CN101393184B - Analytical method of heterocyclic amine compound in cigarette mainstream flue gas - Google Patents
Analytical method of heterocyclic amine compound in cigarette mainstream flue gas Download PDFInfo
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- CN101393184B CN101393184B CN2008102306586A CN200810230658A CN101393184B CN 101393184 B CN101393184 B CN 101393184B CN 2008102306586 A CN2008102306586 A CN 2008102306586A CN 200810230658 A CN200810230658 A CN 200810230658A CN 101393184 B CN101393184 B CN 101393184B
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Abstract
The invention relates to a method for analyzing heterocyclic amine compounds in mainstream cigarette smoke. The method is characterized in that the analytic method utilizes a cambridge filter to trap the heterocyclic amine compounds in the mainstream cigarette smoke; the heterocyclic amine compounds are extracted by a HCL/ methanol solution, are purified through an MCX ion exchange column, condensed and detected by liquid chromatography-tandem mass spectrometry (HPLC-MS/MS); and the contents of the main heterocyclic amine compounds in the mainstream cigarette smoke are mensurated. Compared with the prior method for analyzing the heterocyclic amine compounds in the mainstream cigarette smoke, the analytic mensuration method does not need a complicated sample treatment step, does not need to derive a sample, has high sensitivity, good repeatability and reclaiming rate, and is suitable for analyzing the samples with large batches.
Description
Technical field
The invention belongs to the new method of heterocyclic amine compound pre-treatment and analysis in a kind of cigarette mainstream flue gas.This method utilizes cambridge filter to capture main heterocyclic amine compound in the main flume granule phase substance, utilizes the MCX solid-phase extraction column to purify pre-treatment, adopts liquid chromatography-tandem mass spectrometry analysis then.
Background technology
Smoking is paid close attention to by the whole world health affected, and the burst size that reduces objectionable constituent in the cigarette smoke is a tobacco business worker obligation one can't decline.HOFFMANN has announced 69 kinds of objectionable constituent inventories in calendar year 2001, and wherein heterocyclic amine compound is 8 kinds.These compounds are that organic compound pyrolysis such as protein, amino acid produce, and extensively exist in environment and daily bread, and they have strong mutagenesis activity, and some also are proved to be the tumour that can cause the multiple tissue of animal used as test.In order to separate the content situation of this compounds in cigarette main flume and the environment flue gas, and set up corresponding harm reduction method, must set up a kind of sensitivity, quick, easy analytical approach.
Although several different methods has been set up in the assay determination of heterocyclic amine, because this kind compound content is extremely low, and cigarette smoke is very complicated, disturbs morely, and the analysis and research of heterocyclic amine are remained an extremely challenging job.Employing liquid-liquid extraction methods such as Moldoveanu have extracted the heterocyclic amine in the cigarette mainstream flue gas, the back employing gas chromatography-mass spectrum-chemical source negative ion mode of deriving detects (Sasaki, T.A., Wilkins, J.M., Forehand, J.B., Moldoveanu, S.C., Anal.Lett.2001,34:1749.); Kataoka etc. are with combine heterocyclic amine in the treatment of cigarette master stream flue gas of blue cotton absorption and liquid-liquid extraction, and gas chromatography-nitrogen phosphorous detector detection is adopted in the back of deriving.(Kataoka, H., Kijima, K.Maruo, G., Bull.Environ.Contam.Toxic.1998,60:60.) all there are shortcomings such as complex pretreatment, detection sensitivity in said method, therefore improve existing pre-treating method and set up a kind of to all hydridization aminated compoundss all be suitable for and comparatively simply, selectivity is good, detection sensitivity is high analytical approach, significant.
Summary of the invention
The analytical approach that the purpose of this invention is to provide heterocyclic amine compound in a kind of easy and simple to handle, selectivity good, detection sensitivity is high cigarette mainstream flue gas.
The objective of the invention is to be achieved through the following technical solutions: promptly utilize the heterocyclic amine compound in the cambridge filter capture cigarette mainstream flue gas, after the extraction of HCl/ methanol solution, purify with the MCX ion exchange column, concentrate the back and adopt liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) to detect.
Concrete steps of the present invention are as follows:
(1) capture of heterocyclic amine compound in the cigarette mainstream flue gas, extraction and purification: capture the cigarette mainstream flue gas granule phase substance by cambridge filter, then cambridge filter is placed conical flask, add inner mark solution, after HC l/ methanol solution (volume ratio 2: the 1) ultrasonic extraction with 0.1mo l/L, get MCX solid-phase extraction column on the part solution, use HCl respectively, methyl alcohol, methanol/ammoniacal liquor (volume ratio 25: 5: 75) solution washs pillar, remove impurity, adopt the mixed solution of methyl alcohol/ammoniacal liquor (volume ratio 95: 5) to carry out wash-out then, concentrate the back and adopt HPLC-MS/MS to detect;
(2) analysis of flue gas sample:
HPLC-MS/MS analysis condition: adopt C4 (YMC pack, 250mm * 4.6mm i.d., 5 μ m) liquid-phase chromatographic column to separate column temperature: 30 ℃; Moving phase is acetic acid/ammonium acetate buffer solution (being respectively A and B) of acetonitrile and pH 3.2, flow velocity 1000L μ L/min, and condition of gradient elution is as follows: 0min, 100%B; 10min, 90%B; 20min, 50%B; 30min, 50%B; 40min, 100%B;
The mass spectrum condition: electron spray positive ion mode, detection mode are multiple-reaction monitoring (MRM) pattern, gas curtain gas 20psi, atomization gas 55psi, the auxiliary gas 50psi of heating, 600 ℃ of auxiliary heating temperature degree, ionization voltage 4000V.
In mark be chosen as (2-amino-3,4,7,8-tetramethyl-imidazo[4,5-f] quinoxalin, TriMeIQx, 2-amino-3,4,7,8-tetramethyl-imidazoles [4,5-f]] quinoxaline) or D3-IQ (deuterium is for 2-amino-3-methyl-imidazoles [4,5-f]] quinoline)
In the flue gas trapping process, cigarette smoking adopts the rotating disc type smoking machine according to the suction of YC/T 29-1996 specified standard condition, 20 cigarette of each experiment suction.
Utilize method of the present invention that the standard article of following 8 kinds of heterocyclic amine compounds are measured, the retention time of its relevant data such as compound, parent ion, daughter ion and optimize after go bunch voltage CE and collision energy DP value as shown in the table:
Annotate: Glu-p-2:2-aminodipyrido[1,2-a:3 ', 2 '-d] imidazole (2-amino-pyridine [1,2-a:3 ', 2 '-d] imidazoles); IQ:2-amino-3-methylimidazo[4,5-f] quinoline (2-amino-3-methyl-imidazoles [4,5-f]] quinoline); Glu-p-1,2-amino-6-methyldipyrido[1,2-a:3 ', 2 '-d] imidazole (2-amino-6-methyl two pyridines [1,2-a:3 ', 2 '-d]] imidazoles); PHIP:2-amino-1-methyl-6-phenylimidazo[4,5-b] and pyridine (2-amino-1-methyl-6-phenylimidazole [4,5-b]] pyridine), Trp-p-2:3-amino-1-methyl-5H-pyrido[4,3-b] indole (3-amino-1-methyl-5H-pyridine [4,3-b] indoles); Trp-p-1:3-amino-1,4-dimethyl-5H-pyrido[4,3-b] indole (3-amino-1,4-dimethyl-5H-pyridine [4,3-b] indoles), A α C:2-amino-9H-pyrido[2,3-b] indole (2-amino-9H-pyridine [2,3-b] indoles); MeA α C:2-amino-3-methyl-9H-pyrido[2,3-b] indole (2-amino-3-methyl-9H-pyridine [2,3-b] indoles), in be designated as (2-amino-3,4,7,8-tetramethyl-imidazo[4,5-f] quinoxalin, TriMeIQx, 2-amino-3,4,7,8-tetramethyl-imidazoles [4,5-f]] quinoxaline).
This method is compared with the analytical approach of original main flume heterocyclic amine material, does not need the complicated sample treatment step, and sample does not need to derive, and method is highly sensitive, and the repeatability and the recovery are fine, are applicable to the analysis of batch samples.
Description of drawings
Accompanying drawing is a test flow chart of the present invention.
Embodiment
Below by embodiment the present invention is further specified:
Embodiment 1
Cigarette after balance and the screening according to the suction of YC/T 29-1996 specified standard condition, is captured the gas granule phase substance of 20 cigarette main flues with cambridge filter.
Put into conical flask with the cambridge filter that captures granule phase substance is folding, pipette 0.1mol/L HCl/ methyl alcohol (volume ratio 2: the 1) extract that 60mL contains mark (TriMeIQx) in the 60ng, ultrasonic extraction 30min leaves standstill 5min under the room temperature.Get sample MCX solid-phase extraction column on the 45mL extract (10ml methyl alcohol and 10ml water activate in advance), use 10ml 0.1mol/L HCl, 15ml methyl alcohol, 15ml methanol/ammonia spirit (volume ratio 25: 5: 75) washing then respectively, with the mixed solution wash-out of 30ml methyl alcohol/ammoniacal liquor (volume ratio 95: 5), carry out HPLC-MS/MS after eluent concentrates and analyze.
HPLC-MS/MS analysis condition: adopt C4 (YMC pack, 250mm * 4.6mm i.d., 5 μ m) liquid-phase chromatographic column to separate column temperature: 30 ℃; Moving phase is acetonitrile and acetic acid/ammonium acetate buffer solution (being respectively A and B), flow velocity 1000 μ L/min, and condition of gradient elution is as follows: 0min, 100%B; 10min, 90%B; 20min, 50%B; 30min, 50%B; 40min, 100%B.
The mass spectrum condition: electron spray positive ion mode, detection mode are multiple-reaction monitoring (MRM) pattern, gas curtain gas 20psi; Atomization gas 55psi; The auxiliary gas 50psi of heating.600 ℃ of auxiliary heating temperature degree; Ionization voltage 4000V.
Cigarette sample to 2 trades mark is measured, and the result is as shown in the table:
Annotate: nd-does not detect.
Embodiment 2
The Kentucky is aspirated according to YC/T 29-1996 specified standard condition with reference to cigarette 3R4F, and cambridge filter is collected the granule phase substance of 20 cigarette.Filter disc is placed conical flask, on filter disc, add a certain amount of Glu-p-2 with the micro-sampling pin, Glu-p-1, IQ and PHIP mixed solution carry out the sample purification Treatment Analysis according to the described step of embodiment 1 then.Carry out 5 parallel laboratory tests, the result shows that the relative standard deviation of each compound determination illustrates that the reappearance of this method and stability are fine between 1.62-6.76%.
Claims (2)
1. the analytical approach of heterocyclic amine compound in the cigarette mainstream flue gas, it is characterized in that: this analytical approach is the 2-amino-pyridine [1 that utilizes in the cambridge filter capture cigarette mainstream flue gas, 2-a:3 ', 2 '-d] imidazoles, 2-amino-3-methyl-imidazoles [4,5-f] quinoline, 2-amino-6-methyl two pyridines [1,2-a:3 ', 2 '-d] imidazoles, 2-amino-1-methyl-6-phenylimidazole [4,5-b] pyridine, 3-amino-1-methyl-5H-pyridine [4,3-b] indoles, 3-amino-1,4-dimethyl-5H-pyridine [4,3-b] indoles, 2-amino-9H-pyridine [2,3-b] indoles, 2-amino-3-methyl-9H-pyridine [2,3-b] eight kinds of heterocyclic amine compounds of indoles, after the extraction of HCl/ methanol solution, purify with the MCX ion exchange column, concentrate the back and adopt liquid chromatography-tandem mass spectrometry HPLC-MS/MS to detect, measure the content of heterocyclic amine compound main in the cigarette mainstream flue gas; Concrete steps are as follows:
(1) capture of heterocyclic amine compound in the cigarette mainstream flue gas, extraction and purification: capture the cigarette mainstream flue gas granule phase substance by cambridge filter, then cambridge filter is placed conical flask, add 2-amino-3,4,7,8-tetramethyl-imidazoles [4,5-f] quinoxaline or deuterium be for 2-amino-3-methyl-imidazoles [4,5-f] the quinoline inner mark solution, use 60ml, after the HCl/ methanol solution ultrasonic extraction of 2: 1 0.1mol/L of volume ratio, get MCX solid-phase extraction column on the part solution, use 10ml 0.1mol/L HCl respectively, 15ml methyl alcohol, methanol/ammonia spirit of 25: 5: 75 of 15ml volume ratio washs pillar, remove impurity, adopt the mixed solution of methyl alcohol/ammoniacal liquor of 95: 5 of 30ml volume ratio to carry out wash-out then, concentrate the back and adopt HPLC-MS/MS to detect;
(2) analysis of flue gas sample:
The HPLC-MS/MS analysis condition: adopt YMC-pack, 250mm * 4.6mm i.d., the C4 liquid-phase chromatographic column of 5 μ m separates column temperature: 30 ℃; Mobile phase A is an acetonitrile, and Mobile phase B is acetic acid/ammonium acetate buffer solution of pH 3.2, flow velocity 1000 μ L/min, and condition of gradient elution is as follows: 0min, 100%B; 10min, 90%B; 20min, 50%B; 30min, 50%B; 40min, 100%B;
The mass spectrum condition: electron spray positive ion mode, detection mode are the multiple-reaction monitoring pattern, gas curtain gas 20psi, atomization gas 55psi, the auxiliary gas 50psi of heating, 600 ℃ of auxiliary heating temperature degree, ionization voltage 4000V.
2. the analytical approach of heterocyclic amine compound in the cigarette mainstream flue gas according to claim 1, it is characterized in that: in the flue gas trapping process, cigarette smoking adopts the rotating disc type smoking machine according to the suction of YC/T 29-1996 specified standard condition, 20 cigarette of each experiment suction.
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| CN101936840A (en) * | 2009-06-30 | 2011-01-05 | 上海谱尼测试技术有限公司 | Heterocyclic amine analysis method in urban catering exhaust emission |
| CN101980011B (en) * | 2010-05-25 | 2012-10-10 | 江西中烟工业有限责任公司 | Method for measuring main active ingredient propyl gallate of Chinese medicinal material additive in cigarettes |
| FR2961711B1 (en) * | 2010-06-23 | 2012-08-17 | Millipore Corp | POCKET FOR CIRCUIT OF A BIOLOGICAL LIQUID TREATMENT FACILITY |
| CN102608232B (en) * | 2012-03-17 | 2013-09-04 | 中国烟草总公司郑州烟草研究院 | Method for detecting 10 types of aromatic amines compounds in cigarette mainstream smoke by liquid chromatography-tandem mass spectrometry |
| CN102608233B (en) * | 2012-03-17 | 2013-04-17 | 中国烟草总公司郑州烟草研究院 | Method for detecting four main types of aromatic amines in cigarette filters by liquid chromatography-tandem mass spectrometry |
| CN102759588B (en) * | 2012-07-16 | 2014-05-07 | 上海烟草集团有限责任公司 | Method for separating and preparing key acid flavor components in cigarette mainstream smoke and application of key acid volatile components |
| CN102879250A (en) * | 2012-11-01 | 2013-01-16 | 云南烟草科学研究院 | Smoke extract and method for determining HRMS information content in smoke extract |
| CN103149316B (en) * | 2013-03-04 | 2014-08-13 | 常州市疾病预防控制中心 | Method for simultaneously detecting acrylamide and heterocyclic amine in food |
| CN105911201A (en) * | 2016-07-06 | 2016-08-31 | 云南中烟工业有限责任公司 | Method for determining amine and carbohydrate compounds in main smoke of cigarette by virtue of supercritical fluid chromatography-gas chromatography-mass spectrum |
| CN109596559A (en) * | 2018-11-08 | 2019-04-09 | 苏州宝化炭黑有限公司 | The associated detecting method and detection system of carbon black tail gas each component content |
| CN109580864B (en) * | 2019-02-18 | 2019-09-06 | 华南农业大学 | The remaining detection method of Nosiheptide in a kind of animal food |
| CN114047267B (en) * | 2021-11-15 | 2023-11-21 | 贵州省烟草科学研究院 | Method for analyzing nicotinic acid in tobacco root system by derivatization-gas chromatography-mass spectrometry |
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