CN103808824A - Method for detecting urotropin in cigarette mainstream smoke through gas chromatography-tandem mass spectrum - Google Patents
Method for detecting urotropin in cigarette mainstream smoke through gas chromatography-tandem mass spectrum Download PDFInfo
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- CN103808824A CN103808824A CN201410068904.8A CN201410068904A CN103808824A CN 103808824 A CN103808824 A CN 103808824A CN 201410068904 A CN201410068904 A CN 201410068904A CN 103808824 A CN103808824 A CN 103808824A
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Abstract
The invention discloses a method for detecting urotropin in cigarette mainstream smoke through gas chromatography-tandem mass spectrum. The method comprises the steps of gathering mainstream smoke total particulate matter of 20 cigarettes according to the rule of ISO4387:2000, then putting a cambridge filter with the mainstream smoke total particulate matter into a 250mL bread bottle, adding 40 mL of ethanol extract liquor containing triethylamine to oscillate for extracting the cambridge filter for 40 minutes, accurately taking out 20mL of the extract liquor to pass through an activated silica gel columella, washing the columella by using 30ml of dichloromethane firstly, dropping leacheate, then washing the columella by using 40mL of methyl alcohol, collecting the leacheate to concentrate to 1mL, accurately adding 50 microliters of 10mg/L internal standard solution to detect by using GC-MS/MS (Gas Chromatography-Mass Spectrometry/ Mass Spectrometry). According to the method, the GC-MS/MS is used for detecting the urotropin in the cigarette side stream smoke; a multi-reaction monitoring mode is adopted for determining the nature; the method is capable of effectively improving the qualitative accuracy and sensitivity of the method, suitable for the detection of urotropin in various types of cigarette side stream smoke, wide in application and capable of accurately detecting; meanwhile, the method is simple, environment-friendly, and good in practicability.
Description
Technical field
The invention belongs to cigarette smoke technical field, be specifically related to the method for urotropine in a kind of gas chromatography-tandem mass spectrum (GC-MS/MS) detection cigarette mainstream flue gas.
Background technology
Urotropine is a kind of harmful chemical component, and tool corrosivity can cause human body and burn, 263 ℃ of its fusing points, as exceed this fusing point and distil and decompose, but not melting.While being warming up to 300 ℃, emit hydrogen cyanide, when temperature raises, be decomposed into methane, hydrogen and nitrogen again.In the time that human body contacts these product, mainly cause dermatitis and eczema.Urotropine all has distribution in cigarette main flow and side-stream smoke, and the urotropine in flue gas is the secondary metabolite of flue gas, is to be generated by the ammonia in flue gas and formaldehyde reaction, and wherein the content in side-stream smoke will be higher than the content in main flume.Along with the growing interest of the public to smoking and health problem, harmful constituents in cigarette flue gas is paid close attention to day by day widely, and at present about the relevant report of urotropine detection in flue gas is fewer, Given this, the present invention has designed the method for urotropine in a kind of GC-MS/MS of application detection cigarette mainstream flue gas.
Summary of the invention
Goal of the invention: for the deficiencies in the prior art, the object of the present invention is to provide a kind of gas chromatography-tandem mass spectrum to detect the method for urotropine in cigarette mainstream flue gas, energy is the sensitive mensuration that is applicable to urotropine in all kinds of cigarette side-stream smokes accurately.
Technical scheme: for achieving the above object, the present invention by the following technical solutions:
A kind of gas chromatography-tandem mass spectrum detects the method for urotropine in cigarette mainstream flue gas: according to the mainstream smoke total particulate matter of 20 cigarette of regulation trapping of ISO4387:2000, there is the cambridge filter of mainstream smoke total particulate matter to put into 250mL bread bottle trapping, the alcohol extraction liquid oscillation extraction cambridge filter 40min that adds 40mL to contain triethylamine, accurately pipette 20mL extract and cross the silica gel pillar having activated, first use 30mL eluent methylene chloride pillar, discard after leacheate, use again 40mL methyl alcohol drip washing pillar, collect leacheate, be concentrated into after 1mL, accurately add 50 μ L 10mg/L inner mark solutions, application GC-MS/MS detects, instrument condition: chromatographic column: HP-5 MS, injector temperature: 220 ℃, temperature programme: rise to 112 ℃ at 80 ℃ with 12 ℃/min speed, then rise to 118 ℃ with 1 ℃/min speed, 280 ℃ of maintenance 6 min of rear operation, carrier gas: helium, 1.0mL/min, sample size 1uL, split sampling, split ratio 10:1, transmission line temperature: 250 ℃, mass spectrum condition is: ion source temperature: 230 ℃, quadrupole rod temperature: 150 ℃, ionization mode: EI-MRM, ion energy: 70ev, lamp current: 35mA, the solvent delay time: 3min, collision airshed: nitrogen 1mL/min, suppress airshed: helium 2.25mL/min, selection and impact energy qualitative, quota ion see the following form:
The volume of described alcohol extraction liquid is more than 40mL.
More than described extraction time 30 min.
The required extract loading volume of described solid phase extraction column is more than 10mL.
Described internal standard compound is methyl phenylacetate, and concentration is 0.5 μ g/mL.
Described inner mark solution volume is less than 0.5mL.
Described methyl alcohol elution volume is greater than 20mL.
Described eluent methylene chloride volume is greater than 20mL.
Beneficial effect: compared with prior art, GC-MS/MS of the present invention measures the method for urotropine in cigarette side-stream smoke, undertaken qualitative by adopting multiple-reaction monitoring pattern (MRM), can effectively improve the sensitivity of qualitative accuracy and method, be applicable to the mensuration of urotropine in all kinds of cigarette side-stream smokes, not only be widely used, measure precisely, and method is simple, environmental friendliness, has good practicality.
Embodiment
Below in conjunction with specific embodiment, the present invention is described further.
In following examples, the key instrument and the reagent that use are as follows:
Gas phase-triple quadrupole bar tandem mass spectrum combined instrument: be furnished with 7000B type triple quadrupole bar tandem mass spectrometer and 7890A type gas chromatograph (Agilent company of U.S. product); RM20H rotating disc type smoking machine (German Borgwaldt KC company); AL204 electronic balance (sensibility reciprocal: 0.0001 g, Mettler Toledo company of Switzerland); HY-5A cyclotron oscillation device (Xun Sheng instrument plant of Jintan City of Jiangsu Province); E300 climatic chamber (Australian Steridium company); Solid-phase extraction device (SUPELCO company of the U.S.).
Ethanol (AR, Chemical Reagent Co., Ltd., Sinopharm Group); Urotropine (purity >=99%, Chemical Reagent Co., Ltd., Sinopharm Group); Triethylamine (HPLC, TEDIA company of the U.S.); Methylene chloride (AR, Chemical Reagent Co., Ltd., Sinopharm Group); Methyl alcohol (AR, Chemical Reagent Co., Ltd., Sinopharm Group); Solid-phase extraction column SUPELCO(LC-Si, 3mL).
Embodiment 1
Gas chromatography-tandem mass spectrum detects a method for urotropine in cigarette mainstream flue gas, specific as follows:
According to the mainstream smoke total particulate matter of 20 cigarette of regulation trapping of ISO4387:2000, there is the cambridge filter of mainstream smoke total particulate matter to put into 250mL bread bottle trapping, the alcohol extraction liquid oscillation extraction cambridge filter 40min that adds 40mL to contain triethylamine, accurately pipette 20mL extract and cross the silica gel pillar having activated, first use 30mL eluent methylene chloride pillar, discard after leacheate, use again 40mL methyl alcohol drip washing pillar, collect leacheate, be concentrated into after 1mL, accurately add 50 μ L 10mg/L inner mark solutions, application GC-MS/MS detects.
Instrument condition: chromatographic column: mm × 0.25, HP-5 MS(30m × 0.25 μ rn); Injector temperature: 220 ℃; Temperature programme: rise to 112 ℃ at 80 ℃ with 12 ℃/min speed, then rise to 118 ℃ with 1 ℃/min speed; 280 ℃ of maintenance 6 min of rear operation; Carrier gas: helium, 1.0mL/min; Sample size 1uL, split sampling, split ratio 10:1; Transmission line temperature: 250 ℃.
Mass spectrum condition is: ion source temperature: 230 ℃; Quadrupole rod temperature: 150 ℃; Ionization mode: EI-MRM; Ion energy: 70ev; Lamp current: 35mA.The solvent delay time: 3min; Collision airshed: nitrogen 1mL/min; Suppress airshed: helium 2.25mL/min.Selection and impact energy qualitative, quota ion see the following form:
The preparation of extraction solution: accurately add 4mL triethylamine in 1 L ethanolic solution.
The preparation of standard reserving solution: with the accurately urotropine standard reserving solution of preparation 2 mg/L of ethanol.
The preparation of inner mark solution: the methyl phenylacetate inner mark solution of accurately preparing respectively 100 μ g/L, 1mg/L with ethanol.
The 2mg/L urotropine standard reserving solution that accurately pipettes respectively 250 μ L, 500 μ L, 1mL, 2mL, 3mL, 4mL mixes and obtains 6 grade standard solution to marking in storing solution dilution in 5mL 100 μ g/L, with this series standard solution making internal standard method calibration curve.6 grades of calibration solution have been set up internal standard method calibration curve after analyzing.Within the scope of 0.05～0.8 μ g, linear equation is Y=0.1022X-0.0038, linearly dependent coefficient
r 2 be 0.9996.
Detect after analysis by above-mentioned GC-MS/MS, in this cigarette mainstream flue gas, the burst size of urotropine is 19.91 ng/cig.
Embodiment 2
According to the method for embodiment 1, by standard solution least concentration continuous sample introduction 10 times, measure its standard deviation, take 3 times of standard deviations as detection limit, take 10 times of standard deviations as quantitative limit, result is as table 1, and detecting of urotropine is limited to 0.46 ng/cig, lower limit of quantitation is 1.54 ng/cig.Virginian-type cigarette flue gas urotropine content, generally in 30 ng/cig left and right, is measured so this method can meet the analysis of cigarette sample.
The interpretation of result that the minimum standard specimen sample introduction of table 1 is 10 times
Embodiment 3
According to the method for embodiment 1, choose Virginian-type cigarette sample, measure every day 4 times simultaneously, measure altogether 3 days, calculate the in a few days repeatability and in the daytime reappearance of assay method, result is respectively 4.33,3.72 and 3.98 as the relative standard deviation (%) in table 2 day, and relative standard deviation (%) is in the daytime 4.35, so the method precision is better.
The precision analysis result (unit: ng/cig) of table 2 method
Embodiment 4
According to the method for embodiment 1, in the cambridge filter that contains certain cigarette mainstream flue gas granule phase substance, add the urotropine standard solution of variable concentrations, calculate the recovery of standard addition of assay method, the results are shown in table 3, in this cigarette mainstream flue gas, the burst size of urotropine is 19.91 ng/cig, recovery of standard addition (%) is 93.43～97.35, and the recovery of standard addition of method is good as can be seen here.
Table 3 recovery of standard addition result (unit: ng/cig)
The above embodiment of the present invention is only for example of the present invention is clearly described, not the restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here cannot give exhaustive to all embodiments.Everyly belong to apparent variation or the still row in protection scope of the present invention of variation that technical scheme of the present invention extends out.
Claims (1)
1. the method for urotropine in gas chromatography-tandem mass spectrum detection cigarette mainstream flue gas, it is characterized in that: according to the mainstream smoke total particulate matter of 20 cigarette of regulation trapping of ISO4387:2000, there is the cambridge filter of mainstream smoke total particulate matter to put into 250mL bread bottle trapping, the alcohol extraction liquid oscillation extraction cambridge filter 40min that adds 40mL to contain triethylamine, accurately pipette 20mL extract and cross the silica gel pillar having activated, first use 30mL eluent methylene chloride pillar, discard after leacheate, use again 40mL methyl alcohol drip washing pillar, collect leacheate, be concentrated into after 1mL, accurately add 50 μ L 10mg/L inner mark solutions, application GC-MS/MS detects, wherein, instrument condition: chromatographic column: HP-5 MS, injector temperature: 220 ℃, temperature programme: rise to 112 ℃ at 80 ℃ with 12 ℃/min speed, then rise to 118 ℃ with 1 ℃/min speed, 280 ℃ of maintenance 6 min of rear operation, carrier gas: helium, 1.0mL/min, sample size 1uL, split sampling, split ratio 10:1, transmission line temperature: 250 ℃, mass spectrum condition is: ion source temperature: 230 ℃, quadrupole rod temperature: 150 ℃, ionization mode: EI-MRM, ion energy: 70ev, lamp current: 35mA, the solvent delay time: 3min, collision airshed: nitrogen 1mL/min, suppress airshed: helium 2.25mL/min, selection and impact energy qualitative, quota ion see the following form:
.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114034790A (en) * | 2021-10-29 | 2022-02-11 | 中国烟草总公司郑州烟草研究院 | Method for determining sensory related amide compounds in tobacco and tobacco products |
| CN115097021A (en) * | 2022-05-27 | 2022-09-23 | 国家烟草质量监督检验中心 | Method for researching chemical component difference of cigarette smoke based on gas chromatography-quadrupole electrostatic field orbit trap high-resolution mass spectrometry |
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| CN103063759A (en) * | 2012-12-06 | 2013-04-24 | 国家烟草质量监督检验中心 | Method for determining maleic hydrazide content in cigarette sidestream smoke |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114034790A (en) * | 2021-10-29 | 2022-02-11 | 中国烟草总公司郑州烟草研究院 | Method for determining sensory related amide compounds in tobacco and tobacco products |
| CN114034790B (en) * | 2021-10-29 | 2024-03-08 | 中国烟草总公司郑州烟草研究院 | Method for determining sensory related amide compounds in tobacco and tobacco products |
| CN115097021A (en) * | 2022-05-27 | 2022-09-23 | 国家烟草质量监督检验中心 | Method for researching chemical component difference of cigarette smoke based on gas chromatography-quadrupole electrostatic field orbit trap high-resolution mass spectrometry |
| CN115097021B (en) * | 2022-05-27 | 2024-05-17 | 国家烟草质量监督检验中心 | Method for researching chemical composition difference of cigarette smoke based on gas chromatography-quadrupole electrostatic field orbit trap high-resolution mass spectrum |
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