CN105675757B - It is a kind of at the same determine cigarette mainstream flue gas in the peculiar N nitrosamine of tobacco and polycyclic aromatic hydrocarbon method - Google Patents
It is a kind of at the same determine cigarette mainstream flue gas in the peculiar N nitrosamine of tobacco and polycyclic aromatic hydrocarbon method Download PDFInfo
- Publication number
- CN105675757B CN105675757B CN201610051476.7A CN201610051476A CN105675757B CN 105675757 B CN105675757 B CN 105675757B CN 201610051476 A CN201610051476 A CN 201610051476A CN 105675757 B CN105675757 B CN 105675757B
- Authority
- CN
- China
- Prior art keywords
- tobacco
- nitrosamine
- peculiar
- polycyclic aromatic
- aromatic hydrocarbon
- 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.)
- Active
Links
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
-
- 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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- 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
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/027—Liquid 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 cigarette smoke chemical analysis technical field, specifically disclose a kind of while determining the method for the peculiar N nitrosamine of tobacco and polycyclic aromatic hydrocarbon in cigarette mainstream flue gas.This method traps cigarette mainstream flue gas with smoking machine smoking cigarette with cambridge filter, extracts filter disc with the solution of containing the internal standard, the detection of line gel chromatography gas-chromatography tandem mass spectrum combined instrument is used directly in after extract solution filtering.Compared with standard method, this method determines two class compounds together, improves testing efficiency；Only need to filter flue gas extract solution and can detect, have the advantages that easy to operate, rapidly and efficiently；Detect there is that automaticity height, organic solvent consumption are few with online gel chromatography gas-chromatography tandem mass spectrum combined instrument.
Description
Technical field
The invention belongs to cigarette smoke chemical analysis technical field, and in particular to a kind of to determine simultaneously in cigarette mainstream flue gas
The method of the peculiar N- nitrosamine of tobacco and polycyclic aromatic hydrocarbon, is entered by online gel chromatography-gas chromatography tandem mass spectrometry combined instrument
Row detection.
Background technology
Polycyclic aromatic hydrocarbon is tobacco unburnt product under the conditions of high temperature, at present in cigarette mainstream flue gas
In identify about 30 condensed-nuclei aromatics for having carcinogenicity, Hoffmann in 1967 etc. demonstrates polycyclic aromatic hydrocarbon by toxicological experiment
Carcinogenicity, the medical report then delivered determines that benzo [a] pyrene is most important a kind of carcinogenic substance in polycyclic aromatic hydrocarbon.Tobacco is special
There is N- nitrosamine to be primarily referred to as N- nitrosonornicotines（NNN）, N- nitrosoanatabines（NAT）, N- nitroso anabasines
（NAB）And 4-（Nitrosomethylamino）- 1- β-pyridine radicals -1- butanone（NNK）, it is the carcinogenic substance of generally existing in cigarette smoke,
Early in 1962, just there is article to report in the world and contain N- nitrosamine and its potential carcinogenicity in tobacco.Therefore cigarette is detected
The burst size of the peculiar N- nitrosamine of tobacco and polycyclic aromatic hydrocarbon is significant to smoking and the research of health in main flume.
Smoke components produced by cigarette burning process are sufficiently complex, and the smoke components having been detected by present are alreadyd exceed
More than 5000 plant, and the peculiar N- nitrosamine of tobacco therein and polycyclic aromatic hydrocarbon content are generally in ng/ branch ranks.Therefore, to main flow
The peculiar N- nitrosamine of tobacco and polycyclic aromatic hydrocarbon in flue gas usually require certain sample pretreatment process when being detected.But
It is that lengthy and tedious time-consuming sample pretreatment process does not occupy most times of whole detection process, is also testing result
The main source of error.Importantly, sample pretreatment process and follow-up Instrumental Analysis process are typically offline coupling, survey
Examination is inefficient.
Early stage, we successively develop benzo in the main flume based on online gel chromatography-gas chromatography tandem mass spectrometry
Pyrene（CN 104569253 A）With the peculiar N- nitrosamine of tobacco in electronic cigarette liquid（201510564296.4）Assay method.But
Instrumental conditions and parameter under two methods（Mobile phase, gel chromatography acquisition time and mass spectrometry parameters etc.）It is very big Deng existing
Difference.Therefore, it is necessary to develop a kind of while determining the peculiar N- nitrosamine of tobacco and polycyclic aromatic hydrocarbon method in cigarette mainstream flue gas.
The content of the invention
The purpose of the present invention is exactly improved for prior art situation, and cigarette main flow is determined while specially design
The method of the peculiar N- nitrosamine of tobacco and polycyclic aromatic hydrocarbon in flue gas.Compared with the conventional method, the present invention does not need sample pre-treatments
Process, have the advantages that automaticity it is high, simple to operate, rapidly and efficiently, organic solvent consumption it is few and test flux it is high.
The purpose of the present invention is achieved through the following technical solutions：
It is a kind of at the same determine cigarette mainstream flue gas in the peculiar N- nitrosamine of tobacco and polycyclic aromatic hydrocarbon method, specifically include with
Lower step：
1）The preparation of standard serial solution：Using volume ratio as 1:1 ethyl acetate and acetone is solvent, three kinds of polycyclic aromatic hydrocarbons
（BaP, BaA and Chry）Grown tobacco peculiar N- nitrosamine with four（NAB, NAT, NNN and NNK）Standard items be solute, BaP-
D12, NAB-d4, NAT-d4, NNN-d4 and NNK-d4 are internal standard, prepare the standard serial solution of the containing the internal standard of various concentrations；
2）The preparation of sample solution：Cigarette is according to GB/T 19609-2004, and condition as defined in the ︰ 2000 of ISO 4387 is with directly
Line style smoking machine every time suction 5 after, by trap have mainstream smoke total particulate matter filter disc be placed in container, add extract solution and
Mixing inner mark solution is extracted, and internal standard concentration is identical with internal standard concentration in standard serial solution, then with 0.22 μm of organic filter membrane
Filtering produces sample solution.Wherein extract solution can be ethyl acetate, dichloromethane, hexamethylene, cyclohexane/ethyl acetate（v/v
=5/5）, preferably ethyl acetate；Extraction pattern is ultrasound or vibration, and extraction time is 10-60 min, preferably 20 min；Carry
The volume for taking liquid is 10-50 mL, preferably 20 mL；
3）Standard serial solution and sample solution carry out online gel chromatography-gas-chromatography-series connection matter under the same conditions
Analysis of spectrum, whole analysis system is made up of gel permeation chromatograph and gas-chromatography-tandem mass spectrometer two parts.Wherein, gel
The condition of permeation chromatograph is：Chromatographic column is Shodex CLNpak EV-200,16 μm, the mm of 2 mm * 150 or Silica
5SIL 4D, 5 μm, mm the or Silica 5SIL 4E of 4.6 * 150,5 μm, 4.6 * 250 mm, preferably Shodex
CLNpak EV-200,16 μm, the mm of 2 mm * 150；Mobile phase is cyclohexane/ethyl acetate（The volume basis of ethyl acetate
Number is 10-50%）Or cyclohexane/acetone（The percentage by volume of acetone is 10-50%）, preferably cyclohexane/ethyl acetate, v/v=
5/5；Flow velocity is 0.1 mL/min；Column temperature is 40 °C；Sample size is 10 mL；It is 3.0-7.0 to collect gel chromatography retention time
Min component, and its all on-line is imported into the analysis of gas chromatography tandem mass spectrometry instrument；The condition of gas chromatography tandem mass spectrometry instrument
For：Inertia pre-column is the mm of 5 m * 0.53 void column；Pre-column is the mm of 0.25 mm * of DB-35 ms, 5 m * 0.25；Point
It is the mm of 0.25 mm * of DB-35 ms, 25 m * 0.25 from post；Chromatographic column heating schedule is：82 °C of initial temperature, keeps 5
Min, then rise to 300 °C with 8 °C/min and keep 7.75 min, run time is 40 min；Using Splitless injecting samples mode,
Sample injection time is 7.0 min；Using high-purity He as carrier gas, nebulizer gas pressure program is：By 120 kPa, with 100 kPa/min liters
Recover to 220 kPa and 6.0 min of holding, then with 49.8 kPa/min to reset pressure, and keep 31 min；Temperature programming is entered
Sample mouthful, injection port heating schedule is：120 °C of 5 min of holding, then rise to 280 °C with 100 °C/min and keep 33.4 min；Blow
Sweeping flow program is：Initial flow is 5.0 mL/min, is down to 0 with 10 mL/min speed and keeps 7.0 min, then with same
The speed of sample rises to initial flow, and keeps 32.0 min；Interface temperature and ion source temperature are respectively 300 and 200 °C；Mass spectrum
Ionization source is EI sources；Ionization voltage is 70 ev；The solvent delay time is 18 min, reacts prison target analytes and interior target more
Survey parameter as shown in table 1；
4）The peculiar N- nitrosamine of tobacco and polycyclic aromatic hydrocarbon are quantified：Grown tobacco peculiar N- nitrosamine by benzo [a] pyrene and four
Peak area and the ratio between internal standard peak area quantified, specific method is：With the peculiar N- nitrosamine of tobacco in standard serial solution
It is ordinate with the ratio between the peak area and internal standard peak area of polycyclic aromatic hydrocarbon, the concentration of standard serial solution is abscissa, draws work
Make curve；According to the peculiar N- nitrosamine of tobacco in sample solution and the ratio between polycyclic aromatic hydrocarbon peak area and internal standard peak area, according to work
Make curve, obtain the content of the peculiar N- nitrosamine of tobacco in sample and polycyclic aromatic hydrocarbon.
In the present invention, the concentration gradient of NNN, NAT, NAB and BaP in standard serial solution be 0.5,1.0,2.0,
5.0th, 10.0,20 and 50.0 ng/mL, NNK concentration gradient are 0.545,1.09,2.18,5.45,10.9,21.8 and 54.5
Ng/mL, BaA concentration gradient are 1.095,2.19,4.38,10.95,21.9,43.8 and 109.5 ng/mL, Chry concentration
Gradient is 1.33,2.66,5.32,13.3,26.6,53.2 and 133 ng/mL, and NAT-d4, NAB-d4 in standard serial solution
The internal standard concentration for being 10 ng/mL, NNN-d4 and BaP-d12 with NNK-d4 internal standard concentration is respectively 12 and 10.6 ng/mL.
The test limit of the inventive method and quantitatively it is limited to the peculiar N- nitrosamine of tobacco and polycyclic aromatic hydrocarbon signal to noise ratio（S/N）For 3
Corresponding concentration during with 10.
In the present invention, we are carried out to the instrument parameter and condition, sample solution preparation process that influence testing result
Investigate and optimize.In order to which by the peculiar N- nitrosamine of tobacco and polycyclic aromatic hydrocarbon, all on-line turns from gel permeation chromatography simultaneously
Move to gas chromatography tandem mass spectrometry instrument to be analyzed, we successively optimize gel permeation chromatographic column, mobile phase and corresponding receipts
The collection time.As a result Shodex CLNpak EV-200 are shown（16 μm, the mm of 2 mm * 150）It is hexamethylene/acetic acid in mobile phase
Ethyl ester（v/v=5/5）With preferable separating effect, corresponding acquisition time is 3.0-7.0 min.Due to be transferred to gas-chromatography-
The sample solution volume of tandem mass spectrometer increases to 400 mL by 200 mL, thus we also to sample introduction pressure, injector temperature and
Purge flow rate is optimized, and the nebulizer gas pressure program finally chosen is：By 120 kPa, risen to 100 kPa/min
220 kPa simultaneously keep 6.0 min, then recover to reset pressure with 49.8 kPa/min, and keep 31 min；Injection port heating journey
Sequence is：120 °C of 5 min of holding, then rise to 280 °C with 100 °C/min and keep 33.4 min；Purge flow rate program is：Just
Beginning flow is 5.0 mL/min, is down to 0 with 10 mL/min speed and keeps 7.0 min, then rises at the same rate initial
Flow, and keep 32.0 min.In order to which the peculiar N- nitrosamine of tobacco and polycyclic aromatic hydrocarbon are extracted from granule phase substance simultaneously, we
The factor of influence extraction effect is investigated（Extract solution type and volume, extraction time and extraction pattern etc.）.As a result show, with
20 mL ethyl acetate are the extraction effect of extraction solution, the min of mechanical shaking extraction 20 N- nitrosamine peculiar to tobacco and polycyclic aromatic hydrocarbon
Preferably.Meanwhile, in order to obtain higher sensitivity, we have carried out excellent to target analytes and interior target multiple-reaction monitoring parameter
Change, including quota ion pair and collision energy etc., the target analytes of final choice and interior target multiple-reaction monitoring parameter such as table 1
It is shown.
The present invention is handled cigarette mainstream flue gas extract using gel chromatography, is made using the size exclusion of stationary phase
Separated with by the peculiar N- nitrosamine of tobacco and polycyclic aromatic hydrocarbon with macromolecular chaff interference, then the peculiar N- nitrosamine of tobacco will be contained and polycyclic
The component of aromatic hydrocarbons imports gas chromatography tandem mass spectrometry instrument and carries out separation analysis online, finally using internal mark method determination cigarette main flow
The content of the peculiar N- nitrosamine of tobacco and polycyclic aromatic hydrocarbon in flue gas.The method of the present invention overcomes pre-treatment in existing determination techniques
It is lengthy and tedious it is time-consuming, the deficiencies such as automatic continuous analysis, organic reagent consumption be more can not be realized, for cigarette mainstream flue gas extract
The property of feature and target analytes, improves method of testing.The inventive method analyzes a sample during Instrument measuring
The organic reagent volume that extract solution is consumed is less than 10 mL, and the time used is 50 min or so, and can realize continuous automatic
Analysis.Therefore, the inventive method have simple to operate, automaticity it is high, rapidly and efficiently, organic reagent consumption it is few and test
The high advantage of flux, can be greatly improved testing efficiency, reduction testing cost.
Brief description of the drawings
Fig. 1 is the peculiar N- nitrosamine of tobacco of the present invention and the chromatogram of polycyclic aromatic hydrocarbon.
Embodiment
The present invention is described further with reference to example, but is not intended to limit the present invention.
Embodiment 1：
The assay method of the peculiar N- nitrosamine of tobacco and polycyclic aromatic hydrocarbon, the specific steps of operation in a kind of cigarette mainstream flue gas
For：
The first step, the preparation of standard serial solution：Using volume ratio as 1:1 ethyl acetate and acetone is solvent, four kinds of cigarettes
The peculiar N- nitrosamine of grass（NAB, NAT, NNN and NNK）With three kinds of polycyclic aromatic hydrocarbons（BaP, BaA and Chry）Standard items be solute,
NAB-d4, NAT-d4, NNN-d4, NNK-d4 and BaP-d12 are internal standard, and the standard series for preparing the containing the internal standard of various concentrations is molten
Liquid；
Second step, the preparation of sample solution：By the cigarette after balance and screening with linear pattern smoking machine according to GB/T
Standard conditions as defined in the ︰ 2000 of 19609-2004, ISO 4387 are aspirated, every time 5 cigarette of experiment suction.Trapping there is into mainstream smoke
The filter disc of gas TPM is placed in 50 mL containers, is added 20 mL ethyl acetate and 200 μ L mixing inner mark solutions, is shaken
20 min of extraction are swung, then with 0.22 μm of organic membrane filtration sample solution is produced to extract solution；
3rd step, standard serial solution and sample solution carry out online gel chromatography-gas-chromatography-string under the same conditions
Join mass spectral analysis：Whole analysis system is made up of gel permeation chromatograph and gas-chromatography-tandem mass spectrometer two parts；Wherein,
The condition of gel permeation chromatograph is：Chromatographic column is Shodex CLNpak EV-200 (16 μm, the mm of 2 mm * 150)；Stream
Dynamic is mutually cyclohexane/ethyl acetate（5/5, v/v）；Flow velocity is 0.1 mL/min；Column temperature is 40 °C；Sample size is 10 mL；Receive
Integrate component of the gel chromatography retention time as 3.0-7.0 min（0.4 mL altogether）, and by its all on-line import gas-chromatography-
Tandem mass spectrometer is analyzed；The condition of gas chromatography tandem mass spectrometry instrument is：Inertia pre-column is the mm of 5 m * 0.53 void column；In advance
Post is the mm of 0.25 mm * of DB-35 ms, 5 m * 0.25；Splitter is the mm * 0.25 of DB-35 ms, 25 m * 0.25
mm；Chromatographic column heating schedule is：82 °C of initial temperature, keeps 5 min, then rise to 300 °C and holding 7.75 with 8 °C/min
Min, run time is 40 min；Using Splitless injecting samples mode, sample injection time is 7.0 min；Using high-purity He as carrier gas, carrier gas
Pressure program is：By 120 kPa, rise to 220 kPa with 100 kPa/min and keep 6.0 min, then with 49.8 kPa/
Min recovers to reset pressure, and keeps 31 min；Programmed temperature sampling mouthful, injection port heating schedule is：120 °C keep 5
Min, then rise to 280 °C with 100 °C/min and keep 33.4 min；Purge flow rate program is：Initial flow is 5.0 mL/
Min, is down to 0 with 10 mL/min speed and keeps 7.0 min, then rises to initial flow at the same rate, and keeps 32.0
min；Interface temperature and ion source temperature are respectively 300 and 200 °C；Mass spectrum ionization source is EI sources；Ionization voltage is 70 ev；It is molten
Agent time delay is 18 min, and target analytes and interior target multiple-reaction monitoring parameter are as shown in table 1.Under this condition, obtain
Object chromatogram it is as shown in Figure 1.
4th step, the peculiar N- nitrosamine of tobacco and polycyclic aromatic hydrocarbon are quantified：It is sub- with the peculiar N- of tobacco in standard serial solution
The ratio between peak area and internal standard peak area of nitramine and polycyclic aromatic hydrocarbon are ordinate, and the concentration of standard serial solution is abscissa, is painted
Working curve processed, is shown in Table 2, wherein the test limit of the inventive method and is quantitatively limited to the peculiar N- nitrosamine of tobacco and polycyclic aromatic hydrocarbon letter
Make an uproar ratio（S/N）For 3 and 10 when corresponding concentration；According to the peculiar N- nitrosamine of tobacco in sample solution and polycyclic aromatic hydrocarbon peak area
The ratio between with internal standard peak area, according to working curve, obtain the content of the peculiar N- nitrosamine of tobacco in sample and polycyclic aromatic hydrocarbon.
Target analytes and interior target multiple-reaction monitoring parameter in the inventive method of table 1.
The range of linearity, working curve, quantitative limit and test limit of the inventive method of table 2.
In order to investigate the reappearance of this method, the sample of basic, normal, high three kinds of concentration is prepared, with 4 samples prepared in one day
Product are measured, and calculate the in a few days relative standard deviation under various concentrations；It is measured, is calculated with the sample prepared for three days on end
Relative standard deviation in the daytime under various concentrations.As a result as shown in table 3, target analytes are in various concentrations（Basic, normal, high concentration
Corresponding value is respectively the 2 of each object range of linearity minimum, 10 and 40 times）Under in a few days and day to day precision is respectively smaller than
11.4% and 13.3%, illustrate that this method has preferable reappearance.
The precision of the inventive method of table 3.
In different type cigarette（Mixed type A and fire-cured tobacco type B）Main flume extract solution in add target analytes standard
Solution, basic, normal, high concentration is respectively the 2 of each object range of linearity minimum, 10 and 40 times, is entered afterwards with the inventive method
Row analysis, the standard working curve that the ratio between peak area of gained is substituted into target analytes calculates measured concentration, and with reality
Border addition is compared and obtains relative recovery.As shown in table 4, under various concentrations target analytes relative recovery between
Between 77.1-108.6%, show that the accuracy of method is good, the peculiar N- nitrous of tobacco in daily cigarette mainstream flue gas can be met
Amine and the requirement of polycyclic aromatic hydrocarbon analysis.
The rate of recovery of the peculiar N- nitrosamine of tobacco and polycyclic aromatic hydrocarbon in the different type cigarette of table 4.
Using the above method and standard method to the peculiar N- nitrosamine of main flume tobacco in different trade mark cigarette and many
PAH burst size is determined.As a result it is as shown in table 5：Significance difference is not present in the inventive method and standard method testing result
It is different.
The testing result of the peculiar N- nitrosamine of tobacco and polycyclic aromatic hydrocarbon in the different trade mark cigarette of table 5.（In ng/ branch, bracket
For standard method measurement result）
| Numbering | NNN | NAT | NAB | NNK | BaA | Chry | BaP |
| 1 | 56.2 (62.7) | 63.6 (70.2) | 11.0 (12.6) | 46.2 (57.6) | 30.4 (26.1) | 30.3 (28.6) | 8.8 (8.4) |
| 2 | 5.0 (5.1) | 12.0 (15.0) | 1.8 (1.9) | 4.5 (4.1) | 28.2 (27.1) | 30.8 (28.9) | 8.0 (8.1) |
| 3 | 3.9 (3.6) | 10.9 (9.3) | 1.2 (1.1) | 2.8 (2.9) | 29.4 (31.1) | 32.7 (34.2) | 8.1 (8.9) |
| 4 | 44.6 (51.3) | 47.0 (51.8) | 9.5 (11.1) | 9.7 (12.5) | 21.2 (23.5) | 21.2 (25.4) | 6.5 (7.1) |
| 5 | 5.4 (4.7) | 14.1 (13.5) | 1.9 (1.8) | 5.3 (5.1) | 29.3 (26.8) | 29.0 (28.9) | 8.4 (7.5) |
| 6 | 5.6 (5.5) | 12.7 (15.1) | 2.1 (2.1) | 6.6 (6.0) | 25.1 (24.1) | 24.4 (27.0) | 7.5 (7.3) |
Claims (7)
1. it is a kind of while determining the method for the peculiar N- nitrosamine of tobacco and polycyclic aromatic hydrocarbon in cigarette mainstream flue gas, it is characterised in that：
Including step in detail below：
1）The preparation of standard serial solution：Using volume ratio as 1:1 ethyl acetate and acetone is solvent, with three kinds of polycyclic aromatic hydrocarbons：
BaP, BaA, Chry and four grow tobacco peculiar N- nitrosamine：NAB, NAT, NNN, NNK standard items be solute, BaP-d12,
NAB-d4, NAT-d4, NNN-d4 and NNK-d4 are internal standard, prepare the standard serial solution of the containing the internal standard of various concentrations；
2）The preparation of sample solution：Cigarette is according to GB/T 19609-2004, condition linear pattern as defined in the ︰ 2000 of ISO 4387
After suction 5, the filter disc that trapping has mainstream smoke total particulate matter is placed in container every time for smoking machine, adds extract solution and mixing
Inner mark solution is extracted, and internal standard concentration is identical with internal standard concentration in standard serial solution, then with 0.22 μm of organic membrane filtration
Produce sample solution；
3）Standard serial solution and sample solution carry out online gel chromatography-gas chromatography tandem mass spectrometry point under the same conditions
Analysis, whole analysis system is made up of gel permeation chromatograph and gas-chromatography-tandem mass spectrometer two parts；Wherein, gel infiltration
Chromatographic condition is：Chromatographic column is Shodex CLNpak EV-200,16 μm, the mm of 2 mm * 150；Mobile phase is hexamethylene
Alkane/ethyl acetate, v/v=5/5, flow velocity is 0.1 mL/min；Column temperature is 40 °C；Sample size is 10 mL；Gel chromatography is collected to protect
The component that the time is 3.0-7.0 min is stayed, and the component all on-line is imported into gas chromatography tandem mass spectrometry instrument and is analyzed；Gas phase
The condition of chromatogram-tandem mass spectrometer is：Inertia pre-column is the mm of 5 m * 0.53 void column；Pre-column is DB-35 ms, 5 m *
0.25 mm * 0.25μm；Splitter is 0.25 μm of 0.25 mm * of DB-35 ms, 25 m *；Chromatographic column heating schedule is：Just
82 °C of beginning temperature, keeps 5 min, then rises to 300 °C with 8 °C/min and keep 7.75 min, and run time is 40 min；Adopt
Splitless injecting samples mode is used, sample injection time is 7.0 min；Using high-purity He as carrier gas, nebulizer gas pressure program is：Opened by 120 kPa
Begin, rise to 220 kPa with 100 kPa/min and keep 6.0 min, then recovered with 49.8 kPa/min to reset pressure, and protect
Hold 31 min；Programmed temperature sampling mouthful, injection port heating schedule is：120 °C of 5 min of holding, then risen to 100 °C/min
280 °C and 33.4 min of holding；Purge flow rate program is：Initial flow is 5.0 mL/min, is down to 10 mL/min speed
0 and 7.0 min of holding, then initial flow is risen at the same rate, and keep 32.0 min；Interface temperature and ion source temperature
Respectively 300 and 200 °C；Mass spectrum ionization source is EI sources；Ionization voltage is 70 ev；The solvent delay time is 18 min, target point
Analyse thing and interior target multiple-reaction monitoring parameter is as shown in the table；
4）The peculiar N- nitrosamine of tobacco and polycyclic aromatic hydrocarbon are quantified：By the peculiar N- nitrosamine of tobacco and polycyclic aromatic hydrocarbon peak area and
The ratio between internal standard peak area is quantified.
2. the side as claimed in claim 1 for determining the peculiar N- nitrosamine of tobacco and polycyclic aromatic hydrocarbon in cigarette mainstream flue gas simultaneously
Method, it is characterised in that：Wherein extract solution is any one in ethyl acetate, dichloromethane, hexamethylene, cyclohexane/ethyl acetate
Kind；Extraction pattern is ultrasound or vibration, and extraction time is 10-60 min, and the volume of extract solution is 10-50 mL.
3. the side as claimed in claim 1 for determining the peculiar N- nitrosamine of tobacco and polycyclic aromatic hydrocarbon in cigarette mainstream flue gas simultaneously
Method, it is characterised in that：The concentration gradient of NNN, NAT, NAB and BaP in the standard serial solution are 0.5,1.0,2.0,
5.0th, the concentration gradient of the NNK in 10.0,20 and 50.0 ng/mL, the standard serial solution be 0.545,1.09,2.18,
5.45th, the concentration gradient of the BaA in 10.9,21.8 and 54.5 ng/mL, the standard serial solution be 1.095,2.19,
4.38th, the concentration gradient of the Chry in 10.95,21.9,43.8 and 109.5 ng/mL, the standard serial solution be 1.33,
2.66th, 5.32,13.3,26.6,53.2 and 133 ng/mL, and NAT-d4, NAB-d4 and NNK-d4 internal standard in standard serial solution
The internal standard concentration that concentration is 10 ng/mL, NNN-d4 and BaP-d12 is respectively 12 and 10.6 ng/mL.
4. the side as claimed in claim 1 for determining the peculiar N- nitrosamine of tobacco and polycyclic aromatic hydrocarbon in cigarette mainstream flue gas simultaneously
Method, it is characterised in that：Step 4）Specific method be：With the peculiar N- nitrosamine of tobacco in standard serial solution and polycyclic aromatic hydrocarbon
The ratio between peak area and internal standard peak area are ordinate, and the concentration of standard serial solution is abscissa, drawing curve；According to sample
The peculiar N- nitrosamine of tobacco and the ratio between polycyclic aromatic hydrocarbon peak area and internal standard peak area in product solution, according to working curve, obtain sample
The content of the peculiar N- nitrosamine of tobacco and polycyclic aromatic hydrocarbon in product.
5. the side as claimed in claim 2 for determining the peculiar N- nitrosamine of tobacco and polycyclic aromatic hydrocarbon in cigarette mainstream flue gas simultaneously
Method, it is characterised in that：The ratio of cyclohexane/ethyl acetate used is v/v=5/5 in extract solution.
6. the side as claimed in claim 2 for determining the peculiar N- nitrosamine of tobacco and polycyclic aromatic hydrocarbon in cigarette mainstream flue gas simultaneously
Method, it is characterised in that：The extraction time is preferably 20 min；The volume of extract solution is preferably 20 mL.
7. the side as claimed in claim 2 for determining the peculiar N- nitrosamine of tobacco and polycyclic aromatic hydrocarbon in cigarette mainstream flue gas simultaneously
Method, it is characterised in that：Extract solution is preferably ethyl acetate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610051476.7A CN105675757B (en) | 2016-01-26 | 2016-01-26 | It is a kind of at the same determine cigarette mainstream flue gas in the peculiar N nitrosamine of tobacco and polycyclic aromatic hydrocarbon method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610051476.7A CN105675757B (en) | 2016-01-26 | 2016-01-26 | It is a kind of at the same determine cigarette mainstream flue gas in the peculiar N nitrosamine of tobacco and polycyclic aromatic hydrocarbon method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105675757A CN105675757A (en) | 2016-06-15 |
| CN105675757B true CN105675757B (en) | 2017-10-31 |
Family
ID=56303178
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610051476.7A Active CN105675757B (en) | 2016-01-26 | 2016-01-26 | It is a kind of at the same determine cigarette mainstream flue gas in the peculiar N nitrosamine of tobacco and polycyclic aromatic hydrocarbon method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105675757B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106248835B (en) * | 2016-09-28 | 2019-05-31 | 云南省烟草质量监督检测站 | The method for detecting 22 kinds of multiring aromatic hydrocarbon substance contents in cigarette smoke simultaneously |
| CN108627600B (en) * | 2017-03-20 | 2021-03-12 | 上海烟草集团有限责任公司 | Method for analyzing aroma components in smoke |
| CN108387654A (en) * | 2018-02-09 | 2018-08-10 | 深圳瀚星翔科技有限公司 | The detection method of NNN and NNK in a kind of atomization vapour of electronic cigarette release |
| CN108956802B (en) * | 2018-05-24 | 2021-06-18 | 中国烟草总公司郑州烟草研究院 | Processing method of tobacco and tobacco products and detection method of various components in tobacco and tobacco products |
| WO2020217543A1 (en) * | 2019-04-24 | 2020-10-29 | 和一 早川 | Method for identifying generation sources of fine particulates in atmosphere |
| CN110274977B (en) * | 2019-08-06 | 2021-09-28 | 南通市产品质量监督检验所 | Method for detecting N-nitrosamine compounds in meat products |
| CN110261517B (en) * | 2019-08-06 | 2021-10-29 | 南通市产品质量监督检验所 | Method for determining N-nitrosamine compounds in meat products by using GPC-GC/MS/MS |
| CN112730663A (en) * | 2020-12-22 | 2021-04-30 | 华测检测认证集团湖北有限责任公司 | Method for rapidly and accurately measuring volatile nitrosamine in food |
| CN116660425B (en) * | 2023-07-18 | 2023-12-05 | 山东杰诺检测服务有限公司 | Method for rapidly determining various pesticide residues in fruits and vegetables and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104569253B (en) * | 2014-12-16 | 2016-03-23 | 国家烟草质量监督检验中心 | The assay method of benzo [a] pyrene in a kind of cigarette mainstream flue gas |
| CN105158392B (en) * | 2015-09-08 | 2016-09-07 | 国家烟草质量监督检验中心 | The assay method of tobacco peculiar N-nitrosamine in a kind of tobacco juice for electronic smoke |
-
2016
- 2016-01-26 CN CN201610051476.7A patent/CN105675757B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105675757A (en) | 2016-06-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105675757B (en) | It is a kind of at the same determine cigarette mainstream flue gas in the peculiar N nitrosamine of tobacco and polycyclic aromatic hydrocarbon method | |
| CN105527356B (en) | The peculiar N nitrosamine of tobacco and assay method while polycyclic aromatic hydrocarbon in a kind of cigarette mainstream flue gas based on suction nozzle micro-extraction | |
| CN103323543B (en) | Method for detecting 17 polycyclic aromatic hydrocarbons in cigarette gas | |
| CN101140268B (en) | Analysis method for semi-volatility component in cigarette main stream flue gas | |
| 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 | |
| CN105158392B (en) | The assay method of tobacco peculiar N-nitrosamine in a kind of tobacco juice for electronic smoke | |
| 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 | |
| CN102608244A (en) | Detection method for simultaneously determining several kinds of fragrant substances in cigarette tobacco shreds | |
| CN104133031A (en) | Method and device for determination of cigarette smoke benzo[alpha]pyrene by on-line solid phase extraction | |
| CN104535695B (en) | A kind of gas chromatography tandem mass spectrometry detects the method for phenol in cigarette mainstream flue gas, NNK and benzo [a] pyrene simultaneously | |
| CN104267118A (en) | Method for determining carbonyl compound in mainstream smoke of cigarette | |
| CN104237431A (en) | Method for measuring TSNAs (tobacco-specific nitrosamines) in electronic cigarette smoke | |
| CN104076108A (en) | Method for measuring low-molecular-weight aldehyde ketone in electronic cigarette smoke | |
| CN106324122A (en) | Determination method of volatile N-nitrosamine in tobacco, tobacco products and smoke | |
| CN104142374A (en) | Method for measuring content of carbonyl compound in electronic tobacco juice by adopting direct derivation/high performance liquid chromatography | |
| CN104049050B (en) | A kind of assay method based on benzo [a] pyrene in the cigarette mainstream flue gas of Magnetic solid phases extraction | |
| CN104535694A (en) | Method for detecting four tobacco-specific nitrosamines (TSNAs) in lateral exhaust gas of cigarettes by virtue of gas chromatography-tandem mass spectrometry | |
| CN107271584A (en) | The capture method of carbonyls and tobacco-specific nitrosamine, extracting method and assay method in a kind of cigarette mainstream flue gas | |
| CN103954707A (en) | Method for analyzing speciation of arsenic elements in smoke of cigarettes | |
| CN106248835A (en) | The method of 22 kinds of multiring aromatic hydrocarbon substance content in detection cigarette smoke simultaneously | |
| CN103257195B (en) | GC-MS/MS (Gas chromatography-tandem mass spectrometry) method for simultaneously analyzing benzo [a] BaA, chrysene and benzo [a] BaP in main stream smoke of cigarettes | |
| CN106442753A (en) | Method for measuring content of TSNAs (tobacco-specific nitrosamines) in mainstream smoke of cigarettes | |
| CN108931596A (en) | Method that is a kind of while detecting acetic acid and nicotine in cigarette mainstream flue gas | |
| CN104569253B (en) | The assay method of benzo [a] pyrene in a kind of cigarette mainstream flue gas | |
| CN106841474A (en) | The extraction of the peculiar N nitrosamine of tobacco and assay method in a kind of tobacco or tobacco product based on hydrophobic nonionic exchange SPE |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |