CN107085053A - The analysis method of perchlorate, kit and its application in reconstituted tobacoo - Google Patents
The analysis method of perchlorate, kit and its application in reconstituted tobacoo Download PDFInfo
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- CN107085053A CN107085053A CN201710284772.6A CN201710284772A CN107085053A CN 107085053 A CN107085053 A CN 107085053A CN 201710284772 A CN201710284772 A CN 201710284772A CN 107085053 A CN107085053 A CN 107085053A
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- Prior art keywords
- perchlorate
- water
- tobacco sheet
- mobile phase
- tobacco
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- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 title claims abstract description 66
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000004458 analytical method Methods 0.000 title claims abstract description 20
- 241000208125 Nicotiana Species 0.000 claims abstract description 63
- 235000002637 Nicotiana tabacum Nutrition 0.000 claims abstract description 63
- 150000002500 ions Chemical class 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000001514 detection method Methods 0.000 claims abstract description 19
- 239000000284 extract Substances 0.000 claims abstract description 11
- 238000004451 qualitative analysis Methods 0.000 claims abstract description 10
- 238000004445 quantitative analysis Methods 0.000 claims abstract description 6
- 238000001294 liquid chromatography-tandem mass spectrometry Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 11
- 239000012528 membrane Substances 0.000 claims description 10
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 10
- 239000012498 ultrapure water Substances 0.000 claims description 10
- 238000002386 leaching Methods 0.000 claims description 9
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical group [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 8
- 238000004811 liquid chromatography Methods 0.000 claims description 7
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 7
- 238000010829 isocratic elution Methods 0.000 claims description 6
- 238000010828 elution Methods 0.000 claims description 5
- 238000001471 micro-filtration Methods 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- 238000012544 monitoring process Methods 0.000 claims description 4
- 101100447665 Mus musculus Gas2 gene Proteins 0.000 claims description 3
- 238000000132 electrospray ionisation Methods 0.000 claims description 3
- 238000010812 external standard method Methods 0.000 claims description 3
- 101100348341 Caenorhabditis elegans gas-1 gene Proteins 0.000 claims description 2
- 101100447658 Mus musculus Gas1 gene Proteins 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 claims description 2
- 229910001487 potassium perchlorate Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 9
- 238000000605 extraction Methods 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 13
- 239000012086 standard solution Substances 0.000 description 7
- 235000020188 drinking water Nutrition 0.000 description 6
- 239000003651 drinking water Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 235000013365 dairy product Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 210000001685 thyroid gland Anatomy 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- -1 gums Substances 0.000 description 2
- 238000004255 ion exchange chromatography Methods 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000002552 multiple reaction monitoring Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000001814 pectin Substances 0.000 description 2
- 229920001277 pectin Polymers 0.000 description 2
- 235000010987 pectin Nutrition 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000002798 spectrophotometry method Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- 208000024770 Thyroid neoplasm Diseases 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 230000037396 body weight Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 210000003754 fetus Anatomy 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000004885 tandem mass spectrometry Methods 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 201000002510 thyroid cancer Diseases 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention belongs to tobacco detection technique field, it is related to a kind of analysis method of perchlorate in reconstituted tobacoo, comprises the following steps：(1) flooding reconstituted tobacoo sample is used, extract solution is obtained；(2) Liquid Chromatography-Tandem Mass Spectrometry Detection and Extraction liquid is used；(3) perchlorate in testing result qualitative analysis and/or quantitative analysis reconstituted tobacoo sample；In step (3), qualitative analysis is carried out by the abundance ratio for calculating two ion pairs of 98.9/82.8 in testing result (m/z) and 100.9/84.8 (m/z).The invention further relates to a kind of kit and its application in analyzing or detecting reconstituted tobacoo in perchlorate.The inventive method can be in effectively qualitative reconstituted tobacoo perchlorate, and can Accurate Determining its content.
Description
Technical Field
The invention belongs to the technical field of tobacco detection, and particularly relates to a method for analyzing perchlorate in a tobacco sheet, a kit and application of the kit in analyzing or detecting the perchlorate in the tobacco sheet.
Background
At present, the perchlorate serving as a raw material can be used for various products such as solid propellants, aerospace equipment, military fires, fireworks and crackers, blasting agents, textile fixing agents, electroplating products, rubber products, dyes, coatings, smelting workpieces, safety airbags, magnesium batteries and the like, and the application range is wide. Since perchlorate is readily soluble in water, for example, in ground water, surface water, and drinking water during product processing or use; and the perchlorate in the water is easy to further enrich in the bodies of animals and plants.
The perchlorate is stable in chemical structure and not easy to degrade. In addition, researches show that perchlorate and iodine compete in the thyroid entering process, the perchlorate inhibits the normal absorption of the thyroid to iodine, influences the normal function of the thyroid, is easy to cause metabolic disturbance and abnormal development of nerve centers of fetuses and infants, and even causes thyroid cancer due to high-concentration perchlorate. In 2002, the national environmental protection agency (US EPA) stipulates that the maximum allowable content of perchlorate in drinking water is 1 mug/L. The european food safety agency reissues "scientific opinion on public health risks of perchlorate in food" at 26 months 5/2015, in which an allowable intake of 0.3 μ g perchlorate per kg body weight per day is set. In recent years, reports of excessive chlorate in milk powder, tea and drinking water appear successively, which arouses attention to monitoring the content of the perchlorate in food.
Heretofore, research on perchlorate detection analysis has been mainly directed to samples having simple components such as drinking water and dairy products. Common analytical methods include spectrophotometry, electrode methods, and ion chromatography.
The tobacco sheet is also called reconstituted tobacco, and mainly comprises tobacco powder, tobacco fragments, tobacco stems and/or inferior tobacco leaves and other raw materials, adhesive and other additives. Common adhesives include carboxymethylcellulose, various cellulose derivatives, pectins, gums, and other extracts of natural materials. The preparation process of the tobacco sheet is a paper making method which is commonly used, and specifically comprises the following steps: extracting raw materials with water, pulping and making paper by using insoluble substances alone or adding natural fibers to form a paper web, mixing the water-soluble extract with additives after concentrating, coating the mixture on the paper web, and drying to obtain the tobacco sheet. Perchlorate may be enriched in the preparation of tobacco sheets and it is therefore necessary to monitor the perchlorate in the tobacco sheets.
Different from samples such as drinking water and dairy products, the components of the tobacco sheets are extremely complex, mainly due to the variety of raw materials and the variety of additives of the tobacco sheets. When the tobacco sheets were analyzed by the perchlorate analysis method commonly used in drinking water and dairy products, it was found that: impurity interference is serious when detecting perchlorate in the tobacco sheets by a spectrophotometry method and an electrode method, and the accuracy is low; when the ion chromatography is used for detection, the pretreatment of the sample is very complicated, and the interference of chloride and sulfate in the sample is serious and cannot be eliminated. Therefore, there is no method for analyzing perchlorate in tobacco sheets effectively.
At present, a method for effectively analyzing the perchlorate in the tobacco sheet is needed to monitor the content of the perchlorate in the tobacco sheet.
Disclosure of Invention
The invention provides a method capable of effectively analyzing perchlorate in a tobacco sheet, and realizes monitoring of the content of the perchlorate in the tobacco sheet. Moreover, the invention also provides a kit for detecting and analyzing the perchlorate in the tobacco sheets.
The invention relates to a method for analyzing perchlorate in a tobacco sheet, which comprises the following steps:
(1) leaching a tobacco sheet sample with water to obtain an extracting solution;
(2) detecting the extract by liquid chromatography tandem mass spectrometry;
(3) qualitatively analyzing perchlorate in the tobacco sheet sample according to the detection result;
in the step (3), the abundance ratio of two ion pairs of 98.9/82.8(m/z) and 100.9/84.8(m/z) in the detection result is calculated for qualitative analysis.
In one embodiment of the invention, the perchlorate is contained in the tobacco sheet sample when the abundance ratio of 98.9/82.8(m/z) to 100.9/84.8(m/z) is 2.8-3.2 (preferably 3.08).
In one embodiment of the invention, the sample of tobacco lamina is free of perchlorate in the absence of an abundance ratio of ion pairs of 98.9/82.8(m/z) and/or 100.9/84.8(m/z) or 98.9/82.8(m/z) and 100.9/84.8(m/z) outside the range of 2.8 to 3.2.
In one embodiment of the present invention, when the perchlorate-containing salt in the tobacco sheet sample is analyzed quantitatively, the analysis method further comprises the step (4):
quantitatively analyzing perchlorate in a tobacco sheet sample, wherein the adopted quantitative ion pair is 98.9/82.8 (m/z);
preferably, the quantitative analysis uses an external standard method.
In one embodiment of the present invention, in the step (2), the mobile phase of the liquid chromatography is composed of a mobile phase a and a mobile phase B, wherein the mobile phase a is water, and the mobile phase B is an aqueous ammonia solution.
In one embodiment of the present invention, the molar concentration of the aqueous ammonia solution is 20 to 80mmol/L, preferably 35 to 65mmol/L, and more preferably 47mmol/L, 50mmol/L or 55 mmol/L.
In one embodiment of the present invention, the water is ultrapure water.
In one embodiment of the present invention, in the step (2), the liquid chromatography is performed by isocratic elution;
preferably, in the isocratic elution process, the volume ratio of the mobile phase A to the mobile phase B is (92-98): 3-7, and more preferably 95:5, 93:6 or 97: 4;
preferably, the elution time is 0 to 12 minutes, more preferably 0 to 10 minutes, such as 4 minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, 10 minutes or 11 minutes.
In one embodiment of the invention, one or more of the following 1) to 7) are also included:
1) in the step (1), the water is ultrapure water;
2) in the step (1), the weight ratio of water to the tobacco sheet sample is (40-170): 1, preferably (60-140): 1, more preferably 50:1, 70:1, 90:1, 100:1 or 120: 1;
3) in the step (1), the leaching time is 10-60 minutes, preferably 20-40 minutes, and more preferably 25 minutes, 30 minutes, 36 minutes or 40 minutes;
4) in the step (1), the leaching temperature is 20-40 ℃, preferably 25 ℃, 30 ℃, 32 ℃, 37 ℃ or 40 ℃;
5) in the step (1), leaching is carried out under the ultrasonic condition;
6) the method also comprises a step (1-A) between the steps (1) and (2): filtering the extractive solution, and collecting filtrate as extractive solution;
preferably, the filtering comprises: filtering the extractive solution with qualitative filter paper, collecting filtrate, and microfiltering the filtrate;
more preferably, the aperture of the microfiltration membrane is 0.1-0.4 μm, and even more preferably 0.2-0.3 μm;
7) the perchlorate is sodium perchlorate and/or potassium perchlorate.
In one embodiment of the present invention, the operating conditions of the liquid chromatography in step (2) include one or more of the following (a) to (D):
(A) the chromatographic column is a Dian IonPac AS11-HG chromatographic column;
(B) the specification of the chromatographic column is 4mm multiplied by 250 mm;
(C) the temperature of the chromatographic column is 30-50 ℃, preferably 32 ℃, 37 ℃, 40 ℃, 43 ℃, 45 ℃ or 48 ℃;
(D) the flow rate is 700 to 900. mu.L/min, preferably 750. mu.L/min, 780. mu.L/min, 800. mu.L/min, 820. mu.L/min, 860. mu.L/min or 890. mu.L/min.
In one embodiment of the present invention, the operating conditions of the mass spectrum in step (2) include one or more of the following (a) to (h):
(a) the ion source is an electrospray ionization source;
(b) the scanning mode is negative ion scanning;
(c) the detection mode is multi-reaction monitoring;
(d) the electrospray voltage is-5000 to-4000V, preferably-4700V, -4500V, -4300V and-4100V;
(e) the ion source temperature is 300-400 ℃, preferably 320 ℃, 330 ℃, 350 ℃, 370 ℃ or 390 ℃;
(f) the pressure of the auxiliary Gas Gas1 and/or Gas2 is 40-70 psi, preferably 50psi or 60 psi;
(g) the declustering voltage is-50 to-30V, preferably-40V;
(h) the collision energy is-30 to-10V, preferably-27V, -24V, -20V, -19V, -17V, -15V or-13V.
Another aspect of the invention relates to a kit comprising: water, an ammonia water solution, qualitative filter paper, a filter membrane with the aperture of 0.1-0.4 mu m and a Dyan IonPac AS11-HG chromatographic column.
In one embodiment of the invention, the kit comprises one or more of the following (i) to (iii):
the molar concentration of the ammonia water solution is 20-80 mmol/L, preferably 35-65 mmol/L, more preferably 47mmol/L, 50mmol/L or 55 mmol/L;
(II) the aperture of the filter membrane is 0.2-0.3 μm;
(III) the column size is 4mm X250 mm.
A further aspect of the invention relates to the use of said kit according to any of the preceding aspects of the invention for analyzing or detecting perchlorate in tobacco sheet.
In the present invention, unless otherwise specified,
the term "tobacco sheet" is also called reconstituted tobacco, and mainly comprises tobacco powder, tobacco fragments, tobacco stems and/or inferior tobacco leaves and other raw materials, adhesive and other additives. Common adhesives include carboxymethylcellulose, various cellulose derivatives, pectins, gums, and other extracts of natural materials.
The term "leaching" refers to a process of soaking a solid sample with a liquid solvent to extract the solute therefrom.
The term "qualitative analysis" refers to the analysis of the "quality" of the study, and is intended to solve the problem of "presence or absence" or "not presence or absence" of the study.
The term "quantitative analysis" refers to the determination of the content of various components in a substance.
The term "abundance" refers to the relative amount of an object under study in a study system, expressed as a mass percentage.
The term "ultrapure water" means water having an electrical conductivity of less than 0.1. mu.s/cm, a pH of 6.8 to 7.0 and free of other impurities and bacteria at a temperature of 25 ℃.
The term "isocratic elution" refers to an elution pattern in which the composition ratio and flow rate of a mobile phase are constant during an analysis cycle of a sample component.
The term "ultrasound" refers to sound waves having a frequency above 20000 hertz.
The term "filtration" refers to the operation of separating solids and other materials from a liquid by the liquid in a suspension passing through a media, the solid particles and other materials being retained by the filtration media under the influence of a driving force or other external forces.
The term "qualitative filter paper" refers to "qualitative analysis filter paper" as opposed to quantitative analysis filter paper and chromatographic qualitative analysis filter paper. Qualitative analysis filter paper generally has more residual ash, is only used for general qualitative analysis and filtration of sediment or suspension in solution, and cannot be used for mass analysis.
The term "microfiltration" is also called microfiltration, which is filtration performed using a porous membrane (microfiltration membrane) as a filtration medium.
The term "chromatography column" refers to a column tube packed with a stationary phase for separating mixed components.
The term "mobile phase" refers to a gas or liquid used to carry a sample and eluted components in a chromatographic separation.
The term "external standard method" refers to relative comparison of a reference substance of a component to be tested to determine the content of a test sample.
The term "ion source" refers to the component of a mass spectrometry particle accelerator that dissociates sample molecules to produce fast moving ions.
The term "kit" refers to a box for holding the required chemical reagents and laboratory supplies.
The invention achieves at least one of the following beneficial effects:
1. the method can effectively determine the perchlorate in the tobacco sheet.
2. The method can accurately determine the content of the perchlorate in the tobacco sheets.
3. The kit can be used for detecting and analyzing the content of the perchlorate in the tobacco sheets.
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 chromatogram of a standard solution of S5 in example 1 of the present invention.
FIG. 2 is a chromatogram of an extract liquid in example 1 of the present invention.
Detailed Description
Example 1
1. Material
Tobacco sheet: purchased from minjia reconstituted tobacco limited.
And (3) filtering the membrane: purchased from Hippo technologies, Inc. and having a pore size of 0.22 μm.
Sodium perchlorate standard: purchased from national drug control stock gmbh.
50mM aqueous ammonia solution: purchased from national drug control stock gmbh.
2. Detection method
(1) Preparing an extracting solution:
0.5g of tobacco sheet (accurate to 0.000lg) was sampled and put into a 250mL ground flask, 50.0mL of ultrapure water was added, the flask was closed, extraction was carried out under ultrasonic conditions for 30 minutes with the extraction temperature controlled at room temperature, and the liquid was collected. The liquid was filtered through qualitative filter paper and the first 5 ml of filtrate was discarded, and the further filtrate was collected. Filtering the subsequent filtrate with a filter membrane with pore diameter of 0.22 μm to obtain filtrate as extractive solution.
(2) Preparing a standard solution:
a plurality of sodium perchlorate standard substances are taken and respectively added with ultrapure water to prepare serial concentration standard solutions S1-S6, the concentration of which is respectively 0.05 mug/L, 0.L0 mug/L, 0.50 mug/L, 1 mug/L, 5 mug/L and L0 mug/L.
(3) Liquid chromatography tandem mass spectrometry:
the extract and the standard solutions of the respective concentrations were subjected to detection analysis by a liquid chromatography tandem mass spectrometer (AB corporation, Qtrap 5500). Wherein, the chromatogram of the S5 standard solution is shown in figure 1; the chromatogram of the extract is shown in FIG. 2 (wherein a weak peak having a short retention time represents an impurity).
Wherein, the operating conditions of the liquid chromatogram are as follows:
a chromatographic column: a Dyan IonPac AS11-HG chromatographic column with the specification of 4mm multiplied by 250 mm;
temperature of the column: 40 ℃;
mobile phase: the mobile phase A is ultrapure water, and the mobile phase B is 50mM ammonia water solution;
isocratic elution: the elution time was 10 minutes; and during elution, the volume ratio of the mobile phase A to the mobile phase B is 95: 5;
flow rate: 800 muL/min;
sample introduction amount: 5 μ L.
The mass spectrum operating conditions were as follows:
an ion source: electrospray ionization source (ESI);
the scanning mode is as follows: scanning negative ions;
the detection mode is as follows: multiple Reaction Monitoring (MRM);
electrospray voltage: -4500V;
ion source temperature: 350 ℃;
pressure of assist Gas 1: 60 psi; pressure of assist Gas 2: 50 psi;
declustering voltage (DP): -40V;
collision Energy (CE): -20V;
the qualitative ion pair of perchlorate was 98.9/82.8(m/z) and 100.9/84.8(m/z), and when the abundance ratio of the 98.9/82.8(m/z) and 100.9/84.8(m/z) ion pair was 3.08, it was characterized as containing perchlorate;
quantitative ion pair of perchlorate: 98.9/82.8 (m/z).
(4) The perchlorate content in the sample was calculated:
according to the detection results of the series of concentration standard solutions in the step (3), the mass concentration X of the sodium perchlorate is linearly regressed by the peak area Y of the sodium perchlorate to obtain a standard working curve: Y217778X +55222, R2 0.9997. Therefore, the curve has good linearity in the concentration range of 0.05-10 mug/L and is suitable for quantitative analysis.
The S1 standard solution was serially diluted and detected according to the method in (3), and the limit of quantification of the (sodium) perchlorate was 0.02 μ g/L and the limit of detection was 0.005 μ g/L, respectively, in terms of the signal-to-noise ratio S/N >10 and S/N ═ 3.
Substituting the peak area of the perchlorate detected by the extracting solution into the standard working curve to obtain the content A of the perchlorate in the extracting solution. And calculating the content of the perchlorate in the tobacco sheet sample by the following formula.
m＝(A×S)/n
Wherein,
m-content of perchlorate in tobacco sheet sample (. mu.g/kg);
a-content of perchlorate in the extract (. mu.g/L);
the sum (L) of the volume of the S-extract and the volume of the discarded filtrate;
n-weight of tobacco sheet sample (kg).
The content of perchlorate in the tobacco sheet sample of this example was calculated to be 10.73. mu.g/kg.
Example 2
The tobacco sheet samples of example 1 were tested in duplicate 6 times a day for 3 days for 18 replicates, according to the method of example 1, and the results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the relative standard deviation in the day and the relative standard deviation in the day of the method for analyzing the perchlorate in the tobacco sheet sample are both less than 5%, which indicates that the method for analyzing the chlorate in the tobacco sheet sample has good repeatability.
Example 3
Three sodium perchlorate standard samples (the manufacturer and the model are the same as those in example 1) with three concentration levels are respectively added into a plurality of tobacco sheet samples with the same mass, the mixture is mixed evenly, and the perchlorate content of the added standard samples is determined according to the method in example 1. Each concentration level was determined in triplicate. The recovery was calculated and the results are shown in table 2.
TABLE 2
As can be seen from Table 2, the recovery rate of perchlorate by the analytical method of the present invention is between 93.8% and 97.1%, and the analytical method meets the requirements of chemical detection.
Comparative example 1 Effect of the column
The procedure of example 1 was followed using an Agilent C18 column (100 mm. times.3 mm i.d.,2.6 μm standard) instead of the Dyan IonPac AS11-HG column of example 1.
As a result, it was found that the peak of the other anion was not separated from the peak of the perchlorate, and thus the perchlorate could not be detected.
Comparative example 2 Effect of the Mobile phase
(1) The mobile phase in example 1 was replaced with ultrapure water, and the remainder was conducted by referring to example 1.
The detection result shows that: when ultrapure water was used as the mobile phase, the peak area of the target was 169900, which is significantly lower than the peak area of the target when 50mM ammonia water was used as the mobile phase (27800).
(2) The areas of the peaks of the target substances detected with different aqueous ammonia solutions instead of mobile phase B in example 1 are shown in the table below:
| concentration of ammonia | 10mM | 30mM | 50mM | 70mM | 90mM |
| Peak area | 21200 | 25300 | 27800 | 27400 | 26500 |
The peak area of the target gradually increases as the concentration of ammonia increases. When the peak area reaches the maximum when the ammonia concentration reaches 50mM, the ammonia concentration is continuously increased, and the peak area of the target object is reduced.
Comparative example 3 Effect of qualitative analysis method
With reference to the method of example 1(3), when other substances than perchlorate were subjected to LC tandem mass spectrometry, ion pairs of 98.9/82.8(m/z) or 100.9/84.8(m/z) were observed; alternatively, 98.9/82.8(m/z) and 100.9/84.8(m/z) ion pairs can occur simultaneously, but the abundance ratio of the two ion pairs is not in the range of 2.8-3.2. Therefore, the perchlorate cannot be correctly characterized by using the 98.9/82.8(m/z) ion pair or the 100.9/84.8(m/z) ion pair alone or by using the 98.9/82.8(m/z) and 100.9/84.8(m/z) ion pairs, but whether the abundance ratio is in the range of 2.8-3.2 or not is not examined.
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 (10)
1. A method for analyzing perchlorate in tobacco sheets comprises the following steps:
(1) leaching a tobacco sheet sample with water to obtain an extracting solution;
(2) detecting the extract by liquid chromatography tandem mass spectrometry;
(3) qualitatively analyzing perchlorate in the tobacco sheet sample according to the detection result;
in the step (3), qualitative analysis is carried out by calculating the abundance ratio of two ion pairs of 98.9/82.8(m/z) and 100.9/84.8(m/z) in the detection result;
preferably, the perchlorate is contained in the tobacco sheet sample when the abundance ratio of 98.9/82.8(m/z) to 100.9/84.8(m/z) is 2.8-3.2 (preferably 3.08);
preferably, the sample of tobacco sheet is free of perchlorate in the absence of an abundance ratio of ion pairs of 98.9/82.8(m/z) and/or 100.9/84.8(m/z) or 98.9/82.8(m/z) and 100.9/84.8(m/z) outside the range of 2.8 to 3.2.
2. The analysis method according to claim 1, wherein, when the perchlorate-containing salt is qualitatively analyzed in the tobacco sheet sample, the analysis method further comprises the step (4):
quantitatively analyzing perchlorate in a tobacco sheet sample, wherein the adopted quantitative ion pair is 98.9/82.8 (m/z);
preferably, the quantitative analysis uses an external standard method.
3. The analytical method according to claim 1, wherein in the step (2), the mobile phase of the liquid chromatography comprises mobile phase A and mobile phase B, wherein the mobile phase A is water, and the mobile phase B is an aqueous ammonia solution;
preferably, the molar concentration of the ammonia water solution is 20-80 mmol/L, more preferably 35-65 mmol/L, and further preferably 50 mmol/L;
preferably, the water is ultrapure water.
4. The analytical method according to claim 3, wherein in the step (2), the liquid chromatography is performed by isocratic elution;
preferably, in the isocratic elution process, the volume ratio of the mobile phase A to the mobile phase B is (92-98): 3-7, and more preferably 95: 5;
preferably, the elution time is 0 to 12 minutes, more preferably 0 to 10 minutes.
5. The analytical method according to claim 1, characterized by one or more of the following 1) to 7):
1) in the step (1), the water is ultrapure water;
2) in the step (1), the weight ratio of water to the tobacco sheet sample is (40-170): 1, preferably (60-140): 1, and more preferably 100: 1;
3) in the step (1), the leaching time is 10-60 minutes, preferably 20-40 minutes, and more preferably 30 minutes;
4) in the step (1), the leaching temperature is 20-40 ℃;
5) in the step (1), leaching is carried out under the ultrasonic condition;
6) the method also comprises a step (1-A) between the steps (1) and (2): filtering the extractive solution, and collecting filtrate as extractive solution;
preferably, the filtering comprises: filtering the extractive solution with qualitative filter paper, collecting filtrate, and microfiltering the filtrate;
more preferably, the aperture of the microfiltration membrane is 0.1-0.4 μm, and even more preferably 0.2-0.3 μm;
7) the perchlorate is sodium perchlorate and/or potassium perchlorate.
6. The analytical method according to claim 1, wherein the operating conditions of the liquid chromatography in step (2) include one or more of the following (A) to (D):
(A) the chromatographic column is a Dian IonPac AS11-HG chromatographic column;
(B) the specification of the chromatographic column is 4mm multiplied by 250 mm;
(C) the temperature of the chromatographic column is 30-50 ℃, and preferably 40 ℃;
(D) the flow rate is 700-900 μ L/min, preferably 800 μ L/min.
7. The analytical method of claim 1, wherein the operating conditions of the mass spectrometer in step (2) comprise one or more of the following (a) to (h):
(a) the ion source is an electrospray ionization source;
(b) the scanning mode is negative ion scanning;
(c) the detection mode is multi-reaction monitoring;
(d) the electrospray voltage is-5000 to-4000V, preferably-4500V;
(e) the ion source temperature is 300-400 ℃, and preferably 350 ℃;
(f) the pressure of the auxiliary Gas Gas1 and/or Gas2 is 40-70 psi, preferably 50psi or 60 psi;
(g) the declustering voltage is-50 to-30V, preferably-40V;
(h) the collision energy is-30 to-10V, preferably-20V.
8. A kit, comprising: water, ammonia water solution, qualitative filter paper, a filter membrane with the aperture of 0.1-0.4 mu m and a Dyan IonPacAS11-HG chromatographic column.
9. The kit according to claim 8, characterized by one or more of the following (I) to (III):
the molar concentration of the ammonia water solution is 20-80 mmol/L, preferably 35-65 mmol/L, and more preferably 50 mmol/L;
(II) the aperture of the filter membrane is 0.2-0.3 μm;
(III) the column size is 4mm X250 mm.
10. Use of a kit according to claim 8 or 9 for the analysis or detection of perchlorate in tobacco sheet.
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