CN107638871B - Adsorption composition and method for determining dithiocarbamate compounds - Google Patents
Adsorption composition and method for determining dithiocarbamate compounds Download PDFInfo
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Abstract
The invention belongs to the field of detection and analysis, and particularly relates to an adsorption composition which comprises Florisil diatomite and aminopropyl silica gel; wherein the weight ratio of the Florisil to the aminopropyl silica gel is (0.1-5): 1. Furthermore, the invention also relates to a method for determining the dithiocarbamate compounds in a sample. The adsorption composition can adsorb interferents in a sample, so that the accuracy of measuring the dithiocarbamate compounds in the sample can be improved, and the method can respectively measure the content of various dithiocarbamate compounds in the sample.
Description
Technical Field
The invention belongs to the field of detection and analysis, and particularly relates to an adsorption composition and a method for determining dithiocarbamate compounds in a sample.
Background
Dithiocarbamates (DTCs) are widely used fungicides worldwide, can control more than four hundred pathogens in over seventy crops, and are the fungicides which are used in large quantities at the earliest. Because DTCs have low cost, wide application and low toxicity, the DTCs are still widely used for preventing and controlling downy mildew, spot disease, gibberellic disease and the like caused by phycomycetes 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 Ethylene Thiourea (ETU), which is a substance having carcinogenicity, teratogenicity and mutagenicity and affects thyroid function for a long time, is produced metabolically in crops to which DTCs have been applied and in animals which have eaten such crops, and that ethylene thiourea has been listed as a carcinogen by the national occupational safety and health agency of the united states, and that dithiocarbamates themselves cause moderate irritation to the skin and respiratory system of mammals, manifested as itching, sore throat, inflammation of the trachea, and the like. For the above reasons, there is a need to monitor the residual dithiocarbamate content in animals and plants.
Dithiocarbamates are a large class of compounds, and are mainly classified into methyldithiocarbamate compounds (DMDCs), Ethylenedithiocarbamates (EBDCs), and propylenedithiocarbamate compounds (PBDCs). Wherein, the methyl dithiocarbamate compounds comprise sodium ferbamate, ziram, thiram and other compounds, the ethylene dithiocarbamate compounds comprise sodium metiram, maneb, zineb, mancozeb, metiram, amobam, metiram and zineb and other compounds, and the propylene dithiocarbamate compounds comprise sodium propineb, propineb and other compounds. Generally, the toxicity of the dithiocarbamate compounds is not great, but the toxicity is remarkably enhanced when heavy metal ions are encountered, and moreover, the toxicity of different dithiocarbamate compounds is different.
Hitherto, various methods for detecting and analyzing pesticide residues of dithiocarbamates have been internationally reported, including spectrophotometry, gas chromatography, liquid chromatography, and the like. Wherein, the spectrophotometry has more operation steps, more influencing factors and more methodsThe accuracy and repeatability are poor. Although the gas chromatography and the liquid chromatography are simpler and more accurate than the spectrophotometry, both methods require-CS in the dithiocarbamate compound to be detected before detection2The group is reduced into carbon disulfide, and the content of the dithiocarbamate compound is determined by measuring the content of the carbon disulfide, so the operation is still complicated. In addition, the total amount of dithiocarbamate compounds measured by the conventional method is not enough to measure the content of each dithiocarbamate compound.
There is a need for a method for determining the respective amounts of various dithiocarbamate compounds.
Disclosure of Invention
The invention provides an adsorption composition, which can improve the accuracy of detecting dithiocarbamate compounds by adsorbing interferents in a sample to be detected. In addition, the invention also provides a method for determining the dithiocarbamate compounds in the sample, and the method can accurately determine the content of various dithiocarbamate compounds in the sample to be determined.
The invention relates in a first aspect to an adsorbent composition comprising flory diatomaceous earth and aminopropyl silica gel; wherein the weight ratio of the Florisil to the aminopropyl silica gel is (0.1-5) to 1, such as 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1.4:1, 1.6:1, 1.8:1, 2:1, 2.5:1, 2.8:1, 3:1, 3.3:1, 3.8:1, 4:1, 4.5:1, 4.7:1, 5: 1.
In one embodiment of the first aspect of the present invention, the weight ratio of the florisil to the aminopropyl silica gel in the adsorption composition is (0.2-4): 1.
In one embodiment of the first aspect of the present invention, one or more of the following a to F are included:
A. the purity of the Florisil is more than or equal to 90 percent, preferably more than or equal to 95 percent, more than or equal to 96 percent, more than or equal to 97 percent, more than or equal to 98 percent, more than or equal to 99 percent, more than or equal to 99.9 percent and more than or equal to 99.99 percent;
B. the mesh number of the Florisil is 30-150 meshes, preferably 40-120 meshes, such as 60-100 meshes and 50-110 meshes;
C. the specific surface area of the Florisil is more than or equal to 200m2,/g, preferably ≥ 240m2/g、260～2000m2/g、260～1000m2/g or 270 to 800m2G, e.g. 240m2/g、280m2/g、290m2/g、300m2/g、340m2/g、500m2/g、600m2/g、700m2/g、760m2/g、900m2/g、1400m2/g、1700m2/g；
D. The average particle size of the aminopropyl silica gel is 20-130 μm, preferably 30-100 μm, such as 40-75 μm, 40-110 μm, 30-90 μm, 30-80 μm;
E. the specific surface area of the aminopropyl silica gel is more than or equal to 100m2/g, preferably ≥ 120m2/g、≥140m2/g、160～2000m2/g、180～1000m2/g or 180 to 600m2G, e.g. 170m2/g、200m2/g、260m2/g、300m2/g、400m2/g、700m2/g、900m2/g、1000m2/g、1400m2/g、1600m2/g、1800m2/g；
F. The aminopropyl group content in the aminopropyl silica gel is not less than 0.3mmol/g, preferably 0.3 to 30mmol/g, more preferably 0.3 to 3mmol/g, for example, 0.4mmol/g, 0.6mmol/g, 0.8mmol/g, 1mmol/g, 3mmol/g, 5mmol/g, 8mmol/g, 9mmol/g, 11mmol/g, 13mmol/g, 14mmol/g, 16mmol/g, 18mmol/g, 20mmol/g, 22mmol/g, 24mmol/g, 25mmol/g, 27mmol/g, 29 mmol/g.
In one embodiment of the first aspect of the present invention, the aminopropyl silica gel has a hydroxyl group content of 20mmol/g or less, preferably 15mmol/g or less, more preferably 10mmol/g or less, for example 8mmol/g, 7mmol/g or less, 5mmol/g or less, 4mmol/g or less, 3mmol/g or less, 1mmol/g or less, 0.0001 to 8mmol/g, 0.0001 to 2mmol/g, 0.0001 to 1mmol/g, 0.001mmol/g, 0.005mmol/g, 1.5mmol/g, 3mmol/g, 6mmol/g, 0.5 mmol/g.
In one embodiment of the first aspect of the present invention, the average pore size of the diatomaceous earth is
Preferably, it is
For example
In one embodiment of the first aspect of the present invention, the aminopropyl silica gel has an average pore size of
Preferably, it is
For example
In the invention, the purity of the Florisil refers to the mass percentage of magnesium silicate in the Florisil.
A second aspect of the invention relates to a process for preparing the adsorbent composition of the first aspect of the invention comprising the step of mixing florisil and aminopropyl silica gel.
In a third aspect, the present invention relates to a method for extracting dithiocarbamate compounds from a sample, comprising the steps of:
1) mixing a sample, an adsorption composition according to any one of the first aspect of the invention and an alkaline solution to obtain a mixture;
2) filtering the mixture obtained in the step 1) to obtain filtrate, namely extracting solution.
In one embodiment of the third aspect of the present invention, it comprises one or more of the following (a) to (i):
(a) in the step 1), mixing is carried out under vortex oscillation;
(b) in the step 1), the mixing time is 10 to 70 minutes, preferably 15 to 50 minutes, more preferably 20 to 40 minutes, such as 14 minutes, 18 minutes, 20 minutes, 25 minutes, 30 minutes, 36 minutes, 40 minutes, 50 minutes, 60 minutes, and 70 minutes;
(c) in step 1), the weight ratio of the sample to the adsorption composition is (0.2-6): 1, preferably (0.6-4): 1, such as 0.2:1, 0.5:1, 0.8:1, 1:1, 1.2:1, 1.4:1, 1.5:1, 1.7:1, 2:1, 2.2:1, 2.5:1, 2.8:1, 3:1, 3.4:1, 4:1, 5:1, 6: 1;
(d) in the step 1), the mixed feed-liquid ratio is 0.05-1 g/m L, preferably 0.1-0.8 g/m L, such as 0.08g/m L0, 0.12g/m L1, 0.14g/m L2, 0.16g/m L3, 0.2g/m L4, 0.24g/m L5, 0.28g/m L6, 0.3g/m L, 0.4g/m L, 0.5g/m L, 0.6g/m L, 0.7g/m L, 0.8g/m L, 0.9g/m L and 1g/m L;
(e) the sample is tobacco (e.g., at least one selected from the group consisting of flue-cured tobacco, burley tobacco, and flavoured tobacco) and/or a tobacco product (e.g., cigarette and/or cut filler);
(f) the dithiocarbamate compound is at least one selected from the group consisting of thiram, ziram, ferbam, mancozeb, zineb, maneb, metiram, amobam, metiram, sodium and propineb;
(g) in the step 1), the pH value of the alkaline solution is 12-14, preferably 13-14;
(h) in the step 1), the alkaline solution is at least one selected from a sodium hydroxide solution, a potassium hydroxide solution and an ammonia water solution;
(i) in the step 2), filtering by adopting a filter membrane; preferably, the pore size of the filter is 0.2 to 0.4. mu.m, such as 0.22. mu.m.
In one embodiment of the third aspect of the present invention, in the step 1), the temperature of the mixing is normal temperature.
In the third aspect of the present invention, the "mixed feed-liquid ratio" refers to the ratio of the sum of the masses of the sample and the adsorption composition in step 1) to the volume of the alkaline solution, and has a unit of g/m L.
In the invention, the extract contains dithiocarbamic acid ester compounds;
the fourth aspect of the present invention relates to a method for measuring a dithiocarbamate compound in a sample, comprising the steps of:
(1) obtaining an extract according to the extraction method of the third aspect of the present invention;
(2) performing liquid chromatography-mass spectrometry/mass spectrometry detection on the extracting solution obtained in the step (1) to obtain a detection result;
(3) and (3) calculating the content of the dithiocarbamate compounds in the sample according to the detection result obtained in the step (2).
In one embodiment of the fourth aspect of the present invention, in step (3), the content of each dithiocarbamate compound in the sample is calculated based on the detection result obtained in step (2).
In one embodiment of the fourth aspect of the present invention, in the step (3), the calculation is performed by an external standard method.
In one embodiment of the fourth aspect of the present invention, the dithiocarbamate compound is at least one selected from the group consisting of thiram, ziram, ferbam, mancozeb, zineb, maneb, metiram, amobam, metiram, sodium and propineb.
In one embodiment of the fourth aspect of the present invention, step (3) further comprises one or more of the following (i) to (vi):
(i) a qualitative ion pair of any one compound selected from thiram, ziram and ferumyl 121/45 and/or 121/87;
(ii) the quantitative ion pair of any one compound selected from thiram, ziram and ferme is 121/45 or 121/87;
(iii) a qualitative ion pair of any one compound selected from mancozeb, zineb, maneb, metiram, amobam, metiram and sodium is 211/135 and/or 211/177;
(IV) the quantitative ion pair of any compound selected from mancozeb, zineb, maneb, metiram, amobam, metiram and sodium is 211/135 or 211/177;
(v) the qualitative ion pair of propineb is 225/149 and/or 225/191;
(VI) the quantitative ion pair of propineb is 225/149 or 225/191.
In one embodiment of the fourth aspect of the present invention, one or more of the following (a) to (O) are included:
(A) in the step (2), C18 chromatographic column is adopted in liquid chromatography;
(B) in the step (2), the mobile phase of the liquid chromatography is 1-70 mmol/L ammonia water solution, preferably 3-60 mmol/L ammonia water solution, such as 2 mmol/L0, 5 mmol/L1, 7 mmol/L2, 10 mmol/L3, 13 mmol/L4, 15 mmol/L5, 20 mmol/L6, 24 mmol/L7, 27 mmol/L8, 30 mmol/L9, 33 mmol/L, 36 mmol/L0, 40 mmol/L1, 45 mmol/L2, 48 mmol/L3, 50 mmol/L4, 55 mmol/L, 58 mmol/L, 60 mmol/L, 62 mmol/L, 64 mmol/L, 67 mmol/L, 70 mmol/L ammonia water solution;
(C) in the step (2), the elution mode of the liquid chromatogram is isocratic elution;
(D) in the step (2), the flow rate of the mobile phase of the liquid chromatography is 100-300 mu L/min, preferably 200-300 mu L/min, such as 220 mu L/min, 250 mu L/min and 280 mu L/min;
(E) in the step (2), the column temperature of the liquid chromatography is 35-50 ℃, preferably 35-45 ℃, for example 40 ℃;
(F) in the step (2), the ion source of the mass spectrum is an electrospray ion source;
(G) in the step (2), the detection mode of the mass spectrum is a selective ion scanning mode, and the detection mode of the mass spectrum is multi-reaction monitoring;
(H) in the step (2), the electrospray voltage of the mass spectrum is 4500-5500V, preferably 4700-5200V, for example 5000V;
(I) in the step (2), the ion source temperature of the mass spectrum is 300-400 ℃, preferably 330-370 ℃, for example 350 ℃;
(J) in the step (2), the gas curtain gas of the mass spectrum is 0.1-0.2 MPa nitrogen, such as 0.15MPa nitrogen;
(K) in the step (2), the atomization gas of the mass spectrum is 0.3-0.7 MPa nitrogen, such as 0.5MPa nitrogen;
(L) in the step (2), the collision gas of the mass spectrum is 0.01-0.04 MPa nitrogen, such as 0.02 MPa nitrogen and 0.03MPa nitrogen;
(M) in the step (2), the collision energy of the mass spectrum is 10-25V, preferably 13-22V, such as 20V and 15V;
(N) in the step (2), the residence time of the mass spectrum is 30-60 ms, preferably 40-60 ms, such as 50 ms;
(O) the sample is tobacco and/or a tobacco product; for example, the tobacco is at least one selected from flue-cured tobacco, burley tobacco, and aromatic tobacco; for example, the tobacco product is a cigarette and/or cut tobacco.
A fifth aspect of the present invention relates to a kit for extracting or measuring (in a sample) a dithiocarbamate compound, comprising the adsorption composition according to any one of the first aspect of the present invention, an alkaline solution, a filter membrane, a liquid chromatography column, and an aqueous ammonia solution; preferably, nitrogen is also included.
In one embodiment of the fifth aspect of the present invention, one or more of the following (i) to (v) are included:
(i) the alkaline solution is at least one selected from sodium hydroxide, potassium hydroxide and ammonia water solution;
(ii) the pH value of the alkaline solution is 12-14, preferably 13-14;
(iii) the aperture of the filter membrane is 0.2-0.4 μm, such as 0.22 μm;
(iv) the liquid chromatographic column is a C18 chromatographic column;
(v) the molar concentration of the ammonia solution is 1-70 mmol/L, preferably 3-60 mmol/L, such as 2 mmol/L0, 5 mmol/L1, 7 mmol/L2, 10 mmol/L3, 13 mmol/L4, 15 mmol/L5, 20 mmol/L6, 24 mmol/L7, 27 mmol/L8, 30 mmol/L9, 33 mmol/L, 36 mmol/L0, 40 mmol/L1, 45 mmol/L2, 48 mmol/L3, 50 mmol/L4, 55 mmol/L, 58 mmol/L, 60 mmol/L, 62 mmol/L, 64 mmol/L, 67 mmol/L and 70 mmol/L.
In one embodiment of the fifth aspect of the present invention, the sample is tobacco and/or a tobacco product; for example, the tobacco is at least one selected from flue-cured tobacco, burley tobacco, and aromatic tobacco; for example, the tobacco product is a cigarette and/or cut tobacco.
In one embodiment of the fifth aspect of the present invention, the dithiocarbamate compound is at least one selected from the group consisting of thiram, ziram, ferbam, mancozeb, zineb, maneb, metiram, amobam, metiram, sodium and propineb.
A sixth aspect of the invention relates to the use of an adsorption composition according to the first aspect of the invention or a kit according to the fifth aspect of the invention for extracting or determining a dithiocarbamate compound in a sample.
In one embodiment of the sixth aspect of the present invention, the dithiocarbamate compound is at least one selected from the group consisting of thiram, ziram, ferbam, mancozeb, zineb, maneb, metiram, amobam, metiram, sodium and propineb.
In one embodiment of the sixth aspect of the present invention, the sample is tobacco and/or a tobacco product; for example, the tobacco is selected from at least one of flue-cured tobacco, burley tobacco, and aromatic tobacco; for example, the tobacco product is a cigarette and/or cut tobacco.
A seventh aspect of the invention relates to the use of an adsorption composition according to the first aspect of the invention for improving the accuracy of the determination of dithiocarbamates in a sample.
In one embodiment of the seventh aspect of the present invention, the dithiocarbamate compound is at least one selected from the group consisting of thiram, ziram, ferbam, mancozeb, zineb, maneb, metiram, amobam, metiram, sodium and propineb.
In one embodiment of the seventh aspect of the present invention, the sample is tobacco and/or a tobacco product; for example, the tobacco is selected from at least one of flue-cured tobacco, burley tobacco, and aromatic tobacco; for example, the tobacco product is a cigarette and/or cut tobacco.
In the present invention, unless otherwise specified,
the term "Florisil" refers to a substance containing magnesium silicate as the major component and small or trace amounts of other components (e.g., water, fluorine, soluble salts, free bases, heavy metals, etc.); melting point is 191 deg.C, white to off-white fine powder, odorless, tasteless, no sense of gravel, slightly hygroscopic, easily decomposed by inorganic acid, and insoluble in water and ethanol. Can be used as anticaking agent, filter aid, coating agent, candy polishing and glazing agent, chewing gum powder, rice coating agent, etc. Its CAS number is 1343-88-0.
The term "silica gel" refers to inorganic silica gels having the formula mSiO2·nH2O, which is a highly active adsorbent material, is an amorphous substance, is chemically stable, is frosty, glassy, translucent particles, is insoluble in water and inorganic acids, but is soluble in hydrofluoric acid and concentrated caustic soda solutions.
The term "aminopropyl silica gel" refers to a substance formed by partially or totally replacing hydroxyl groups contained in silica gel with aminopropyl groups on a silica gel (the definition of silica gel is as described above), for example, a substance represented by the formula (I),
the term "thiram", also known as thiuram, celosia, alurnine, belongs to a low-toxicity fungicide and has a stimulating effect on the skin and mucous membranes. The chemical name of the compound is tetramethyl thiuram disulfide, the CAS number is 137-26-8, and the flash point is higher than 300 ℃. Thiram is a protective bactericide, and a broad-spectrum protective thiram series bactericide has better control on downy mildew, epidemic disease, anthracnose, cereal smut and seedling yellow blight of various crops.
The chemical name for the term "ziram" is zinc dimethyldithiocarbamate, white powder. Can be used as bactericide and pesticide, and can also be used as promoter for natural glue, synthetic glue and latex. The CAS number is 137-30-4.
The term "ferbamate" is also known as formet and is chemically known as iron N, N-dimethyldithiocarbamate or iron dimethylaminosulfonate. A dark brown powder, slightly odorous, which decomposed before melting. The bactericide is agriculturally used as a bactericide for orchards and can prevent and treat apple rust, scab, pear scab, grape downy mildew, celery blight, spinach downy mildew and the like. But can not contact with the copper agent, thereby preventing the occurrence of phytotoxicity. The pesticide is generally processed into wettable powder for use. The CAS number is 14484-64-l.
The term "mancozeb" has a chemical name of complex salt of ethylene bis-dithiocarbamyl manganese and zinc, the pure product is white powder, the industrial product is off-white or light yellow powder, has odor egg taste, is unstable to light, heat and humidity, is easy to decompose carbon disulfide, is easy to decompose to release carbon disulfide when meeting alkaline substances or copper, mercury and the like to reduce the effect, and has small volatility. The compound is a broad-spectrum protective bactericide for preventing and treating various fungal diseases of wheat, fruits, vegetables and the like, and the protection is to provide Zn element for plants, enhance the capability of resisting diseases for the plants besides solving the symptom of zinc deficiency, thereby relatively playing a role in sterilization. The CAS number is 8018-1-7.
The term "zineb" is known as ethylene bis (zinc dithiocarbamate), which is a protective organosulfur fungicide. The pure product is off-white powder, and the industrial product is off-white or light yellow powder with sulfur smell. Is unstable under alkaline, high temperature, humid and sun-light conditions. Has low toxicity to human and livestock, but has irritation to skin, nose and throat. Is safe and pollution-free to plants. The zineb is safe to plants, has active waves with chemical properties, can be easily oxidized into an isothiocyanic compound in water, has strong inhibiting effect on-SH group-containing enzyme in pathogenic bacteria, can directly kill pathogenic bacteria spores, inhibit the germination of the spores and prevent pathogenic bacteria from invading the plants, but has small killing effect on pathogenic bacteria mycelia invading the plants. The CAS number is 12122-67-7.
The term "maneb" has the chemical name of manganese ethylene-1, 2-bis (dithiocarbamate), a pale yellow solid, and is used as an agricultural fungicide. Can be used for seed treatment, foliage spray, soil treatment, agricultural equipment disinfection and the like. Its CAS number is 12427-38-2.
The chemical name of the term "metiram" is ethylene dithiocarbamate, the pure product of which is white powder, and the industrial product of which is off-white or light yellow powder and has fishy smell. The metiram is used as a protective bactericide and has good control effect on various diseases caused by oomycetes fungi. Its CAS number is 9006-42-2.
The term "amobam" has the chemical name 1, 2-ethylenebisdithiocarbamate, which belongs to organic sulfur preparations. The pure product is colorless crystal and is soluble in water; the industrial product is light yellow liquid which is neutral or alkalescent and has the smell of the eggs. The chemical property is stable, but the decomposition is easy after the high temperature of more than 40 ℃. The ambam has the main protection function for preventing and treating diseases, and has low toxicity to human and livestock because the liquid medicine can permeate into the plant epidermis and has the treatment function. The CAS number is 3366-10-7.
The chemical name of "Dyson Fumei Zinc" is bis (dimethyldithiocarbamate) zinc ethylene dithiocarbamate, a fungicide. The CAS number is 64440-88-6.
The term "sodium" is known under the chemical name disodium ethylene bis (dithiocarbamate) and is a solid crystal containing six crystal waters, m.p.230 ℃, which is unstable to heat, light and moisture and decomposes into flammable decomposition products before the melting point. The sodium metiram is an important intermediate of the bactericides such as zineb, mancozeb and the like. Its CAS number is 142-59-6.
The term "propineb" is known under the chemical name zinc propenyl bisdithiocarbamate, as a white or yellowish powder. Decomposing at 160 deg.C or higher. Propineb is a broad-spectrum, quick-acting protective fungicide. The CAS number is 12071-83-9.
The term "tobacco" refers to solanaceae, the genus Nicotiana (Nicotiana L.) or annual or perennial herbs, favorite crops, the genus has over 60 species, most wild species, and the major cultivars are tabacco rubra and tabacco flava.
The term "tobacco product" refers to a hobby commodity made from tobacco leaves. According to the characteristics of different types of tobacco leaves, different processing and manufacturing methods are applied to produce a variety of tobacco products so as to meet the hobby requirements of different consumers. Among them, cigarettes account for the vast majority, and the cigarettes are high in mechanization degree and large in production quantity.
The term "liquid chromatography-mass spectrometry/mass spectrometry" refers to the combination of liquid chromatography with multi-stage tandem mass spectrometry, most commonly liquid chromatography with two-stage tandem mass spectrometry.
The invention obtains at least one of the following beneficial effects:
1. the adsorption composition can adsorb interferents in a sample, so that the accuracy of measuring the dithiocarbamate compounds in the sample can be improved.
2. The method can measure the respective contents of various dithiocarbamate compounds and has high accuracy.
Drawings
In order that the present disclosure may be more readily and clearly understood, reference is now made to the following detailed description of the embodiments of the present disclosure taken in conjunction with the accompanying drawings, in which
FIG. 1 is a flow chart for determining dithiocarbamate compounds in a sample;
FIG. 2 shows a portion of chromatographic peaks in a chromatogram of a standard solution in a series of standard solutions.
Detailed Description
Flory diatomaceous earth: purchased from maohang makeqi boxing biotechnology limited; purity 99% (chromatographic purity); the mesh number is 60-100 meshes; has an average pore diameter of
The specific surface area is 290m2/g。
Aminopropyl silica gel: purchased from Shenzhen comma biotechnology, Inc.; cargo number NH-1-100; the aminopropyl content in aminopropyl silica gel is 0.6 mmol/g; the hydroxyl content in the aminopropyl silica gel is 1 mmol/g; the specific surface area is 200m2(ii)/g; the average grain diameter is 40-75 μm; has an average pore diameter of
The thiram standard, the mancozeb standard, the zineb standard, the maneb standard, the metiram standard, the amobam standard, the metiram standard, the sodium metiram standard and the propineb standard are purchased from a national standard substance center, the purity of the standard is more than 99.9 percent, and the standard is frozen and stored for later use.
And (3) accurately weighing a proper amount of each standard product in different 100m L beakers, dissolving the standard products in acetonitrile, fixing the volume in a 100m L volumetric flask, preparing each single-standard mother solution with the mass concentration of 100 mg/L, and storing the single-standard mother solution at the temperature of below 18 ℃ in a dark place.
And (3) first-stage mixed standard liquid, namely accurately transferring a proper amount of each single-standard mother liquid into the same 100m L volumetric flask, and performing constant volume by using acetonitrile to obtain the first-stage mixed standard liquid.
And (3) precisely transferring the first-stage mixed standard solutions with different volumes into different 100m L volumetric flasks, and respectively metering the volume with acetonitrile to obtain the series of standard solutions.
Example 1
According to the scheme shown in figure 1, Florisil and aminopropyl silica gel are mixed according to the weight ratio of 1:1 to obtain a Florisil-aminopropyl silica gel mixture, 1g of flue-cured tobacco sample and 0.6g of the Florisil-aminopropyl silica gel mixture are placed in a 50m L centrifugal tube, 10m L of sodium hydroxide aqueous solution with the pH value of 13 is added for extraction at normal temperature, vortex oscillation is carried out for 20 minutes, and filtration is carried out through a filter membrane with the pore diameter of 0.22 mu m to obtain an extracting solution, and a series of standard solutions and extracting solutions are measured by liquid chromatography-mass spectrometry/mass spectrometry, wherein:
the liquid chromatography is carried out under the conditions of C18 column, 40 deg.C column temperature, 5 mmol/L ammonia solution mobile phase, isocratic elution mode, 250 μ L/min flow rate, and 10 μ L sample volume;
the operating conditions of the mass spectrum were: the ion source is an electrospray ion source; the detection mode is a selective ion scanning mode; the detection mode is multi-reaction monitoring (MRM); the electrospray voltage is 5000V; the ion source temperature is 350 ℃; the gas curtain gas is 0.15MPa nitrogen; the atomization gas is 0.50MPa nitrogen; the collision gas is 0.03MPa nitrogen; the collision energy is 20V or 15V; the residence time is 50 ms;
the qualitative ion pair and the quantitative ion pair for each component are shown in table 1:
TABLE 1
In this example, a part of chromatographic peaks of a standard solution chromatogram in a series of standard solutions is shown in fig. 2. The propineb content in the flue-cured tobacco sample obtained by calculation by an external standard method according to the measurement results of the series of standard solutions and the extraction solution and the quantitative ion pair 225/149 is shown in table 2 (no other dithiocarbamate compounds are detected in the flue-cured tobacco sample).
The content of propineb in the flue-cured tobacco samples obtained in this example was determined as shown in table 2 (no detection of other dithiocarbamate compounds in the flue-cured tobacco samples) by using 0.6g of florisil and 0.6g of aminopropyl silica gel instead of the florisil-aminopropyl silica gel mixture described in this example.
The recovery of the spiked standard was determined for the mixture of Florisil-aminopropyl silica gel, with and without the addition of adsorbent, and for the mixture of Florisil-aminopropyl silica gel, with and without the addition of Florisil, and with the addition of aminopropyl silica gel in this example, and the results are shown in Table 2.
TABLE 2
As can be seen from Table 2, the recovery rate of the added standard far exceeds 100% without adding the adsorbent, which indicates that the interferents in the sample seriously affect the accurate determination of the content of propineb. Compared with the single use of the Florisil or the aminopropyl silica gel as the adsorbent, the invention has higher measurement accuracy (the addition standard recovery rate is closer to 100%) when the Florisil-aminopropyl silica gel mixture is used as the adsorbent.
Example 2
The method comprises the steps of mixing Florisil and aminopropyl silica gel in a weight ratio of 0.8:1 to obtain a Florisil-aminopropyl silica gel mixture, placing 5g of burley tobacco sample and 2g of the Florisil-aminopropyl silica gel mixture into a 50m L centrifugal tube, adding 25m of sodium hydroxide aqueous solution with the pH value of 14 to extract at normal temperature, carrying out vortex oscillation for 25 minutes, filtering through a filter membrane with the pore diameter of 0.22 mu m to obtain an extracting solution, and measuring a series of standard solutions and extracting solutions by using liquid chromatography-mass spectrometry/mass spectrometry, wherein the operation conditions are the same as those in example 1 except that the mobile phase of the liquid chromatography is 10 mmol/L aqueous ammonia.
The contents of ziram and fermet in the burley tobacco samples calculated by the external standard method according to the measurement results of the series of standard solutions and extracts and the quantitative ion pair 121/87 are shown in table 3 (no other dithiocarbamate compounds in the burley tobacco samples are detected).
The respective amounts of ziram and fermet in burley tobacco samples were determined as shown in table 3 (no other dithiocarbamate compounds were detected) using 2g of each of the respective florisil and the respective 2g of the aminopropyl silica gel in place of the florisil-aminopropyl silica gel mixture described above in this example, except as described above in this example.
The recovery of spiked samples was determined for the mixture of Florisil-aminopropyl silica gel without adsorbent and with the addition of Florisil, with the addition of Florisil and with the addition of aminopropyl silica gel as described above in this example, and the results are shown in Table 3.
TABLE 3
As can be seen from Table 3, the recovery rate of the added standard far exceeds 100% without adding the adsorbent, which indicates that the interferents in the sample seriously affect the accurate determination of the ziram and the ziram. Compared with the single use of the Florisil or the aminopropyl silica gel as the adsorbent, the invention has higher measurement accuracy (the addition standard recovery rate is closer to 100%) when the Florisil-aminopropyl silica gel mixture is used as the adsorbent.
Example 3
The procedure of example 1 was repeated except that the mobile phase of the liquid chromatography was 50 mmol/L aqueous ammonia, and the procedure was repeated except that 10g of the aromatic tobacco sample and 5g of the mixture of Florisil silica gel were placed in a 100m L centrifuge tube, and a 50m L aqueous sodium hydroxide solution having a pH of 13.5 was added at room temperature for extraction, vortexed and shaken for 30 minutes, and filtered through a 0.22 μm pore size filter to obtain an extract solution.
According to the measurement results of the series of standard solutions and the extraction solution and the quantitative ion pair 211/135 in table 1, the content of zineb in the cigarette sample is calculated by an external standard method and is shown in table 4 (no detection of other dithiocarbamate compounds in the cigarette sample).
The amounts of zineb in the resulting flavor samples were determined as shown in table 4 (no other dithiocarbamate compounds were detected in the flavor smoke sample) using 5g of florisil and 5g of aminopropyl silica gel, respectively, in place of the florisil-aminopropyl silica gel mixture described above in this example, except as described in this example.
The recovery of spiked samples was determined for the mixture of Florisil-aminopropyl silica gel without adsorbent and with the addition of Florisil, with the addition of Florisil and with the addition of aminopropyl silica gel as described above in this example, and the results are shown in Table 4.
TABLE 4
As can be seen from Table 4, the recovery rate of the added standard far exceeds 100% without adding the adsorbent, which indicates that the interferents in the sample seriously affect the accurate determination of the zineb content. Compared with the single use of the Florisil or the aminopropyl silica gel as the adsorbent, the method has higher accuracy (the spiked recovery rate is closer to 100%) when the Florisil-aminopropyl silica gel mixture is used as the adsorbent.
Example 4
The vortex mixing time was adjusted to 2 minutes, 10 minutes, 30 minutes and 40 minutes, respectively, and the rest was the same as in example 1, and the determined propineb content and the normalized recovery (the normalized amount is the same as in example 1) of the flue-cured tobacco samples are shown in table 5.
TABLE 5
As can be seen from tables 2 and 5, the accuracy of the measurement method gradually increased with the increase of the vortex oscillation time, and gradually decreased after the vortex oscillation time reached 30 minutes. The vortex oscillation time is selected to be 20-40 minutes, and the effect is good.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (53)
1. A method for extracting dithiocarbamate compounds from a sample, comprising the steps of:
1) mixing the sample, the adsorption composition and the alkaline solution to obtain a mixture; the adsorption composition comprises Florisil diatomite and aminopropyl silica gel, wherein the weight ratio of the Florisil diatomite to the aminopropyl silica gel is (0.1-5): 1;
2) filtering the mixture obtained in the step 1) to obtain filtrate, namely extracting solution.
2. The method according to claim 1, wherein in the step 1), the weight ratio of the Florisil to the aminopropyl silica gel is (0.2-4): 1.
3. The method according to claim 1, step 1), characterized by one or more of the following a to F:
A. the purity of the Florisil is more than or equal to 90 percent;
B. the mesh number of the Florisil diatomite is 30-150 meshes;
C. the specific surface area of the Florisil is more than or equal to 200m2/g；
D. The average particle size of the aminopropyl silica gel is 20-130 mu m;
E. the specific surface area of the aminopropyl silica gel is more than or equal to 100m2/g；
F. The content of aminopropyl in aminopropyl silica gel is more than or equal to 0.3 mmol/g.
4. The method according to claim 3, wherein the purity of the Florisil in item A is 95% or more.
5. The method according to claim 3, wherein the purity of the Florisil in item A is 97% or more.
6. The method according to claim 3, wherein the purity of the Florisil in item A is 99% or more.
7. The method according to claim 3, wherein the number of meshes of the Florisil in item B is 40 to 120 meshes.
8. The method according to claim 3, wherein, in item C, the specific surface area of the diatomaceous earth is 240m or more2/g。
9. The method according to claim 3, wherein in item C, the specific surface area of the Florisil is 260 to 2000m2/g。
10. The method according to claim 3, wherein in item C, the specific surface area of the Florisil is 260 to 1000m2/g。
11. The method according to claim 3, wherein in item C, the specific surface area of the Florisil is 270 to 800m2/g。
12. The method according to claim 3, wherein in item D, the aminopropyl silica gel has an average particle size of 30 to 100 μm.
13. A process as claimed in claim 3, wherein in item E, the specific surface area of aminopropyl silica gel is 120 or morem2/g。
14. A process as claimed in claim 3, wherein in item E, the specific surface area of aminopropyl silica gel is 140m or more2/g。
15. A process as claimed in claim 3, wherein in item E, the aminopropyl silica gel has a specific surface area of 160 to 2000m2/g。
16. A process as claimed in claim 3, wherein in item E, the aminopropyl silica gel has a specific surface area of 180 to 1000m2/g。
17. A process as claimed in claim 3, wherein in item E, the aminopropyl silica gel has a specific surface area of 180 to 600m2/g。
18. A process according to claim 3, wherein in item F, the aminopropyl group content in the aminopropyl silica gel is from 0.3 to 30 mmol/g.
19. A process according to claim 3, wherein in item F, the aminopropyl group content in the aminopropyl silica gel is from 0.3 to 3 mmol/g.
20. The method of claim 1, wherein the method of making the adsorbent composition comprises the step of mixing flory diatomaceous earth and aminopropyl silica gel.
21. The method according to any one of claims 1 to 20, characterized by one or more of the following (a) to (i):
(a) in the step 1), mixing is carried out under vortex oscillation;
(b) in the step 1), the mixing time is 10-70 minutes;
(c) in the step 1), the weight ratio of the sample to the adsorption composition is (0.2-6) to 1;
(d) in the step 1), the ratio of the mixed materials to the liquid is 0.05-1 g/m L;
(e) the sample is tobacco and/or a tobacco product;
(f) the dithiocarbamate compound is at least one selected from the group consisting of thiram, ziram, ferbam, mancozeb, zineb, maneb, metiram, amobam, metiram, sodium and propineb;
(g) in the step 1), the pH value of the alkaline solution is 12-14;
(h) in the step 1), the alkaline solution is at least one selected from a sodium hydroxide solution, a potassium hydroxide solution and an ammonia water solution;
(i) in the step 2), a filter membrane is adopted for filtration.
22. The method according to claim 21, wherein in the step 1) in the item (b), the mixing time is 15 to 50 minutes.
23. The method according to claim 21, wherein in the step (b), the mixing time in the step 1) is 20 to 40 minutes.
24. The method of claim 21, wherein in item (c), the weight ratio of sample to adsorbent composition in step 1) is (0.6-4): 1.
25. The method according to claim 21, wherein in the step (d), the mixture ratio of the mixture solution and the additive solution is 0.1-0.8 g/m L.
26. The method according to claim 21, wherein in the step 1) in the item (g), the pH value of the alkaline solution is 13 to 14.
27. The method according to claim 21, wherein in the step 2) in the item (i), the pore size of the filter membrane is 0.2 to 0.4. mu.m.
28. The method according to claim 21, wherein in item (i), the pore size of the filter membrane in step 2) is 0.22 μm.
29. A method for determining dithiocarbamate compounds in a sample, comprising the steps of:
(1) obtaining an extract according to the method of any one of claims 1 to 28;
(2) performing liquid chromatography-mass spectrometry/mass spectrometry detection on the extracting solution obtained in the step (1) to obtain a detection result;
(3) and (3) calculating the content of the dithiocarbamate compounds in the sample according to the detection result obtained in the step (2).
30. The method according to claim 29, wherein in the step (3), the content of each dithiocarbamate compound in the sample is calculated according to the detection result obtained in the step (2).
31. The method according to claim 29, wherein the dithiocarbamate compound is at least one selected from the group consisting of thiram, ziram, ferbam, mancozeb, zineb, maneb, metiram, amobam, metiram, sodium and propineb.
32. The process of claim 31, step (3), characterized by one or more of the following (i) to (vi):
(i) a qualitative ion pair of any one compound selected from thiram, ziram and ferumyl 121/45 and/or 121/87;
(ii) the quantitative ion pair of any one compound selected from thiram, ziram and ferme is 121/45 or 121/87;
(iii) a qualitative ion pair of any one compound selected from mancozeb, zineb, maneb, metiram, amobam, metiram and sodium is 211/135 and/or 211/177;
(IV) the quantitative ion pair of any compound selected from mancozeb, zineb, maneb, metiram, amobam, metiram and sodium is 211/135 or 211/177;
(v) the qualitative ion pair of propineb is 225/149 and/or 225/191;
(VI) the quantitative ion pair of propineb is 225/149 or 225/191.
33. The method according to any one of claims 29 to 32, characterized by one or more of the following (a) to (O):
(A) in the step (2), C18 chromatographic column is adopted in liquid chromatography;
(B) in the step (2), the mobile phase of the liquid chromatogram is 1-70 mmol/L ammonia water solution;
(C) in the step (2), the elution mode of the liquid chromatogram is isocratic elution;
(D) in the step (2), the flow rate of a mobile phase of the liquid chromatogram is 100-300 mu L/min;
(E) in the step (2), the column temperature of the liquid chromatogram is 35-50 ℃;
(F) in the step (2), the ion source of the mass spectrum is an electrospray ion source;
(G) in the step (2), the detection mode of the mass spectrum is a selective ion scanning mode, and the detection mode of the mass spectrum is multi-reaction monitoring;
(H) in the step (2), the electrospray voltage of the mass spectrum is 4500-5500V;
(I) in the step (2), the ion source temperature of the mass spectrum is 300-400 ℃;
(J) in the step (2), the gas curtain gas of the mass spectrum is 0.1-0.2 MPa nitrogen;
(K) in the step (2), the atomization gas of the mass spectrum is 0.3-0.7 MPa nitrogen;
(L) in the step (2), the collision gas of the mass spectrum is nitrogen with the pressure of 0.01-0.04 MPa;
(M) in the step (2), the collision energy of the mass spectrum is 10-25V;
(N) in the step (2), the residence time of the mass spectrum is 30-60 ms;
(O) the sample is tobacco and/or a tobacco product.
34. The method according to claim 33, wherein in the step (B), the mobile phase of the liquid chromatography is 3 to 60 mmol/L ammonia solution in step (2).
35. The method according to claim 33, wherein in the step (D), the flow rate of the mobile phase in the liquid chromatography is 200 to 300. mu. L/min.
36. The method according to claim 33, wherein in item (E), the column temperature of the liquid chromatography in step (2) is 35 to 45 ℃.
37. The method according to claim 33, wherein in item (H), the electrospray voltage of the mass spectrum in step (2) is 4700-5200V.
38. The method of claim 33, wherein in item (I), the ion source temperature of the mass spectrum in step (2) is 330-370 ℃.
39. The method of claim 33, wherein in item (M), in step (2), the collision energy of the mass spectrum is 13-22V.
40. The method of claim 33, wherein in item (N), the mass spectrum has a residence time of 40-60 ms in step (2).
41. A kit for extracting or assaying dithiocarbamate compounds, comprising the adsorption composition according to any one of claims 1 to 19, and further comprising an alkaline solution, a filter membrane, a liquid chromatography column and an aqueous ammonia solution.
42. The kit of claim 41, further comprising nitrogen.
43. The kit according to claim 41, wherein the dithiocarbamate compound is at least one selected from the group consisting of thiram, ziram, ferbam, mancozeb, zineb, maneb, metiram, amobam, metiram, sodium and propineb.
44. The kit of claim 41, characterized by one or more of the following (i) to (v):
(i) the alkaline solution is at least one selected from sodium hydroxide, potassium hydroxide and ammonia water solution;
(ii) the pH value of the alkaline solution is 12-14;
(iii) the aperture of the filter membrane is 0.2-0.4 μm;
(iv) the liquid chromatographic column is a C18 chromatographic column;
(v) the molar concentration of the ammonia water solution is 1-70 mmol/L.
45. The kit according to claim 44, wherein in item (ii), the pH of the alkaline solution is 13 to 14.
46. The kit according to claim 44, wherein in item (iii), the pore size of the filter is 0.22. mu.m.
47. The kit according to claim 44, wherein in item (v), the molar concentration of the aqueous ammonia solution is 3 to 60 mmol/L.
48. Use of the adsorption composition of any one of claims 1 to 19 or the kit of any one of claims 41 to 47 for extracting or determining a dithiocarbamate compound in a sample.
49. The use according to claim 48, wherein the dithiocarbamate compound is at least one selected from the group consisting of thiram, ziram, ferbam, mancozeb, zineb, maneb, metiram, amobam, metiram, sodium and propineb.
50. Use according to claim 48, wherein the sample is tobacco and/or a tobacco product.
51. Use of an adsorption composition as claimed in any one of claims 1 to 19 to improve the accuracy of the determination of dithiocarbamates in a sample.
52. The use according to claim 51, wherein the dithiocarbamate compound is at least one selected from the group consisting of thiram, ziram, ferbam, mancozeb, zineb, maneb, metiram, amobam, metiram, sodium and propineb.
53. Use according to claim 51, wherein the sample is tobacco and/or a tobacco product.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006313125A (en) * | 2005-05-09 | 2006-11-16 | Kansai Electric Power Co Inc:The | Method for speedily analyzing pcb on criterion of treated material of pcb waste |
| WO2009086304A1 (en) * | 2007-12-28 | 2009-07-09 | Sigma-Aldrich Co. | Methods and devices for simultaneously detecting ozone and carbonyl- containing compounds |
| KR20110122025A (en) * | 2010-05-03 | 2011-11-09 | 한국해양연구원 | A novel single purification column kit for simultaneously removing sulfur, water and polar organic chemical materials containing sample |
| CN103331037A (en) * | 2013-07-03 | 2013-10-02 | 大连海事大学 | Separation column filler for separating PCBs (Poly Chlorinated Biphenyls) or OCPs (Organic Chlorine Pesticides) in high-fat content sample and separation method |
| CN103353488A (en) * | 2013-06-19 | 2013-10-16 | 中华人民共和国潍坊出入境检验检疫局 | Method for determining residues of chlorothalonil, captan, captafol and folpet in vegetables and fruits |
| CN104535672A (en) * | 2014-12-04 | 2015-04-22 | 苏州国环环境检测有限公司 | Method for detecting residues of mancozeb in cucumber |
| CN106124279A (en) * | 2016-09-09 | 2016-11-16 | 福建中烟工业有限责任公司 | Pre-treatment and detection method containing dithio amino formate compounds sample |
| CN106526044A (en) * | 2017-01-10 | 2017-03-22 | 中国科学院南京土壤研究所 | Pretreatment technology for detecting polybrominated diphenyl ethers residue in vegetables |
| CN106645515A (en) * | 2016-12-29 | 2017-05-10 | 嘉兴学院 | Detection method for content of short-chain chlorinated paraffin in leather |
| CN106706826A (en) * | 2015-11-18 | 2017-05-24 | 中国科学院大连化学物理研究所 | Analysis method of plant hormones in milligram-grade plants |
-
2017
- 2017-09-30 CN CN201710912809.5A patent/CN107638871B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006313125A (en) * | 2005-05-09 | 2006-11-16 | Kansai Electric Power Co Inc:The | Method for speedily analyzing pcb on criterion of treated material of pcb waste |
| WO2009086304A1 (en) * | 2007-12-28 | 2009-07-09 | Sigma-Aldrich Co. | Methods and devices for simultaneously detecting ozone and carbonyl- containing compounds |
| KR20110122025A (en) * | 2010-05-03 | 2011-11-09 | 한국해양연구원 | A novel single purification column kit for simultaneously removing sulfur, water and polar organic chemical materials containing sample |
| CN103353488A (en) * | 2013-06-19 | 2013-10-16 | 中华人民共和国潍坊出入境检验检疫局 | Method for determining residues of chlorothalonil, captan, captafol and folpet in vegetables and fruits |
| CN103331037A (en) * | 2013-07-03 | 2013-10-02 | 大连海事大学 | Separation column filler for separating PCBs (Poly Chlorinated Biphenyls) or OCPs (Organic Chlorine Pesticides) in high-fat content sample and separation method |
| CN104535672A (en) * | 2014-12-04 | 2015-04-22 | 苏州国环环境检测有限公司 | Method for detecting residues of mancozeb in cucumber |
| CN106706826A (en) * | 2015-11-18 | 2017-05-24 | 中国科学院大连化学物理研究所 | Analysis method of plant hormones in milligram-grade plants |
| CN106124279A (en) * | 2016-09-09 | 2016-11-16 | 福建中烟工业有限责任公司 | Pre-treatment and detection method containing dithio amino formate compounds sample |
| CN106645515A (en) * | 2016-12-29 | 2017-05-10 | 嘉兴学院 | Detection method for content of short-chain chlorinated paraffin in leather |
| CN106526044A (en) * | 2017-01-10 | 2017-03-22 | 中国科学院南京土壤研究所 | Pretreatment technology for detecting polybrominated diphenyl ethers residue in vegetables |
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