
Therefore, how to provide a method for detecting a dithiocarbamate compound, which reduces the use of organic reagents in the detection process and improves the sensitivity of the analysis method is a problem to be solved in the art.
Disclosure of Invention
In view of the above, the invention provides a method for detecting dithiocarbamic acid ester compounds, which solves the problems of low detection precision, low sensitivity, large organic solvent consumption and the like of the existing method.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a method for detecting dithio carbamate compounds comprises the following steps:
1) Pretreatment: mixing water, stannous chloride-hydrochloric acid solution, ascorbic acid and different amounts of carbon disulfide to obtain carbon disulfide standard solutions with gradient concentration, respectively placing the carbon disulfide standard solutions in a headspace bottle, and then heating in a water bath to complete pretreatment;
2) Headspace extraction: carrying out headspace extraction on the pretreated mixed solution by adopting an extraction fiber head with a divinylbenzene/carbon molecular sieve/polydimethylsiloxane coating;
3) Drawing a standard curve: introducing the extracted gas into a GC-QTOF instrument for analysis to obtain a processing result and drawing a standard curve;
4) Sample detection: and replacing the carbon disulfide standard solution and water with the sample to be detected, sequentially carrying out pretreatment and headspace extraction, introducing the extracted gas into a GC-QTOF instrument for analysis to obtain the concentration of carbon disulfide, and further calculating the concentration of the dithiocarbamic acid ester compound.
Preferably, in the step 1), the volume mass ratio of water, stannous chloride-hydrochloric acid solution and ascorbic acid is 1.8-2.2 ml:4.5 to 5.5ml: 0.02-0.04 g, wherein the mass concentration of carbon disulfide in the mixed solution in the step 1) is respectively 0.005mg/l, 0.05mg/l, 0.1mg/l, 0.5mg/l, 1mg/l and 2mg/l.
Preferably, the temperature of the water bath heating in the step 1) is 70-90 ℃, the time of the water bath heating is 0.8-1.2 h, and the water bath heating is carried out once every 12-16 min.
Preferably, the extracted fiber head with the divinylbenzene/carbon molecular sieve/polydimethylsiloxane coating is aged before extraction, wherein the aging temperature is 220-260 ℃, and the aging time is 25-35 min;
the temperature of the headspace extraction in the step 2) is 35-45 ℃, the time of the headspace extraction is 8-12 min, and the desorption time after the headspace extraction is 2-5 min.
Preferably, the GC-QTOF instrument parameters are as follows:
GESTEL autosample injection, wherein the chromatographic column is Agilent DB-5MS, and parameters of the chromatographic column are as follows: 60m multiplied by 250 mu m multiplied by 0.25 mu m, the initial temperature of the column temperature box is set to 50 ℃, the heating rate is 20 ℃/min, the temperature is raised to 100 ℃ and kept for 1min, the temperature of the sample injector is 150 ℃, the split ratio is 5:1, the carrier gas is helium, and the purging flow is 3ml/min; the mass spectrum is carried out in a full scanning mode, the emission current is 6 mu A, the electron energy is 70eV, the instrument operation time is 7.5min, the carbon disulfide peak time is 5.3min, and the data analysis adopts the carbon disulfide extraction molecular weight of 76m/z for quantification.
Preferably, the volume mass ratio of the sample to be detected, stannous chloride-hydrochloric acid solution and ascorbic acid in the pretreatment process in the step 4) is 1.8-2.2 g:4.5 to 5.5ml: 0.02-0.04 g.
Preferably, the sample to be detected in the step 4) comprises one of rice fruit, wheat fruit, corn fruit, tea and tobacco, and the particle size of the sample to be detected is 150-850 μm.
Preferably, the dithiocarbamate compound in the step 4) includes one or more of dimethyl dithiocarbamate, ethylene dithiocarbamate and propylene dithiocarbamate.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention discloses a detection method of pesticide residues (dithiocarbamic acid ester compounds), which is a green, automatic and high-sensitivity DTC pesticide detection method. According to the invention, the DTC pesticide is innovatively decomposed into carbon disulfide gas through a derivatization step, and the solid-phase microextraction is adopted as a solvent-free carbon disulfide extraction mode, so that the use of organic reagents is reduced, and the sensitivity of an analysis method is greatly improved by combining GC-QTOF instrument analysis;
2. the equivalent carbon disulfide detection Limit (LOD) of the pesticide residue (dithiocarbamic acid ester compound) detection method disclosed by the invention is 0.05mg/l, and the equivalent carbon disulfide quantitative Limit (LOQ) is 0.05mg/l. By adding two pesticides, namely propineb and zineb, into a sample to be detected, the respective recovery rates are found to be 89-116% and 70-72%, the relative standard deviation is 1.9-7.3% and 3.4-7.6%, and the precision and recovery rate of the method are good;
3. the detection method disclosed by the invention is simple and easy to operate, has high automation degree and has wide application prospect in actual sample detection.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a chromatogram obtained by testing a 0.005mg/l carbon disulfide standard solution;
FIG. 2 is a chromatogram obtained by testing a 0.05mg/l carbon disulfide standard solution;
FIG. 3 is a chromatogram obtained by testing a 0.1mg/l carbon disulfide standard solution;
FIG. 4 is a chromatogram obtained by testing a 0.5mg/l carbon disulfide standard solution;
FIG. 5 is a chromatogram obtained by testing a 1mg/l carbon disulfide standard solution;
FIG. 6 is a chromatogram obtained from a 2mg/l carbon disulfide standard solution test;
FIG. 7 is a graph of the target curve obtained in example 1;
FIG. 8 is a chromatogram obtained from the test of example 2;
fig. 9 is a chromatogram obtained by the ECD test method.
Detailed Description
The invention provides a method for detecting dithiocarbamic acid ester compounds, which comprises the following steps:
1) Pretreatment: mixing water, stannous chloride-hydrochloric acid solution, ascorbic acid and different amounts of carbon disulfide to obtain carbon disulfide standard solutions with gradient concentration, respectively placing the carbon disulfide standard solutions in a headspace bottle, and then heating in a water bath to complete pretreatment;
2) Headspace extraction: carrying out headspace extraction on the pretreated mixed solution by adopting an extraction fiber head with a divinylbenzene/carbon molecular sieve/polydimethylsiloxane coating;
3) Drawing a standard curve: introducing the extracted gas into a GC-QTOF instrument for analysis to obtain a processing result and drawing a standard curve;
4) Sample detection: and replacing the carbon disulfide standard solution and water with the sample to be detected, sequentially carrying out pretreatment and headspace extraction, introducing the extracted gas into a GC-QTOF instrument for analysis to obtain the concentration of carbon disulfide, and further calculating the concentration of the dithiocarbamic acid ester compound.
In the present invention, the gas extracted in the steps 3) and 4) is carbon disulphide.
In the invention, the volume mass ratio of the water, the stannous chloride-hydrochloric acid solution and the ascorbic acid in the step 1) is 1.8-2.2 ml:4.5 to 5.5ml:0.02 to 0.04g, preferably 1.9 to 2.1ml: 4.8-5.2 ml:0.025 to 0.035g, more preferably 2ml:5ml:0.03g; the mass concentration of the carbon disulfide in the mixed solution in the step 1) is respectively 0.005mg/l, 0.05mg/l, 0.1mg/l, 0.5mg/l, 1mg/l and 2mg/l; in the step 1), carbon disulfide is preferably added last, so that loss is avoided.
In the present invention, the water bath heating temperature in the step 1) is 70 to 90 ℃, specifically 72 ℃, 74 ℃, 75 ℃, 76 ℃, 78 ℃, 80 ℃, 82 ℃, 84 ℃, 85 ℃, 86 ℃, 88 ℃; the heating time in water bath is 0.8-1.2 h, and can be specifically 0.9h, 1h and 1.1h; the water bath is heated for one time every 12-16 min, specifically 13min, 14min and 15min.
In the present invention, stannous chloride-hydrochloric acid solution: 7.5g of stannous chloride solid is weighed and dissolved in 33ml of concentrated hydrochloric acid solution (analytically pure), and when the stannous chloride is dissolved completely and the solution is transparent, the solution is poured into a 100ml volumetric flask to be fixed to 100ml by pure water.
In the invention, before extraction, the extracted fiber head with the divinylbenzene/carbon molecular sieve/polydimethylsiloxane coating is aged at 220-260 ℃, specifically 225 ℃, 230 ℃, 235 ℃, 240 ℃, 245 ℃, 250 ℃ and 255 ℃; the aging time is 25-35 min, and can be specifically 26min, 28min, 30min, 32min and 34min.
The temperature of the headspace extraction in the step 2) is 35-45 ℃, and can be 36 ℃, 38 ℃, 40 ℃, 42 ℃ and 44 ℃ specifically; the headspace extraction time is 8-12 min, and can be specifically 9min, 10min and 11min; the desorption time after the headspace extraction is 2-5 min, and can be specifically 2.5min, 3min, 3.5min, 4min and 4.5min.
In the invention, the most preferable temperature of the headspace extraction is 40 ℃, the influence of the temperature on the extraction efficiency of the carbon disulfide is large, and the detection of pesticide residues is not facilitated due to the fact that the temperature of the headspace extraction is too high or too low. For example, the extraction efficiency of carbon disulfide at 60 ℃ is far lower than 35-45 ℃.
In the invention, the peak area of the carbon disulfide and the headspace extraction time show a trend of ascending and then descending, the highest point is 20min, and the peak height of the carbon disulfide is highest and the peak area is largest at the moment. And meanwhile, the peak area of carbon disulfide at 10min is compared, and compared with that at 20min, the peak area of carbon disulfide is 1.5% lower, so that the effect on the result is not great, and the extraction time after optimization is selected for reducing the experimental time is 8-12 min.
In the invention, the extraction effect of the fiber head coating material PDMS/CAR/DVB (divinylbenzene/carbon molecular sieve/polydimethylsiloxane) on carbon disulfide is obviously higher than that of coating materials such as PA, PDMS/DVB and the like.
In the present invention, the GC-QTOF instrument parameters are as follows:
the chromatographic column is Agilent DB-5MS or the same type of chromatographic column (such as HP-5, inert Cap 5 (USP G27), rtx-5MS, rtx-5Sil MS, rxi-5MS, rxi-5Sil MS, VF-5MS, PTE-5, CP-Sil 8CB Low Bleed/MS, BPX-5, AT-5MS, ZB-5MS, SLB-5MS, equipment-5, etc.), and the chromatographic column parameters are as follows: 60m×250 μm×0.25 μm (or 30m×250 μm×0.25 μm), oven initial temperature set to 50deg.C, heating rate 20 ℃/min, heating to 100deg.C, maintaining for 1min, injector temperature 150 ℃, split ratio 5:1, carrier gas helium, purge flow 3ml/min; the mass spectrum is carried out in a full scanning mode, the emission current is 6 mu A, the electron energy is 70eV, the instrument operation time is 7.5min, the carbon disulfide peak time is 5.3min, and the data analysis adopts the carbon disulfide extraction molecular weight of 76m/z for quantification.
In the present invention, agilent DB-5MS may be replaced with Innovax column 60m×250 μm×0.25 μm (or 30m×250 μm×0.25 μm), and chromatographic conditions may be the same as Agilent DB-5MS.
In the invention, the volume mass ratio of the sample to be detected to stannous chloride-hydrochloric acid solution and ascorbic acid in the pretreatment process in the step 4) is 1.8-2.2 g:4.5 to 5.5ml:0.02 to 0.04g, preferably 1.9 to 2.1g: 4.8-5.2 ml:0.025 to 0.035g, more preferably 2g:5ml:0.03g.
In the invention, the specific parameter selection range of the detected sample in the pretreatment process and the headspace extraction process is the same as that of the carbon disulfide standard solution.
In the present invention, the sample to be tested in the step 4) includes one of rice fruit, wheat fruit, corn fruit, tea leaf and tobacco, and the particle size of the sample to be tested may be 150 to 850 μm, specifically 200 μm, 250 μm, 300 μm, 350 μm, 400 μm, 450 μm, 500 μm, 600 μm, 700 μm, 800 μm.
In the present invention, the dithiocarbamate compound in the step 4) includes one or more of dimethyl dithiocarbamate, ethylene dithiocarbamate and propylene dithiocarbamate.
In the invention, the formula of the dithiocarbamic acid ester pesticide is as follows:
formula 1 the linear equation y = 0.8646x +7.7838 for carbon disulphide,
2 y =log 10 s，x＝log 10 n，
The calculation formula for the concentration according to formulas 1 and 2 is:
(wherein n is the concentration of the component to be measured, S is the peak area of the component to be measured, C is the coefficient of conversion of the dithiocarbamate pesticide into carbon disulfide, propineb is 1.9, and zineb is 1.8).
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. 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.
Example 1
The standard curve configuration method comprises the following steps: 2ml of pure water was weighed and placed in a 20ml headspace bottle, and 5ml of stannous chloride-hydrochloric acid solution, 0.02g of ascorbic acid and different amounts of carbon disulfide (the addition of carbon disulfide had little effect on the volume change) were added respectively. In order to reduce the loss of carbon disulfide, finally adding carbon disulfide, quickly pressing a sealing aluminum cover against a bottle opening by using a capping device after adding, shaking by hand, placing a headspace bottle into a water bath kettle, setting the temperature to 80 ℃, carrying out water bath for 1h, and gently shaking once every 15min, wherein the attention is paid to the condition that liquid is not splashed onto the bottle opening.
During extraction, divinylbenzene/carbon molecular sieve/polydimethylsiloxane (PDMS/DVB/CAR) is selected to extract the fiber head, and before extraction, the fiber head is aged for 30min at the temperature of 250 ℃ at a sample inlet. Then extracting 0.005mg/l, 0.05mg/l, 0.1mg/l, 0.5mg/l, 1mg/l and 2mg/l of carbon disulfide standard solution respectively in a 40 ℃ extraction tank by adopting a headspace extraction mode, extracting the head of the extraction fiber deeply into a sample bottle for 10min, and thenDesorbing the fiber head after extraction for 3min in an instrument sample inlet, introducing a GC-QTOF instrument (the parameter is GESTEL automatic sampler, a chromatographic column is Agilent DB-5MS (60 m multiplied by 250 mu m multiplied by 0.25 mu m), the initial temperature of a column temperature box is set to 50 ℃, the heating rate is 20 ℃/min, the temperature of the column temperature box is raised to 100 ℃ and kept for 1min, the temperature of the sampler is 150 ℃, the split ratio is 5:1, the carrier gas is helium, the purging flow is 3ml/min, the mass spectrum is carried out in a full scanning mode, the emission current is 6 mu A, the electron energy is 70eV, the instrument operation time is 7.5min, the carbon disulfide peak outlet time is 5.3min, the data analysis adopts carbon disulfide to extract molecular weight 76m/z for quantification), analyzing, the point values of a plurality of groups of carbon disulfide standard solution concentration and peak area are obtained, and a standard curve is drawn (the carbon disulfide standard solution chromatograms with different concentrations sequentially corresponding to fig. 1-6, and the method can reflect that the invention can detect low-concentration samples). The resulting standard graph is shown in fig. 7, and the linear equation is: y=0.8646 x+7.7838, r 2 = 0.9888. The limit of detection is the lowest concentration of carbon disulphide detected on the mass spectrum. The quantitative limit is the lowest quantitative concentration of propineb and zineb on mass spectrum (the quantitative limit is calculated according to the lowest quantitative concentration of two pesticides on GC-QTOF, and the lowest quantitative concentration of the two pesticides is converted into carbon disulfide concentration to be 0.05 mg/L).
Taking rice particles (without dithiocarbamic acid ester compounds) ground to 150-400 mu m, replacing water and carbon disulfide added in the first step, then adding propineb (equivalent carbon disulfide is added to the concentration of 0.05mg/l, 0.1mg/l, 1mg/l and 2 mg/l) and zineb (equivalent carbon disulfide is added to the concentration of 0.05mg/l, 0.1mg/l and 0.5 mg/l) respectively, sequentially carrying out headspace extraction and detection according to the original technological parameters, repeatedly taking an average three times for each group, obtaining the concentration of the dithiocarbamic acid ester compounds from the graph through the obtained peak area, and calculating the recovery rate, wherein the recovery rate of the propineb is 89-116%, and the relative standard deviation is 1.9-7.3%. The recovery rate of zineb is 70-72%, and the relative standard deviation is 3.4-7.6%. The method has good precision and recovery rate, and can accurately detect pesticide residues. From the results, the recovery rate of propineb is higher, the recovery rate of zineb is lower, but the recovery rate is basically maintained at about 70%, and the stability is better.
Comparative example 1
The comparative example differs from example 1 only in that detection was performed using GC-FPD (autosampling was used, the sample volume was 100 μl).
The linear range of GC-FPD is 0.01-2mg/l, the linear equation is y=1.9198 x+7.3913, R 2 ＝0.9961，R 2 >0.99. The detection limit of the equivalent carbon disulfide of propineb is 0.01mg/l, the quantitative limit of the equivalent carbon disulfide is 0.02mg/l, and the recovery rate is 55-98.5%; the detection limit of the equivalent carbon disulfide of the zineb is 0.05mg/l, the quantitative limit of the equivalent carbon disulfide is 0.1mg/l, and the recovery rate is 77.5% -105%.
Comparative example 1 the results of the measurements related to example 1 are shown in table 1.
Table 1 comparison of the results of the test of example 1 and comparative example 1
The recovery rate of propineb in the equivalent high concentration (1-2 ppm) in the two methods is 100% -116% in example 1 and 98.5% in comparative example 1; the recovery rate of zineb is 77.5% on comparative example 1, which shows that the recovery rate of two DTC pesticides is better at high concentration using the headspace extraction method defined by the present invention.
The recovery rate of propineb in the equivalent medium concentration (0.1-0.5 ppm) in both methods was 89% in example 1 and 75% in comparative example 1, respectively; zineb is 70% -72% in example 1 and 96.5% -105.5% in comparative example 1. Indicating that propineb recovery was better at medium concentrations using the method of example 1.
The recovery rate of propineb in the equivalent low concentration (0.02-0.05 ppm) in both methods was 106.5% in example 1 and 55.5% in comparative example 1, respectively; zineb was 70% in example 1, and was not detected in comparative example 1. It is demonstrated that the recovery rate of both pesticides is better at low concentrations using the method of the present invention.
Example 2
Weighing 1.8g of rice sample ground to 200-600 mu m, adding the rice sample into a 20ml headspace bottle, adding 4.6ml of stannous chloride-hydrochloric acid solution and 0.03g of ascorbic acid, quickly pressing a sealed aluminum cover against a bottle mouth by a gland device after adding, shaking by hands, placing the headspace bottle into a water bath kettle, setting the temperature of 80 ℃, and carrying out water bath for 1h, and gently shaking once every 15min, taking care that liquid is not splashed onto the bottle mouth.
Extraction conditions: during extraction, an extraction fiber head with a divinylbenzene/carbon molecular sieve/polydimethylsiloxane (PDMS/DVB/CAR) coating is selected, and before extraction, the fiber head is put into a sample inlet for aging for 30 minutes at 250 ℃. Putting the sample into an extraction tank with the temperature of 40 ℃, adopting a headspace extraction mode to extract the fiber head into a sample bottle for 10min, desorbing the extracted fiber head in an instrument sample inlet for 5min for sample injection analysis, and processing detection data by using a standard curve measured in the embodiment 1 to obtain the DTC-free pesticide residue.
And (3) verification test: the ECD is used for detecting two pesticides in the rice sample, the ECD detection chromatogram is shown in fig. 9, and the result shows that the pesticides are not detected, and the detection method disclosed by the invention is accurate.
Example 3
Weighing 2.2g of tea leaf sample ground to 400-800 mu m, adding the tea leaf sample into a 20ml headspace bottle, adding 5.5ml of stannous chloride-hydrochloric acid solution and 0.02g of ascorbic acid, quickly pressing a sealed aluminum cover against a bottle mouth by a capping device after adding, shaking by hands, placing the headspace bottle into a water bath kettle, setting the temperature to be 85 ℃, and carrying out water bath for 1.2h, and gently shaking once every 15min, wherein the attention is paid to preventing liquid from splashing onto the bottle mouth.
Extraction conditions: during extraction, an extraction fiber head with divinylbenzene/carbon molecular sieve/polydimethylsiloxane (PDMS/DVB/CAR) coating material is selected, and before extraction, the fiber head is put into a sample inlet for aging for 30 minutes at 250 ℃. Putting the sample into an extraction tank with the temperature of 45 ℃, adopting a headspace extraction mode to extract the fiber head into a sample bottle for 12min, then desorbing the extracted fiber head in an instrument sample inlet for 3min for sample injection analysis, processing detection data by using a standard curve measured in the embodiment 1, and detecting to obtain the DTC-free pesticide residue.
The ECD is used for detecting two pesticides in the tea sample, and the result shows that the detection method disclosed by the invention is accurate.
In the present specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, and identical and similar parts between the embodiments are all enough to refer to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. The method for detecting the dithiocarbamic acid ester compound is characterized by comprising the following steps of:
1) Pretreatment: mixing water, stannous chloride-hydrochloric acid solution, ascorbic acid and different amounts of carbon disulfide to obtain carbon disulfide standard solutions with gradient concentration, respectively placing the carbon disulfide standard solutions in a headspace bottle, and then heating in a water bath to complete pretreatment;
2) Headspace extraction: carrying out headspace extraction on the pretreated mixed solution by adopting an extraction fiber head with a divinylbenzene/carbon molecular sieve/polydimethylsiloxane coating;
3) Drawing a standard curve: introducing the extracted gas into a GC-QTOF instrument for analysis to obtain a processing result and drawing a standard curve;
4) Sample detection: and replacing the carbon disulfide standard solution and water with the sample to be detected, sequentially carrying out pretreatment and headspace extraction, introducing the extracted gas into a GC-QTOF instrument for analysis to obtain the concentration of carbon disulfide, and further calculating the concentration of the dithiocarbamic acid ester compound.
2. The method for detecting a dithiocarbamate compound according to claim 1, wherein the volume mass ratio of water, stannous chloride-hydrochloric acid solution and ascorbic acid in the step 1) is 1.8-2.2 ml:4.5 to 5.5ml: 0.02-0.04 g, wherein the mass concentration of carbon disulfide in the mixed solution in the step 1) is respectively 0.005mg/l, 0.05mg/l, 0.1mg/l, 0.5mg/l, 1mg/l and 2mg/l.
3. The method for detecting the dithiocarbamate compound according to claim 2, wherein the water bath heating temperature in the step 1) is 70-90 ℃, the water bath heating time is 0.8-1.2 h, and the water bath heating process is performed once every 12-16 min.
4. A method for detecting a dithiocarbamate compound according to any one of claims 1 to 3, wherein the fiber head with divinylbenzene/carbon molecular sieve/polydimethylsiloxane coating is aged at 220 to 260 ℃ for 25 to 35 minutes before extraction;
the temperature of the headspace extraction in the step 2) is 35-45 ℃, the time of the headspace extraction is 8-12 min, and the desorption time after the headspace extraction is 2-5 min.
5. The method for detecting a dithiocarbamate compound according to claim 4, wherein the GC-QTOF instrument parameters are as follows:
GESTEL autosample injection, wherein the chromatographic column is Agilent DB-5MS, and parameters of the chromatographic column are as follows: 60m multiplied by 250 mu m multiplied by 0.25 mu m, the initial temperature of the column temperature box is set to 50 ℃, the heating rate is 20 ℃/min, the temperature is raised to 100 ℃ and kept for 1min, the temperature of the sample injector is 150 ℃, the split ratio is 5:1, the carrier gas is helium, and the purging flow is 3ml/min; the mass spectrum is carried out in a full scanning mode, the emission current is 6 mu A, the electron energy is 70eV, the instrument operation time is 7.5min, the carbon disulfide peak time is 5.3min, and the data analysis adopts the carbon disulfide extraction molecular weight of 76m/z for quantification.
6. The method for detecting the dithiocarbamic acid ester compound according to claim 5, wherein the volume mass ratio of the sample to be detected to stannous chloride-hydrochloric acid solution and ascorbic acid in the pretreatment process in the step 4) is 1.8-2.2 g:4.5 to 5.5ml: 0.02-0.04 g.
7. The method for detecting a dithiocarbamate compound according to claim 5 or 6, wherein the sample to be detected in the step 4) comprises one of rice fruit, wheat fruit, corn fruit, tea leaf and tobacco, and the particle size of the sample to be detected is 150 to 850. Mu.m.
8. The method for detecting a dithiocarbamate according to claim 7, wherein the dithiocarbamate in the step 4) comprises one or more of dimethyl dithiocarbamate, ethylene dithiocarbamate and propylene dithiocarbamate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311197091.8A CN117214332A (en) | 2023-09-15 | 2023-09-15 | Method for detecting dithiocarbamic acid ester compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311197091.8A CN117214332A (en) | 2023-09-15 | 2023-09-15 | Method for detecting dithiocarbamic acid ester compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117214332A true CN117214332A (en) | 2023-12-12 |
Family
ID=89045753
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311197091.8A Pending CN117214332A (en) | 2023-09-15 | 2023-09-15 | Method for detecting dithiocarbamic acid ester compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117214332A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102565210A (en) * | 2011-01-02 | 2012-07-11 | 中国医学科学院药用植物研究所 | Method for detecting residual quantity of mancozeb pesticide in Chinese medicinal herb |
| CN103852545A (en) * | 2014-03-07 | 2014-06-11 | 云南省烟草质量监督检测站 | Method for determining content of dithiocarbamate in tobaccos and tobacco products |
| CN109709219A (en) * | 2017-10-25 | 2019-05-03 | 中国石油化工股份有限公司 | Detect the method for polar substances structure and/or content in non-polar substrate |
| CN110596276A (en) * | 2019-10-14 | 2019-12-20 | 普洱市质量技术监督综合检测中心 | Method for measuring dithiocarbamate residues in tea leaves by headspace-gas chromatography-mass spectrometry |
| CN113820431A (en) * | 2021-10-27 | 2021-12-21 | 暨南大学 | Method for measuring sulfur dioxide content in bamboo and wood products |
| CN116008422A (en) * | 2022-12-26 | 2023-04-25 | 舟山市食品药品检验检测研究院 | Method for detecting total residue of dithiocarbamate in plant-derived food |
| CN116297969A (en) * | 2023-03-28 | 2023-06-23 | 中国热带农业科学院分析测试中心 | Dithiocarbamic acid ester pesticide residue detection method |
-
2023
- 2023-09-15 CN CN202311197091.8A patent/CN117214332A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102565210A (en) * | 2011-01-02 | 2012-07-11 | 中国医学科学院药用植物研究所 | Method for detecting residual quantity of mancozeb pesticide in Chinese medicinal herb |
| CN103852545A (en) * | 2014-03-07 | 2014-06-11 | 云南省烟草质量监督检测站 | Method for determining content of dithiocarbamate in tobaccos and tobacco products |
| CN109709219A (en) * | 2017-10-25 | 2019-05-03 | 中国石油化工股份有限公司 | Detect the method for polar substances structure and/or content in non-polar substrate |
| CN110596276A (en) * | 2019-10-14 | 2019-12-20 | 普洱市质量技术监督综合检测中心 | Method for measuring dithiocarbamate residues in tea leaves by headspace-gas chromatography-mass spectrometry |
| CN113820431A (en) * | 2021-10-27 | 2021-12-21 | 暨南大学 | Method for measuring sulfur dioxide content in bamboo and wood products |
| CN116008422A (en) * | 2022-12-26 | 2023-04-25 | 舟山市食品药品检验检测研究院 | Method for detecting total residue of dithiocarbamate in plant-derived food |
| CN116297969A (en) * | 2023-03-28 | 2023-06-23 | 中国热带农业科学院分析测试中心 | Dithiocarbamic acid ester pesticide residue detection method |
Non-Patent Citations (3)
| Title |
|---|
| 何莲 等，: "葱青叶对椒麻糊挥发性物质的影响", 《食品质量安全学报》, vol. 13, no. 19, 31 October 2022 (2022-10-31), pages 6163 - 6170 * |
| 王俊魁;杨帆;包斌;: "顶空固相微萃取结合气质联用分析沙葱中挥发性成分", 食品工业科技, no. 24, 15 December 2012 (2012-12-15), pages 171 - 173 * |
| 高慧;汪洋;邢燕;: "GC-MS法测定植物性样品中二硫代氨基甲酸酯类农药残留", 食品安全导刊, no. 12, 25 April 2020 (2020-04-25), pages 124 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Tariba | Metals in wine—impact on wine quality and health outcomes | |
| Fredes et al. | Quantification of prominent volatile compounds responsible for muskmelon and watermelon aroma by purge and trap extraction followed by gas chromatography–mass spectrometry determination | |
| Tatzber et al. | Determination of organic and inorganic carbon in forest soil samples by mid-infrared spectroscopy and partial least squares regression | |
| CN105264373B (en) | With the microalgae compound powder for optimizing aesthetic quality | |
| Christensen et al. | Method validation for strobilurin fungicides in cereals and fruit | |
| Rapior et al. | Volatile flavor constituents of fresh Marasmius alliaceus (garlic Marasmius) | |
| Kumari et al. | Mineral composition, pigments, and postharvest quality of guava cultivars commercially grown in India | |
| CN109060714B (en) | Method for detecting concentration of isosalix methyl and application | |
| Smith et al. | Essential oils, treatment of compositional data for the characterization of essential oils. Determination of geographical origins of peppermint oils by gas chromatographic analysis | |
| US9921198B2 (en) | Method to determine the crocetin and its derivative amounts and the derivative composition from gardenia yellow | |
| CN110261526A (en) | A kind of tomato flavor quality determination method based on tomato odor characteristic compound | |
| CN111738548B (en) | Jasmine tea aroma quality evaluation method and application thereof | |
| CN117214332A (en) | Method for detecting dithiocarbamic acid ester compound | |
| Gillan et al. | Input and early diagenesis of chlorophylls in a temperate intertidal sediment | |
| CN110674973A (en) | Method for predicting content of raspberry kaempferol-3-O-rutinoside | |
| Takeno et al. | A high-throughput and solvent-free method for measurement of natural polyisoprene content in leaves by Fourier transform near infrared spectroscopy | |
| CN113759047B (en) | Method for detecting content of saponins in ginseng and method for identifying garden ginseng and wild ginseng | |
| CN114994284A (en) | Indirect determination method for basic respiration rates of soils with different vegetation types | |
| CN113484303A (en) | Method for detecting millet carotenoid based on Raman spectrum | |
| Drenjančević et al. | Effects of early leaf removal on volatile compounds concentrations in Cabernet Sauvignon wines from the Ilok vineyards | |
| CN111830165B (en) | Method for pretreatment and simultaneous measurement of phosphine and dithiocarbamate substances | |
| Cherry | Electrophoretic observation on protein changes and variability during development of the peanut | |
| CN114279992B (en) | Extraction and detection method of yellow pigment in yellow Gong Jiao | |
| Capar et al. | Determination and speciation of trace elements in foods | |
| CN107300554B (en) | Rice manganese content simple and fast measuring method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |