CN103063761A - Method for determining maleic hydrazide content in cigarette mainstream smoke - Google Patents
Method for determining maleic hydrazide content in cigarette mainstream smoke Download PDFInfo
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- CN103063761A CN103063761A CN2012105201741A CN201210520174A CN103063761A CN 103063761 A CN103063761 A CN 103063761A CN 2012105201741 A CN2012105201741 A CN 2012105201741A CN 201210520174 A CN201210520174 A CN 201210520174A CN 103063761 A CN103063761 A CN 103063761A
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- maleic acid
- acid hydrazide
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Abstract
The invention discloses a method for determining a maleic hydrazide content in cigarette mainstream smoke. The method comprises using tertbutyl hydroquinone as an internal standard substance, choosing cigarette and injecting standard pesticide samples of the maleic hydrazide, extracting, deriving, using a gas chromatography-mass spectrometry (GC/MS) for derivative determination of the maleic hydrazide content in the cigarette mainstream smoke, and meanwhile optimizing and selecting GC/MS analysis conditions and concentration ranges of prepared standard solutions during a determination process of the maleic hydrazide (MH). The method is simple to operate, rapid, accurate, high in sensitivity and good in repeatability, and has a maleic hydrazide determination limit of 0.14 [mu]g per cigarette, an average recovery rate of 91 %, and an average relative standard deviation (RSD) of 5.4 %.
Description
Technical field
The present invention relates to the assay method of maleic acid hydrazide content in a kind of cigarette mainstream flue gas, belong to technical field of tobacco chemical analysis.
Background technology
Maleic acid hydrazide claims again maleic hydrazide, sterling is white crystalline powder, a kind of low toxicity plant growth regulator and selective herbicide, be used in tobacco leaf planting and developmental process, suck from plant root or blade face, conducted in the plant body by xylem and bast, by the prevention cell division, thus the growth of inhibition plant.Foreign applications is more extensive, and the use amount of China is also in continuous increase in recent years.The residual quantity of maleic acid hydrazide in tobacco is between 0-300 μ g/g.International cancer research institution (IARC) is classified as the Group3 class with it after the carcinogenicity of maleic acid hydrazide is studied.
Study on Cleavage shows, the maleic acid hydrazide sterling has a certain amount of transferring in the pyrolysis product when 750 ℃ of cracking, so the maleic acid hydrazide in the cigarette might be transferred in main flume and the side-stream smoke when burning.Have at present some bibliographical informations to confirm this situation, wherein Liu etc. reported first in 1973 rate of transform of maleic acid hydrazide depend on the content of maleic acid hydrazide in the cigarette, its main flume rate of transform is between 3.94%-10.3%; The discovery main flume rates of transform such as Haeberer only are 0.2%; The main flume rate of transform that United States Department of Agriculture announces is 2-3%; The data of the reports such as Chopra are 2.5-2.8%.Because the report data is inconsistent, therefore be necessary to do further research.
Summary of the invention
The assay method that the purpose of this invention is to provide maleic acid hydrazide content in a kind of cigarette mainstream flue gas.
In order to realize above purpose, the technical solution adopted in the present invention is: the assay method of maleic acid hydrazide content in a kind of cigarette mainstream flue gas comprises the steps:
(1) sample pre-treatments
Select the qualified cigarette of weight and resistance to suction, to wherein evenly adding maleic acid hydrazide agricultural chemicals standard specimen, aspirate cigarette after the balance respectively, collect total particulate matter in mainstream smoke with filter disc, add internal standard compound, the extraction agricultural chemicals will extract liquid nitrogen and blow concentrated after the vibration;
(2) derivatization
Purify concentrate with the C18 solid phase extraction column, behind the activation C18 solid phase extraction column, the concentrate of removing step (1) is transferred on the C18 pillar, and drip washing receives efflux, will flow out liquid nitrogen and blow concentrated afterwards derivatization;
(3) preparation of standard operation solution
The maleic acid hydrazide series concentration standard operation liquid of at least three concentration gradients of preparation is for subsequent use behind the derivatization in 0.1-10.0 μ g/mL scope;
(4) gas chromatography/mass spectrometry (GC/MS) is measured
Standard operation liquid and the internal standard compound of each concentration gradient in the step (3) are carried out GC/MS mensuration, compare its respective concentration with the chromatographic peak area of standard operation liquid and internal standard compound and carry out regretional analysis, obtain standard working curve; Under the same conditions the sample liquid after derivative in the step (2) is injected GC/MS and measure, record the chromatographic peak area ratio of maleic acid hydrazide derivant and internal standard compound in the sample, the substitution typical curve obtains the maleic acid hydrazide content in the sample.
Internal standard compound is ditert-butylhydro quinone.
Maleic acid hydrazide agricultural chemicals standard specimen addition is 10,20 and 50 μ L(MH concentration, 1430 μ g/mL in the step (1)).
The condition of balance is temperature in the step (1): 22 ± 1 ℃, and humidity: 60 ± 3%, equilibration time: 48 hours.
The filter disc that uses in the step (1) is cambridge filter.
Extract is methyl alcohol in the step (1).
The method of derivatization is in step (2) and (3): add 1mL dimethyl formamide (DMF) dissolving in the sample that nitrogen is blown over, then the silylating reagent (BSTFA) that adds 0.5mL, at 75 ℃ of lower derivative 30min, take out to put and carry out GC/MS to room temperature and analyze.
Nitrogen blows under 40 ℃ and carries out in step (1) and (2).
The collocation method of step (3) Plays working fluid is: accurately take by weighing 0.0100g MH standard items, dissolve also with DMF constant volume gets 100 μ g/mL MH standard reserving solutions in the 100mL volumetric flask; Pipette 0.01,0.02,0.05,0.1,0.5 and 1.0mL MH standard reserving solution, place respectively the 10mL volumetric flask, dilute constant volume with DMF, get the MH standard operation solution of 0.1,0.2,0.5,1.0,5.0 and 10.0 μ g/mL concentration.
GC/MS analysis condition in the step (4) is: chromatographic column: DB-WAX Fused-silica capillary column, column length 30m, internal diameter 0.25mm, thickness 0.25 μ m; 275 ℃ of injector temperatures; Carrier gas: He is the shunt mode sample introduction not, sample size: 1 μ L; Constant current mode, flow velocity 1.2mL/min; Temperature programme: 50 ℃ of lasting 2min, rise to 200 ℃ with the speed of 5 ℃ of per minutes, then the speed with 8 ℃ of per minutes rises to 260 ℃, continues 15min; Transmission line temperature: 280 ℃; Ionization pattern: EI, energy 70eV; 230 ℃ of ion source temperatures; Scan mode: select ion monitoring (SIM) pattern.
Method of the present invention has overcome the deficiency of prior art sample treatment, has optimized sample-pretreating method and instrument testing conditions for the maleic acid hydrazide in the cigarette mainstream flue gas.Compared with prior art the inventive method has following excellent results:
(1) cigarette mainstream flue gas matrix is comparatively complicated, directly measure matrix effect stronger, therefore further derivatization after adopting the C18 solid phase extraction column to purify, then the mode that adopts GC/MS to detect, both can reduce matrix effect, and can effectively realize detecting to the maleic acid hydrazide in the main flume again and analyze;
(2) this method has advantages of easy and simple to handle, quick, accurate, highly sensitive and good reproducibility, and the detecting of maleic acid hydrazide is limited to 0.14 μ g/ and props up, and average recovery rate is 91%, and average relative standard deviation (RSD) is 5.4%.
Description of drawings
Fig. 1 is the chromatogram of standard solution, and IS is the internal standard compound peak among the figure, and MH is the maleic acid hydrazide derivative peak;
Fig. 2 is the chromatogram of sample solution, and IS is the internal standard compound peak among the figure, and MH is the maleic acid hydrazide derivative peak;
Fig. 3 is the canonical plotting of maleic acid hydrazide in the specific embodiment of the invention.
Embodiment
The present invention is described further below in conjunction with example, but is not restriction the present invention.
1. instrument and reagent:
Gilson ASPEC XL4-V2 automatic solid-phase extractor (Gilson Labs, France); Buchi Rota vapor R-200 Rotary Evaporators (Buchi, Switzerland); CDS5000 thermal cracking instrument (CDS, USA); 6890N GC/5975B MS gas chromatograph-mass spectrometer (GCMS) (Agilent, USA); BORGWALDT-KC5 duct effluent smoking machine (BORGWALDT-KC, German); Quartz fibre filter disc (diameter 44mm, Millipore, USA); Gas meter (test specification 0-6L/min, A.P.BUCK Inc, USA); Solid phase extraction column: C18 post (500mg, 3mL) is purchased from Supelco company; The 3R4F cigarette (Kentucky university, USA).
Reagent: acetonitrile, methyl alcohol, silylating reagent (BSTFA), DMF are chromatographic grade (Tedia, USA);
Standard substance: maleic acid hydrazide, ditert-butylhydro quinone (internal standard compound) is purchased from German Augsburg company.
2. operation steps:
(1) sample pre-treatments
Get one group of cigarette, select the qualified cigarette of weight and resistance to suction, respectively to wherein adding maleic acid hydrazide agricultural chemicals standard specimen 10,20 and 50 μ L(1430 μ g/mL), evenly inject with micro syringe, it is 22 ± 1 ℃ that the mark-on cigarette is placed temperature, humidity is balance 48 hours in 60 ± 3% the environment, adjust inspection smoking machine suction parameter according to GB/T16450 " conventional analysis defines and standard conditions with smoking machine ", cigarette on the effluent smoking machine of BORGWALDT-KC5 duct after the suction balance, collect total particulate matter in mainstream smoke with cambridge filter, then filter disc is taken off with the merging of absorbent cotton scouring drip catcher inwall and put into the 100mL triangular flask.After adding internal standard compound, 20min extracts agricultural chemicals with the vibration of 50mL methyl alcohol, then is filtered in the nitrogen bottle blowing, blows at 40 ℃ of lower nitrogen to be concentrated into 1mL.
(2) derivatization
Adopt the C18 solid phase extraction column to purify concentrate, first with 5mL methyl alcohol activation C18 solid phase extraction column, pipetting the 1mL concentrate is transferred on the C18 pillar, receive efflux, and with 5mL methyl alcohol drip washing Solid-Phase Extraction and receive, 40 ℃ lower will receive liquid nitrogen blow concentrate closely dried, add 1mL DMF dissolving, then the BSTFA that adds 0.5mL at 75 ℃ of lower derivative 30min, takes out to put and carries out GC/MS to room temperature and analyze.
(3) standard operation solution
Accurately take by weighing 0.0100g MH standard items, place the 100mL volumetric flask, with DMF dissolving, constant volume, get 100 μ g/mLMH standard reserving solutions; Pipette 0.01,0.02,0.05,0.1,0.5 and 1.0mL MH standard reserving solution, place respectively the 10mL volumetric flask, dilute constant volume with DMF, get 0.1,0.2,0.5, the MH standard operation solution of 1.0,5.0 and 10.0 μ g/mL concentration, pipette respectively 1mL working solutions at different levels and add respectively the BSTFA of 0.5mL, at 75 ℃ of lower derivative 30min, take out to put and carry out GC-MS to room temperature and analyze, and with the peak area of MH derivant its respective concentration is carried out regretional analysis, obtain standard working curve.
(4) gas chromatography/mass spectrometry (GC/MS) is measured
The standard operation solution of variable concentrations gradient is injected respectively GC/MS, carry out the quantitative test of maleic acid hydrazide content with internal standard method, namely compare its respective concentration with the chromatographic peak area of maleic acid hydrazide derivant and internal standard compound ditert-butylhydro quinone and carry out regretional analysis, obtain typical curve; Under the same conditions sample extracting solution is injected GC/MS and measure, record the chromatographic peak area ratio of maleic acid hydrazide derivant and internal standard compound ditert-butylhydro quinone, the substitution typical curve is tried to achieve the maleic acid hydrazide content in the sample;
Wherein the GC/MS analysis condition is: chromatographic column: DB-WAX Fused-silica capillary column, column length 30m, internal diameter 0.25mm, thickness 0.25 μ m; 275 ℃ of injector temperatures; Carrier gas: He is the shunt mode sample introduction not, sample size: 1 μ L; Constant current mode, flow velocity 1.2mL/min; Temperature programme: 50 ℃ of lasting 2min, rise to 200 ℃ with the speed of 5 ℃ of per minutes, then the speed with 8 ℃ of per minutes rises to 260 ℃, continues 15min; Transmission line temperature: 280 ℃; Ionization pattern: EI, energy 70eV; 230 ℃ of ion source temperatures; Scan mode: select ion monitoring (SIM) pattern.
Relative retention time and qualitative discriminating ion according to agricultural chemicals carry out qualitative discriminating; The selection ion of maleic acid hydrazide derivant is 241,255, and the selection ion of ditert-butylhydro quinone is 207,222.
Chromatographic peak area with standard operation liquid and internal standard compound ditert-butylhydro quinone carries out regretional analysis to its respective concentration, obtains standard working curve such as table 1.
The typical curve of maleic acid hydrazide in table 1 cigarette mainstream flue gas
(5) detection limit
The maleic acid hydrazide standard operation solution of variable concentrations is injected GC/MS, calculate detection limit with 3 times of signal to noise ratio (S/N ratio)s (S/N=3), the detecting of two maleic acid hydrazides is limited to 0.14 μ g/ and props up (3 times of signal to noise ratio (S/N ratio)s are least concentration, and 6 cigarette are concentrated into 1ml).
Repeatability and recovery of standard addition
Then the standard solution that adds maleic acid hydrazide in not containing the cigarette mainstream flue gas sample of maleic acid hydrazide carries out respectively pre-treatment and GC/MS and analyzes, and calculate its recovery according to adding the scalar sum measured value, the results are shown in Table 2.。As can be seen from Table 2, on 3 mark-on levels, the average recovery rate of maleic acid hydrazide is 91%, and average relative standard deviation (RSD) is 5.4%, illustrates that the recovery of the inventive method is higher, good reproducibility.
The recovery of table 2 maleic acid hydrazide and repeatability (n=6)
(7) actual sample is measured
Prop up and carry out pre-treatment and GC/MS after the residual cigarette sample of maleic acid hydrazide aspirates and analyze containing 17.28 μ g/, record that maleic acid hydrazide is that 0.313 μ g/ props up in the main flume, calculating maleic acid hydrazide is 1.81% to the rate of transform of main flume.
Claims (10)
1. the assay method of maleic acid hydrazide content in the cigarette mainstream flue gas is characterized in that, may further comprise the steps:
(1) sample pre-treatments
Select the qualified cigarette of weight and resistance to suction, to wherein evenly adding maleic acid hydrazide agricultural chemicals standard specimen, aspirate cigarette after the balance respectively, collect total particulate matter in mainstream smoke with filter disc, add internal standard compound, the extraction agricultural chemicals will extract liquid nitrogen and blow concentrated after the vibration;
(2) derivatization
Purify concentrate with the C18 solid phase extraction column, behind the activation C18 solid phase extraction column, the concentrate of removing step (1) is transferred on the C18 pillar, and drip washing receives efflux, will flow out liquid nitrogen and blow concentrated afterwards derivatization;
(3) preparation of standard operation solution
The maleic acid hydrazide series concentration standard operation liquid of at least three concentration gradients of preparation is for subsequent use behind the derivatization in 0.1-10.0 μ g/mL scope;
(4) gas chromatography/mass spectrometry (GC/MS) is measured
Standard operation liquid and the internal standard compound of each concentration gradient in the step (3) are carried out GC/MS mensuration, compare its respective concentration with the chromatographic peak area of standard operation liquid and internal standard compound and carry out regretional analysis, obtain standard working curve; Under the same conditions the sample liquid after derivative in the step (2) is injected GC/MS and measure, record the chromatographic peak area ratio of maleic acid hydrazide derivant and internal standard compound in the sample, the substitution typical curve obtains the maleic acid hydrazide content in the sample.
2. the assay method of maleic acid hydrazide content in a kind of cigarette mainstream flue gas according to claim 1 is characterized in that, internal standard compound is ditert-butylhydro quinone.
3. the assay method of maleic acid hydrazide content in a kind of cigarette mainstream flue gas according to claim 1 is characterized in that, maleic acid hydrazide agricultural chemicals standard specimen addition is 10,20 and 50 μ L(MH concentration, 1430 μ g/mL in the step (1)).
4. the assay method of maleic acid hydrazide content in a kind of cigarette mainstream flue gas according to claim 1 is characterized in that, the condition of balance is temperature in the step (1): 22 ± 1 ℃, and humidity: 60 ± 3%, equilibration time: 48 hours.
5. the assay method of maleic acid hydrazide content in a kind of cigarette mainstream flue gas according to claim 1 is characterized in that, the filter disc that uses in the step (1) is cambridge filter.
6. the assay method of maleic acid hydrazide content in a kind of cigarette mainstream flue gas according to claim 1 is characterized in that, extract is methyl alcohol in the step (1).
7. the assay method of maleic acid hydrazide content in a kind of cigarette mainstream flue gas according to claim 1, it is characterized in that, the method of derivatization is in step (2) and (3): add 1mL dimethyl formamide (DMF) dissolving in the sample that nitrogen is blown over, then the silylating reagent (BSTFA) that adds 0.5mL, at 75 ℃ of lower derivative 30min, take out to put and carry out GC/MS to room temperature and analyze.
8. the assay method of maleic acid hydrazide content in a kind of cigarette mainstream flue gas according to claim 1 is characterized in that, nitrogen blows under 40 ℃ and carries out in step (1) and (2).
9. the assay method of maleic acid hydrazide content in a kind of cigarette mainstream flue gas according to claim 1, it is characterized in that, the collocation method of step (3) Plays working fluid is: accurately take by weighing 0.0100g MH standard items, dissolve also with DMF constant volume gets 100 μ g/mL MH standard reserving solutions in the 100mL volumetric flask; Pipette 0.01,0.02,0.05,0.1,0.5 and 1.0mL MH standard reserving solution, place respectively the 10mL volumetric flask, dilute constant volume with DMF, get the MH standard operation solution of 0.1,0.2,0.5,1.0,5.0 and 10.0 μ g/mL concentration.
10. the assay method of maleic acid hydrazide content in a kind of cigarette mainstream flue gas according to claim 1, it is characterized in that, the GC/MS analysis condition in the step (4) is: chromatographic column: DB-WAX Fused-silica capillary column, column length 30m, internal diameter 0.25mm, thickness 0.25 μ m; 275 ℃ of injector temperatures; Carrier gas: He is the shunt mode sample introduction not, sample size: 1 μ L; Constant current mode, flow velocity 1.2mL/min; Temperature programme: 50 ℃ of lasting 2min, rise to 200 ℃ with the speed of 5 ℃ of per minutes, then the speed with 8 ℃ of per minutes rises to 260 ℃, continues 15min; Transmission line temperature: 280 ℃; Ionization pattern: EI, energy 70eV; 230 ℃ of ion source temperatures; Scan mode: select ion monitoring (SIM) pattern.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105606740A (en) * | 2016-03-01 | 2016-05-25 | 浙江中烟工业有限责任公司 | Detection method for maleic hydrazide residual amount in tobacco and tobacco products |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101876649A (en) * | 2010-07-02 | 2010-11-03 | 中国烟草总公司郑州烟草研究院 | Method for measuring residual maleic hydrazide in tobacco or tobacco product |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101876649A (en) * | 2010-07-02 | 2010-11-03 | 中国烟草总公司郑州烟草研究院 | Method for measuring residual maleic hydrazide in tobacco or tobacco product |
Non-Patent Citations (6)
| Title |
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| 《ANALYTICAL CHEMISTRY》 19731130 Yu-Ying Liu et al. Quantitative Chromatographic Determination of Maleic Hydrazide in Cigarette Smoke 第45卷, 第13期 * |
| ALFRED F. HAEBERER ET AL.: "A Rapid Quantitative Method for Maleic Hydrazide", 《J. AGR. FOOD CHEM.》 * |
| DONNA T. KUBILIUS ET AL.: "Determination of Maleic Hydrazide in Potatoes and Onions by Capillary Electrophoresis", 《J. AGRIC. FOOD CHEM.》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105606740A (en) * | 2016-03-01 | 2016-05-25 | 浙江中烟工业有限责任公司 | Detection method for maleic hydrazide residual amount in tobacco and tobacco products |
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Application publication date: 20130424 |