CN102928544A - Method for analyzing ammonia in cigarette mainstream smoke through gas chromatography-mass spectrometry - Google Patents
Method for analyzing ammonia in cigarette mainstream smoke through gas chromatography-mass spectrometry Download PDFInfo
- Publication number
- CN102928544A CN102928544A CN2012104327583A CN201210432758A CN102928544A CN 102928544 A CN102928544 A CN 102928544A CN 2012104327583 A CN2012104327583 A CN 2012104327583A CN 201210432758 A CN201210432758 A CN 201210432758A CN 102928544 A CN102928544 A CN 102928544A
- Authority
- CN
- China
- Prior art keywords
- ammonia
- cigarette
- main stream
- stream smoke
- benzamide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention provides a method for analyzing ammonia in cigarette mainstream smoke through gas chromatography-mass spectrometry. The method is characterized in that a Cambridge filter and absorption liquid are used for gathering the cigarette mainstream smoke, a hydrochloric acid solution is used for extracting the Cambridge filter with particulate matters, equal extract liquid and the absorption liquid are taken accurately, sodium bicarbonate and benzoyl chloride are added, released ammonia and benzoyl chloride are reacted to generate benzamide, solid-phase extraction is performed on the reaction solution, the benzamide generated through derivatization reaction is detected by a gas chromatography-mass spectrometer (GC-MS), and the ammonia in the cigarette mainstream smoke is analyzed. Compared with a method for quantitative determination of the ammonia in the cigarette mainstream smoke, the method uses mass spectrometry as a detector so as to achieve tracer analysis of isotope labeling ammonia.
Description
?
Technical field
The invention belongs to flue gas analysis determination techniques field, be specifically related to a kind of method of gas chromatography-mass spectrometry analysis ammonia of main stream smoke of cigarette.
Background technology
Ammonia is a kind of colourless and have the gas of intense stimulus stink, and the upper respiratory tract of animal or human's body is had to stimulate and corrosive attack, weakens human body to the resistibility of disease.Ammonia is a kind of alkaline matter, and it has organized corrosion and spread effect to contact, and the moisture in can absorptive tissue makes the histone sex change, and makes the tissue fat saponification, destroys membrane structure, and long-term suction meeting causes serious harm to human body.
Cigarette is after burning, and flue gas gas phase and grain have the ammonia existence in mutually.Ammonia in the cigarette smoke derives from the nitrogen-containing compound in tobacco and other auxiliary material, comprises protein, amino acid, ammonium salt, acid amides, alkaloid and nitrogen-containing heterocycle compound.Adopt
15The N isotope carries out the research method that spike is the source of ammonia in a kind of important research cigarette smoke to containing nitrogen precursor in the tobacco.At present the method for the quantitative test of ammonia in flue gas comprises spectrophotometric method, ion-selective electrode method, capillary electrophoresis, vapor-phase chromatography and the chromatography of ions, wherein the normal method that adopts is tobacco business standard " the mensuration chromatography of ions of ammonia of main stream smoke of cigarette " at present, but these methods only quantitatively detect the ammonia in the flue gas, do not adopt mass spectrum as detecting device, can not change by the abundance of the resulting fragment ion peak of mass spectrogram to distinguish
15N and
14The ammonia of two kinds of isotope forms of N.Carry out ammonia formation mechanism study purpose, a kind of analytical approach take mass spectrometer as detecting device of need exploitation in order to realize tagging.And ammonia is little molecule volatile matter, needs just can carry out GC-MS and analyze after derivatization changes its chromatographic performance.Therefore, the present invention just is being based on this mechanism and is proposing.
?
Summary of the invention
Purpose of the present invention can not be distinguished for the method for existing cigarette smoke ammonia just
15N and
14The ammonia of two kinds of isotope forms of N, and a kind of gas chromatography-mass spectrum that provides detects the method for ammonia of main stream smoke of cigarette.The present invention adopts derivatization method, by the mensuration of gas chromatograph-mass spectrometer (GCMS) to the derivatization product, can be used for the formation mechanism of isotope tracer studies cigarette smoke ammonia.
The objective of the invention is to be achieved through the following technical solutions: adopt cambridge filter and absorption bottle to capture cigarette mainstream flue gas, the ammonia that adds in chlorobenzoyl chloride and absorption liquid and the extract carries out derivatization reaction generation benzamide, reaction solution separates wash-out by solid-phase extraction column, by gas chromatograph-mass spectrometer (GCMS) (GC-MS) chlorobenzoyl chloride in the eluent is measured so that the analysis of cigarette main flume in ammonia.
The objective of the invention is to realize by following scheme:
The assay method of ammonia of main stream smoke of cigarette of the present invention may further comprise the steps:
The capture of a, ammonia of main stream smoke of cigarette, derivative and purification: adopt orthoscopic smoking machine smoking cigarette, by cambridge filter and 0.01molL
-1Absorption by Hydrochloric Acid solution is to the NH in the cigarette smoke
3Capture, cambridge filter is placed 0.01molL
-1In the hcl as extraction agent solution and place and carry out mechanical oscillation on the oscillator; Pipette the absorption liquid of equivalent and extract in conical flask, add sodium bicarbonate and chlorobenzoyl chloride and derive, thereby the hydrochloric acid in sodium bicarbonate and the solution carries out neutralization reaction ammonia is discharged, the simultaneously reaction for chlorobenzoyl chloride and ammonia provides alkali condition; Successively activate with methyl alcohol and distilled water p-poly-phenyl ethene divinylbenzene solid-phase extraction column, the solution behind the derivative reaction joins on the extraction column, adopts distilled water to carry out drip washing, then N again
2Dry up solid-phase extraction column, adopt ethyl acetate to carry out wash-out, add anhydrous sodium sulfate drying in the eluent and can carry out the GC-MS analysis afterwards.
The analysis of b, derivatization product benzamide:
The GC-MS analysis condition:
Injector temperature: 255 ℃; Sample size: 1 μ L; Split ratio: 30:1; Carrier gas: He; Constant current mode, flow velocity 1mLmin
-1Chromatographic column: DB-5MS 30m * 0.25mm * 0.25 μ m; Temperature programme: 60 ℃ keep 3min, then with 6 ℃ of min
-1The speed that heats up rises to 230 ℃, again with 20 ℃ of min
-1Heating rate rise to 260 ℃, keep 8min;
The solvent delay time: 4min; Ionization mode: EI; Transmission line temperature: 280 ℃; Ion source temperature: 230 ℃; Level Four bar temperature: 150 ℃; Sweep limit: 30～300amu; Scan mode: full scan (SCAN).
In cigarette mainstream flue gas capture process, 4 cigarette of each duct suction; The mechanical oscillation time is 30min; The volume of absorption liquid and extract is 30mL.
Institute's consumption of sodium bicarbonate and chlorobenzoyl chloride is respectively 0.5g and 0.3mL in the derivatization step.
The volume that activates used methyl alcohol and distilled water is 6mL; The specification of SPE solid-phase extraction column is: grain diameter 100 μ m, filler gross mass 250mg, filler top volume 3mL.
The volume of distilled water that drip washing is used is 6mL, and the gas flow rate when nitrogen dries up is 30mL/min, and the volume of eluent ethyl acetate liquid is 2mL, and dry quality with anhydrous sodium sulfate is 0.5g.
The present invention's characteristics compared to existing technology are: adopt mass spectrum as detecting device, change the tracer analysis of realization isotope labeling ammonia by the abundance of benzamide fragment ion peak.
Description of drawings
For this reason invention empty of Fig. 1 cigarette and adding contain
15The overlapping chromatogram of the cigarette smoke derivatization product benzamide of N material;
Fig. 2 is the mass spectrogram of blank cigarette smoke derivatization product benzamide;
Fig. 3 contains for adding
15The mass spectrogram of the cigarette smoke derivatization product benzamide of N material.
Embodiment
The present invention is described further in connection with following instance:
Blank cigarette and adding after balance and the screening are contained
15The cigarette of N material is 0.01molL according to the suction of YC/T29-1996 specified standard condition with cambridge filter and 30mL concentration
-1Absorption by Hydrochloric Acid liquid is to the NH in 4 cigarette mainstream flue gas
3Capture, take off in the conical flask that Cambridge sheet is put in 100mL and add the 0.01molL of 30mL
-1Hcl as extraction agent solution, mechanical vibration 30min on oscillator.Pipette each 10mL of absorption liquid and extract and mix and be placed in the 100mL conical flask, add behind the chlorobenzoyl chloride of the sodium bicarbonate of 0.5g and 0.3mL at the oscillator 30min that vibrates.
Adopting specification is the polystyrene divinylbenzene solid-phase extraction column of 250mg, grain diameter 100 μ m, filler top volume 3mL, the methyl alcohol and the distilled water that are 6mL with volume respectively before the loading activate and wash, to join on the solid-phase extraction column through the solution after the derivative reaction, use again the distilled water drip washing of 6mL, afterwards N
2Flow velocity with 30mL/min dries up solid-phase extraction column, and the eluent ethyl acetate solid-phase extraction column of 2mL adds in the eluent with carrying out GC-MS behind the anhydrous sodium sulfate drying of 0.5g and analyzes.
The GC-MS analysis condition:
Injector temperature: 255 ℃; Sample size: 1 μ L; Split ratio: 30:1; Carrier gas: He; The constant current flow velocity, 1mLmin
-1Chromatographic column: DB-5MS 30m * 0.25mm * 0.25 μ m; Temperature programme: 60 ℃ keep 3min, then with 6 ℃ of min
-1The speed that heats up rises to 230 ℃, again with 20 ℃ of min
-1Heating rate rise to 260 ℃, keep 8min;
The solvent delay time: 4min; Ionization mode: EI; Transmission line temperature: 280 ℃; Ion source temperature: 230 ℃; Level Four bar temperature: 150 ℃; Sweep limit: 30～300amu; Scan mode: full scan (SCAN).
By the analysis to chromatogram, the retention time that obtains benzamide is 16.37min, by the integration of peak area being realized the quantitative test of benzamide.
Claims (6)
1. the method for a gas chromatography-mass spectrometry analysis ammonia of main stream smoke of cigarette, it is characterized in that: adopt cambridge filter and absorption bottle to capture cigarette mainstream flue gas, the ammonia that adds in chlorobenzoyl chloride and absorption liquid and the extract carries out derivatization reaction generation benzamide, reaction solution separates wash-out through solid-phase extraction column, by gas chromatograph-mass spectrometer (GCMS) (GC-MS) benzamide in the eluent is measured so that the analysis of cigarette main flume in ammonia.
2. the method for mensuration ammonia of main stream smoke of cigarette according to claim 1, it is characterized in that: the method may further comprise the steps
The capture of a, ammonia of main stream smoke of cigarette, derivative and purification: adopt orthoscopic smoking machine smoking cigarette, by cambridge filter and 0.01molL
-1Absorption by Hydrochloric Acid liquid captures the ammonia in the cigarette, and cambridge filter is placed 0.01molL
-1In the hcl as extraction agent solution and place and carry out mechanical oscillation on the oscillator; The absorption liquid and the extract that pipette equivalent place conical flask, and add sodium bicarbonate and chlorobenzoyl chloride derives; Successively activate and wash with methyl alcohol and distilled water p-poly-phenyl ethene divinylbenzene solid-phase extraction column, the solution after deriving joins on the extraction column, adopts distilled water to carry out drip washing, then N again
2Dry up solid-phase extraction column, adopt ethyl acetate to carry out wash-out, add anhydrous sodium sulfate drying in the eluent and can carry out the GC-MS analysis afterwards;
The analysis of b, derivatization product benzamide:
The GC-MS analysis condition:
Injector temperature: 255 ℃; Sample size: 1 μ L; Split ratio: 30:1; Carrier gas: He; Constant current mode, flow velocity 1mLmin
-1Chromatographic column: DB-5MS 30m * 0.25mm * 0.25 μ m; Temperature programme: 60 ℃ keep 3min, then with 6 ℃ of min
-1The speed that heats up rises to 230 ℃, again with 20 ℃ of min
-1Heating rate rise to 260 ℃, keep 8min; The solvent delay time: 4min; Ionization mode: EI; Transmission line temperature: 280 ℃; Ion source temperature: 230 ℃; Level Four bar temperature: 150 ℃; Sweep limit: 30～300amu; Scan mode: full scan (SCAN).
3. the method for mensuration ammonia of main stream smoke of cigarette according to claim 2 is characterized in that: in cigarette mainstream flue gas capture process, and 4 cigarette of each duct suction; The mechanical oscillation time is 30min; The volume of absorption liquid and extract is 30mL.
4. the method for mensuration ammonia of main stream smoke of cigarette according to claim 2, it is characterized in that: institute's consumption of sodium bicarbonate and chlorobenzoyl chloride is respectively 0.5g and 0.3mL in the derivatization step.
5. the method for mensuration ammonia of main stream smoke of cigarette according to claim 2, it is characterized in that: the volume that activates used methyl alcohol and distilled water is 6mL; The specification of SPE solid-phase extraction column is: grain diameter 100 μ m, filler gross mass 250mg, filler top volume 3mL.
6. the method for mensuration ammonia of main stream smoke of cigarette according to claim 2, it is characterized in that: the volume of distilled water that drip washing is used is 6mL, N
2Flow velocity is 30mL/min, and the volume of eluent ethyl acetate liquid is 2mL, and the quality of anhydrous sodium sulfate is 0.5g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210432758.3A CN102928544B (en) | 2012-11-03 | 2012-11-03 | Method for analyzing ammonia in cigarette mainstream smoke through gas chromatography-mass spectrometry |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210432758.3A CN102928544B (en) | 2012-11-03 | 2012-11-03 | Method for analyzing ammonia in cigarette mainstream smoke through gas chromatography-mass spectrometry |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102928544A true CN102928544A (en) | 2013-02-13 |
| CN102928544B CN102928544B (en) | 2014-04-09 |
Family
ID=47643393
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210432758.3A Active CN102928544B (en) | 2012-11-03 | 2012-11-03 | Method for analyzing ammonia in cigarette mainstream smoke through gas chromatography-mass spectrometry |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102928544B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103472159A (en) * | 2013-10-08 | 2013-12-25 | 江苏中烟工业有限责任公司 | Method for measuring ammonia content in cigarette smoke through ion chromatography |
| CN103616264A (en) * | 2013-12-06 | 2014-03-05 | 江苏中烟工业有限责任公司 | Device for capturing gas phase matters in main stream smoke of solvent in manual puff-by-puff manner |
| CN106959345A (en) * | 2017-03-27 | 2017-07-18 | 上海谱领生物科技有限公司 | A kind of full Isotopic Internal Standard mass spectrum quantitative approach of neurotransmitter metabolite |
| CN108191617A (en) * | 2018-01-18 | 2018-06-22 | 锦州医科大学 | The method of aromatic primary amine in liquid chromatogram coupling orbitrap high resolution mass spectrum analysis flue gases |
| CN108680697A (en) * | 2018-06-28 | 2018-10-19 | 南京信息工程大学 | Ammonium nitrogen isotope ratio values determination method in a kind of atmospheric aerosol based on chemical conversion |
| CN113655167A (en) * | 2020-05-12 | 2021-11-16 | 国家烟草质量监督检验中心 | Method for measuring ammonia content in main stream smoke of cigarette by automatic filter disc liquid coating device |
-
2012
- 2012-11-03 CN CN201210432758.3A patent/CN102928544B/en active Active
Non-Patent Citations (3)
| Title |
|---|
| 侯宏卫等: "固相萃取-气相色谱-质谱法测定卷烟主流烟气中4中芳香胺化合物", 《质谱学报》 * |
| 毛友安等: "气相色谱-质谱联用法测定卷烟主流烟气中烟草特有亚硝胺", 《理化检验-化学分册》 * |
| 石杰等: "气相色谱-质谱法测定卷烟烟气总粒相物中14中芳香胺", 《分析实验室》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103472159A (en) * | 2013-10-08 | 2013-12-25 | 江苏中烟工业有限责任公司 | Method for measuring ammonia content in cigarette smoke through ion chromatography |
| CN103472159B (en) * | 2013-10-08 | 2015-03-04 | 江苏中烟工业有限责任公司 | Method for measuring ammonia content in cigarette smoke through ion chromatography |
| CN103616264A (en) * | 2013-12-06 | 2014-03-05 | 江苏中烟工业有限责任公司 | Device for capturing gas phase matters in main stream smoke of solvent in manual puff-by-puff manner |
| CN103616264B (en) * | 2013-12-06 | 2016-05-25 | 江苏中烟工业有限责任公司 | A kind of device that manually traps gas gas-phase objects in main flume by mouth solvent |
| CN106959345A (en) * | 2017-03-27 | 2017-07-18 | 上海谱领生物科技有限公司 | A kind of full Isotopic Internal Standard mass spectrum quantitative approach of neurotransmitter metabolite |
| CN108191617A (en) * | 2018-01-18 | 2018-06-22 | 锦州医科大学 | The method of aromatic primary amine in liquid chromatogram coupling orbitrap high resolution mass spectrum analysis flue gases |
| CN108680697A (en) * | 2018-06-28 | 2018-10-19 | 南京信息工程大学 | Ammonium nitrogen isotope ratio values determination method in a kind of atmospheric aerosol based on chemical conversion |
| CN113655167A (en) * | 2020-05-12 | 2021-11-16 | 国家烟草质量监督检验中心 | Method for measuring ammonia content in main stream smoke of cigarette by automatic filter disc liquid coating device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102928544B (en) | 2014-04-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102928544B (en) | Method for analyzing ammonia in cigarette mainstream smoke through gas chromatography-mass spectrometry | |
| CN104634897B (en) | A kind of method detecting cigarette mainstream flue gas middle and advanced stage advanced glycation end products | |
| CN103163270B (en) | Method for detecting eight volatile carbonyl compounds in cigarette filter tip through liquid chromatography-tandem mass spectrometry | |
| CN102608232B (en) | Method for detecting 10 types of aromatic amines compounds in cigarette mainstream smoke by liquid chromatography-tandem mass spectrometry | |
| CN102621247B (en) | Method for synchronously analyzing base, nucleotide, organic acid, fatty acid, amino acid and saccharide metabolic product with two-step derivation method | |
| CN102279237B (en) | Method for detecting aromatic amine in cigarette mainstream smoke by using gas chromatography-tandem mass spectrometry | |
| CN103472149B (en) | Method for analyzing influence of mentholated cigarette processing process on production environment | |
| CN103257194B (en) | GC-MS/MS (Gas chromatography - tandem mass spectrometry) method for simultaneously analyzing three polycyclic aromatic hydrocarbons and four tobacco-specific nitrosamines in main stream smoke of cigarettes | |
| CN104267117A (en) | Determination method of volatile organic compounds in main stream cigarette smoke | |
| CN103293245B (en) | GC-MS (Gas Chromatography-Mass Spectrometer)/MS (Mass Spectrometer) method for simultaneously analyzing four tobacco-specific nitrosamines (TSNAs) in main stream smoke of cigarette | |
| CN102788852A (en) | Method for detecting seven aromatic amine compounds in human urine through liquid chromatography-series mass spectrometry | |
| Vitor et al. | Application of molecularly imprinted polymer solid-phase extraction for salivary cotinine | |
| CN104133031A (en) | Method and device for determination of cigarette smoke benzo[alpha]pyrene by on-line solid phase extraction | |
| CN102590386B (en) | Method for detecting nicotine and metabolites thereof in urine sample of smoker | |
| CN104698117A (en) | Simultaneous determination method for nicotine, 1,2-propylene glycol and glycerol in electronic cigarette smoke | |
| CN104267118A (en) | Method for determining carbonyl compound in mainstream smoke of cigarette | |
| CN105954442A (en) | Method for determining formaldehyde in electronic cigarette liquid | |
| Mei et al. | Development of an immunoaffinity chromatography column for selective extraction of a new agonist phenylethylamine A from feed, meat and liver samples | |
| Wang et al. | Mass spectrometric analysis of residual clenbuterol enantiomers in swine, beef and lamb meat by liquid chromatography tandem mass spectrometry | |
| CN111337603A (en) | Method for measuring nicotine content in tobacco product and method for simultaneously measuring water, 1, 2-propylene glycol, glycerol and nicotine content | |
| CN102608233B (en) | Method for detecting four main types of aromatic amines in cigarette filters by liquid chromatography-tandem mass spectrometry | |
| Yassine et al. | Development of a hydrophilic interaction liquid chromatography–mass spectrometry method for detection and quantification of urea thermal decomposition by-products in emission from diesel engine employing selective catalytic reduction technology | |
| Mottier et al. | Determination of hydrogen cyanide in cigarette mainstream smoke by LC/MS/MS | |
| CN103149297B (en) | High performance liquid chromatography-mass spectrum-mass spectrum (HPLC-MS-MS) combined detection method for (S)-NNAL and (R)-NNAL in urine | |
| Nair et al. | Determination of airborne methamphetamine via capillary microextraction of volatiles (CMV) with on-sorbent derivatisation using o-pentafluorobenzyl chloroformate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |