CN109975446A - The measuring method of Alkaloid and nitrosamine in a kind of cigarette mainstream flue gas - Google Patents
The measuring method of Alkaloid and nitrosamine in a kind of cigarette mainstream flue gas Download PDFInfo
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- 235000019504 cigarettes Nutrition 0.000 title claims abstract description 37
- 229930013930 alkaloid Natural products 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 31
- 150000003797 alkaloid derivatives Chemical class 0.000 title claims abstract description 20
- XKLJHFLUAHKGGU-UHFFFAOYSA-N nitrous amide Chemical compound ON=N XKLJHFLUAHKGGU-UHFFFAOYSA-N 0.000 title claims abstract description 19
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000003546 flue gas Substances 0.000 title claims abstract description 18
- 241000208125 Nicotiana Species 0.000 claims abstract description 21
- 235000002637 Nicotiana tabacum Nutrition 0.000 claims abstract description 20
- 238000004896 high resolution mass spectrometry Methods 0.000 claims abstract description 12
- 239000006228 supernatant Substances 0.000 claims abstract description 10
- 230000000155 isotopic effect Effects 0.000 claims abstract description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 4
- 239000008187 granular material Substances 0.000 claims abstract description 4
- 238000004445 quantitative analysis Methods 0.000 claims abstract description 4
- 230000000391 smoking effect Effects 0.000 claims abstract description 4
- 150000002500 ions Chemical class 0.000 claims description 20
- 238000000605 extraction Methods 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000012071 phase Substances 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 10
- 239000007921 spray Substances 0.000 claims description 5
- 238000002414 normal-phase solid-phase extraction Methods 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005695 Ammonium acetate Substances 0.000 claims description 3
- 229940043376 ammonium acetate Drugs 0.000 claims description 3
- 235000019257 ammonium acetate Nutrition 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- MYKUKUCHPMASKF-DNZPNURCSA-N 2,3,4,6-tetradeuterio-5-pyrrolidin-2-ylpyridine Chemical compound [2H]C1=C([2H])C([2H])=NC([2H])=C1C1NCCC1 MYKUKUCHPMASKF-DNZPNURCSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000005485 electric heating Methods 0.000 claims description 2
- 238000000899 pressurised-fluid extraction Methods 0.000 claims description 2
- 241000195955 Equisetum hyemale Species 0.000 claims 1
- 239000003595 mist Substances 0.000 claims 1
- 150000002825 nitriles Chemical class 0.000 claims 1
- MYKUKUCHPMASKF-VIFPVBQESA-N (S)-nornicotine Chemical compound C1CCN[C@@H]1C1=CC=CN=C1 MYKUKUCHPMASKF-VIFPVBQESA-N 0.000 abstract description 16
- OILSPHJMIPYURT-UHFFFAOYSA-N 2,4-dipyridin-3-ylpyridine Chemical compound C1=CN=CC(C=2C=C(N=CC=2)C=2C=NC=CC=2)=C1 OILSPHJMIPYURT-UHFFFAOYSA-N 0.000 abstract description 16
- MYKUKUCHPMASKF-UHFFFAOYSA-N Nornicotine Natural products C1CCNC1C1=CC=CN=C1 MYKUKUCHPMASKF-UHFFFAOYSA-N 0.000 abstract description 16
- DPNGWXJMIILTBS-UHFFFAOYSA-N myosmine Chemical compound C1CCN=C1C1=CC=CN=C1 DPNGWXJMIILTBS-UHFFFAOYSA-N 0.000 abstract description 14
- MTXSIJUGVMTTMU-JTQLQIEISA-N (S)-anabasine Chemical compound N1CCCC[C@H]1C1=CC=CN=C1 MTXSIJUGVMTTMU-JTQLQIEISA-N 0.000 abstract description 11
- 229930014345 anabasine Natural products 0.000 abstract description 11
- 150000004005 nitrosamines Chemical class 0.000 abstract description 8
- UIKROCXWUNQSPJ-VIFPVBQESA-N (-)-cotinine Chemical compound C1CC(=O)N(C)[C@@H]1C1=CC=CN=C1 UIKROCXWUNQSPJ-VIFPVBQESA-N 0.000 abstract description 7
- UIKROCXWUNQSPJ-UHFFFAOYSA-N Cotinine Natural products C1CC(=O)N(C)C1C1=CC=CN=C1 UIKROCXWUNQSPJ-UHFFFAOYSA-N 0.000 abstract description 7
- 229950006073 cotinine Drugs 0.000 abstract description 7
- 238000005259 measurement Methods 0.000 abstract description 5
- 230000035945 sensitivity Effects 0.000 abstract description 2
- BXYPVKMROLGXJI-JTQLQIEISA-N 3-[(2s)-1-nitrosopiperidin-2-yl]pyridine Chemical compound O=NN1CCCC[C@H]1C1=CC=CN=C1 BXYPVKMROLGXJI-JTQLQIEISA-N 0.000 description 10
- XKABJYQDMJTNGQ-VIFPVBQESA-N n-nitrosonornicotine Chemical compound O=NN1CCC[C@H]1C1=CC=CN=C1 XKABJYQDMJTNGQ-VIFPVBQESA-N 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 238000011084 recovery Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- FLAQQSHRLBFIEZ-UHFFFAOYSA-N N-Methyl-N-nitroso-4-oxo-4-(3-pyridyl)butyl amine Chemical compound O=NN(C)CCCC(=O)C1=CC=CN=C1 FLAQQSHRLBFIEZ-UHFFFAOYSA-N 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000000711 cancerogenic effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 239000013618 particulate matter Substances 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004885 tandem mass spectrometry Methods 0.000 description 2
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 description 1
- SOPPBXUYQGUQHE-JTQLQIEISA-N Anatabine Chemical compound C1C=CCN[C@@H]1C1=CC=CN=C1 SOPPBXUYQGUQHE-JTQLQIEISA-N 0.000 description 1
- SOPPBXUYQGUQHE-UHFFFAOYSA-N Anatabine Natural products C1C=CCNC1C1=CC=CN=C1 SOPPBXUYQGUQHE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 238000001294 liquid chromatography-tandem mass spectrometry Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000001394 metastastic effect Effects 0.000 description 1
- 206010061289 metastatic neoplasm Diseases 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000611 regression analysis Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- FKHIFSZMMVMEQY-UHFFFAOYSA-N talc Chemical compound [Mg+2].[O-][Si]([O-])=O FKHIFSZMMVMEQY-UHFFFAOYSA-N 0.000 description 1
- 235000019505 tobacco product Nutrition 0.000 description 1
- 238000004704 ultra performance liquid chromatography Methods 0.000 description 1
- 238000002137 ultrasound extraction Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
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- 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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/062—Preparation extracting sample from raw material
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- 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
This application provides the measuring methods of Alkaloid and nitrosamine in a kind of cigarette mainstream flue gas, comprising: a) smoking cigarette, and the total granules in cigarette mainstream flue gas is collected, extractant is added and deuterated Isotopic Internal Standard is extracted, collects extract liquor；B) by the extract liquor and QuECHERS reagent whirlpool mixing 0.5min~10min, 3~7min is centrifuged with the speed of 9000rpm~11000rpm, obtains supernatant；C) using UPLC-HR-MS in the supernatant Alkaloid and tobacco-specific nitrosamine carry out quantitative analysis.The method of the present invention can measure 6 kinds of Alkaloids (anabasine, nornicotine, myosmine, cotinine, nicotelline and N- formoxyl nornicotine) and 4 kinds of unique nitrosamines (NNN, NNK, NAT and NAB) in cigarette mainstream flue gas simultaneously; sensitivity and accuracy are high; selectivity is strong, the quick measurement of Alkaloid and nitrosamine suitable for batch cigarette filter.
Description
Technical field
The invention belongs to the physical and chemical inspection technical fields of tobacco product chemical component, and in particular to a kind of cigarette mainstream flue gas
The measuring method of middle Alkaloid and nitrosamine.
Background technique
Alkaloid (what N- formoxyl nornicotine of such as anabasine, nornicotine, myosmine, cotinine, nicotelline)
It is one of most important chemical component in tobacco and cigarette smoke.The content of tobacco Alkaloid to the interior quality of tobacco leaf,
Safety and availability have a great influence, Alkaloid and perfume quantity, concentration, miscellaneous gas, irritation there are it is extremely significant just
Correlation, anabasine, anabasine in Alkaloid exist with pleasant impression significant negatively correlated respectively.Micro biology in tobacco
Alkali anatabine and anabasine can be separately converted to N- nitroso anabasine (NAB) and N- nitrosoanabasine (NAT),
N- nitrosonornicotine (NNN) and 4- (methyl nitrosamino group) -1- (3- pyridyl group) -1- butanone (NNK) have 1 grade of carcinogenic work
Property, NAB, NAT have 3 grades of carcinogenic activities.Therefore, in Accurate Determining cigarette nicotiana alkaloids and tobacco-specific nitrosamine content
And its metastatic rule is studied, for guaranteeing the sucking quality of tobacco and objectively evaluating safety cigarette with highly important meaning
Justice.
Up to the present, in cigarette mainstream flue gas the measuring method of Alkaloid mainly have gas chromatography-mass spectrography and
Gas-chromatography tandem mass spectrometry etc., these methods need to carry out pre-treatment, and sodium hydroxide to sample using highly basic-sodium hydroxide
There is certain corrosivity to mass spectrograph device.The measuring method of tobacco-specific nitrosamine mainly has gas phase-in cigarette mainstream flue gas
The sample pretreatment process of thermal energy analyzer method and Liquid Chromatography-Tandem Mass Spectrometry etc., method is often more complicated.
Summary of the invention
In order to solve the above-mentioned technical problem, the purpose of the present invention is to provide Alkaloids in a kind of cigarette mainstream flue gas
With the measuring method of nitrosamine, specific technical solution is as follows:
The measuring method of Alkaloid and nitrosamine in a kind of cigarette mainstream flue gas, comprising the following steps:
A) smoking cigarette, and collect the total granules in cigarette mainstream flue gas, deuterated Isotopic Internal Standard is added and is added
Quick-dissolving agent extraction, collects extract liquor；
B) by the extract liquor and QuECHERS reagent whirlpool mixing 0.5min~10min, with 9000rpm~11000rpm
Speed be centrifuged 3~7min, obtain supernatant；
C) using UPLC-HR-MS in the supernatant Alkaloid and tobacco-specific nitrosamine quantitatively divided
Analysis.
Preferably, the step a) extractant is methanol and/or acetonitrile, and addition volume is 10~100mL.
Preferably, step a) the deuterated Isotopic Internal Standard is anabasine-D4, nornicotine-D4, myosmine-D4, can replace
Rather one of-D3 and nicotelline-D9 or a variety of.
Preferably, the step a) extraction is ultrasonic extraction or oscillation extraction, and extraction time is 20~80min, is extracted molten
The volume of liquid is 10~100mL.
Preferably, the mobile phase of the UPLC-HR-MS includes mobile phase A and Mobile phase B, and the mobile phase A is ammonium acetate
Aqueous solution, the Mobile phase B are methanol；
Its gradient elution program setting are as follows: 0~0.5min:2%B, 0.5~4min:2% → 98%B, 4~7min:98%
B, 7~8min:98% → 2%B balance 2min.
Preferably, the chromatogram column temperature of the UPLC-HR-MS is 25 DEG C~60 DEG C.
Preferably, the flow velocity of the mobile phase is 0.1~0.5mL/min.
Preferably, the ion source of the UPLC-HR-MS is electric heating esi ion source, and spray voltage is 2.5~4.0KV,
Ion source temperature is 250 DEG C~350 DEG C, and auxiliary gas heating temperature is 250 DEG C~350 DEG C, and sheath gas is 25~40mL/
Min, secondary air speed are 5~20mL/min.
Preferably, step b) is described after centrifugation further include: purification, the purification are Solid phase extraction or dispersed solid phase
Extracting and purifying.
Preferably, the condition of the suction are as follows: 20~24 DEG C of temperature, relative humidity 55%~65%, puff interval 60s,
Each duration 2s, pumping volume 35mL.
Compared with prior art, the invention has the following advantages that
1) the method for the present invention can measure 6 kinds of Alkaloids (anabasine, nornicotine, wheats in cigarette mainstream flue gas simultaneously
This bright, cotinine, nicotelline and N- formoxyl nornicotine) and 4 kinds of unique nitrosamines (NNN, NNK, NAT and NAB), detection limit
Between 0.04~4ng/ branch, quantitative limit between 0.132~13.2ng/ branch, recovery of standard addition between 91.8%~111%,
RSD is respectively less than 10%, and sensitivity improves 5~10 times compared with gas chromatography-tandem mass spectrometry, sucks product for guarantee tobacco
It matter and objectively evaluates safety cigarette and has a very important significance；
2) the method for the present invention is extracted using acceleration solvent, QuECHERS purifies test sample, before simplifying sample
Program is managed, and reduces the interference of the impurity in sample, reduces matrix interference, the Alkaloid suitable for batch cigarette filter
With the quick measurement of nitrosamine；
3) present invention chooses deuterated Isotopic Internal Standard and carries out quantitative analysis to each compound, reduces sample pretreatment process
In caused error, improve the accuracy of analysis.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 is the extraction ion flow graph of anabasine；
Fig. 2 is the extraction ion flow graph of nornicotine；
Fig. 3 is the extraction ion flow graph of myosmine；
Fig. 4 is the extraction ion flow graph of cotinine；
Fig. 5 is the extraction ion flow graph of nicotelline；
Fig. 6 is the extraction ion flow graph of N- formoxyl nornicotine；
Fig. 7 is the extraction ion flow graph of NNK；
Fig. 8 is the extraction ion flow graph of NNN；
Fig. 9 is the extraction ion flow graph of NAB；
Figure 10 is the extraction ion flow graph of NAT；
Figure 11 is the operational flowchart that Alkaloid and nitrosamine in cigarette mainstream flue gas are measured in embodiment 1.
Specific embodiment
Below in conjunction with specific embodiments of the present invention, technical solution of the present invention is clearly and completely described, is shown
So, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the reality in the present invention
Example is applied, every other embodiment obtained by those of ordinary skill in the art without making creative efforts all belongs to
In the scope of protection of the invention.
Embodiment 1
As shown in figure 11, the measurement of Alkaloid and nitrosamine includes: in the present embodiment cigarette mainstream flue gas
1) collection of cigarette mainstream smoke total particulate matter
Under conditions of temperature is 22 ± 2 DEG C, relative humidity is (60 ± 5) %, taken out using linear type smoking machine according to ISO
Suction condition (puff interval 60s, duration 2s, pumping volume 35mL) aspirates 5 cigarette, and collects 3 using cambridge filter
Total granules in cigarette mainstream flue gas is labeled as cigarette 1, cigarette 2 and cigarette 3.
2) sample pre-treatments
Cambridge filter is placed in the conical flask of 50mL, the internal standard of 200 μ L accelerated solvent extraction at room temperature is sequentially added
10min is taken, after standing a period of time, takes about 1.5mL supernatant to be added in the centrifuge tube of the reagent containing QuECHERS of 2mL, vortex
Mix 2min, 10000rpm be centrifuged 5min, collect supernatant, purified using dispersive solid-phase extraction, scavenging material can for aluminium oxide,
C18, PSA, Florisil or carbon.Wherein, myosmine-D4, cotinine-D3 and nicotelline-D9, internal standard concentration are inside designated as
For 10ug/mL.
3) sample analysis
It takes purified supernatant to carry out UHPLC-HR-MS analysis, it is peculiar to analyze Alkaloid and tobacco in supernatant
The content of nitrosamine.
Ultra performance liquid chromatography condition: chromatographic column is Waters BEH-C18 (2.1 × 50mm, 1.7 μm), chromatogram column temperature
It is 35 DEG C；The ammonium acetate solution that mobile phase A is 0.2%, Mobile phase B are methanol, and sampling volume is 1 μ L, and flow velocity is set as
0.25mL/min；Condition of gradient elution is set as: 0~0.5min:2%B, 0.5~4min:2% → 98%B, 4~7min:98%
B, 7~8min:98% → 2%B, then balance 2min.
High resolution mass spectrum condition: electric spray ion source (ESI), spray voltage 3.5KV, assist gas by 300 DEG C of ion source temperature
300 DEG C of body heating temperature, sheath gas 35mL/min, secondary air speed is 10mL/min, and scan pattern is PRM cation mould
Formula, instrumental resolution: 17500.
In mass spectrum, anabasine, nornicotine, myosmine, cotinine, nicotelline, N- formoxyl nornicotine, NNK, NNN,
The quota ion pair of NAB and NAT is respectively 163.1230 → 118.0653,149.1073 → 132.0810,147.0917 →
105.0450、177.1022→80.0500、234.1026→207.0920、177.1022→132.0810、208.1080→
122.0602,178.0975 → 120.0683,192.1131 → 162.1150 and 190.0975 → 106.0528.
6 kinds of Alkaloids (anabasine, nornicotine, myosmine, cotinine, nicotelline and N- formyl of the invention
Base nornicotine) and the extraction ion flow graph of 4 kinds of tobacco-specific nitrosamines (NNK, NNN, NAB and NAT) it is as shown in Figures 1 to 10,
Table 1 is the measurement result of 6 kinds of Alkaloids and 4 kinds of tobacco-specific nitrosamines in cigarette mainstream smoke total particulate matter.
Table 1
| Compound | Cigarette 1 (μ g) | Cigarette 2 (μ g) | Cigarette 3 (μ g) |
| Anabasine | 1.11 | 1.18 | 1.98 |
| Nornicotine | 1.99 | 1.86 | 2.10 |
| Myosmine | 1.92 | 1.83 | 1.76 |
| Cotinine | 1.31 | 1.28 | 1.02 |
| Nicotelline | 0.43 | 0.42 | 0.37 |
| Formoxyl nornicotine | 2.07 | 1.89 | 1.57 |
| NNK | 0.016 | 0.013 | 0.011 |
| NNN | 0.029 | 0.022 | 0.014 |
| NAB | 0.003 | 0.002 | 0.002 |
| NAT | 0.036 | 0.022 | 0.027 |
2 methodological study of embodiment
1) standard curve
Using acetonitrile as solvent, the series standard of the Alkaloid and tobacco-specific nitrosamine of preparing various concentration respectively is molten
Liquid carries out UPLC-HR-MS analysis using above-mentioned instrument condition respectively.Then inner mark method ration (internal standard are as follows: myosmine-is used
D4, cotinine-D3 and nicotelline-D9), using target peak area ratio in each object and its as ordinate (Y), each object is dense
Degree is that abscissa (X, ng/mL) carries out regression analysis, and obtaining 6 kinds of Alkaloids, (anabasine, myosmine, can replace nornicotine
Rather, nicotelline and N- formoxyl nornicotine), the regression equations of 4 kinds of tobacco-specific nitrosamines (NNK, NNN, NAB and NAT) and
Its related coefficient, as shown in table 2.
As shown in Table 2, the linear relationship of 6 kinds of Alkaloids and 4 kinds of tobacco-specific nitrosamine standard curves is good, R2?
Between 0.9944~0.9996.The standard solution of minimum concentration is diluted to and carried out UPLC-HR-MS analysis, is with 3 times of signal-to-noise ratio
The detection limit (LOD) of method, 10 times of signal-to-noise ratio are quantitative limit (LOQ), 6 kinds of Alkaloids and 4 kinds of tobacco-specific nitrosamines
LOD and LOQ is respectively 0.04~4.0ng/ branch and 0.132~13.2ng/ branch.Show that the method for the present invention is with higher sensitive
Degree, is suitable for the fast quantitative analysis of 6 kinds of Alkaloids and 4 kinds of tobacco-specific nitrosamines in cigarette mainstream flue gas.
Table 2
2) rate of recovery and precision
Take blank cigarette as test sample, by basic, normal, high 3 kinds of pitch-based spheres addition mark on the cambridge filter of collection
Then quasi- solution is handled sample by the sample-pretreating method of embodiment 1, each pitch-based sphere is measured in parallel 6 times, into
The measurement of the row rate of recovery and precision, experimental result are shown in Table 3.
As shown in Table 3, the average recovery of standard addition of 6 kinds of Alkaloids and 4 kinds of tobacco-specific nitrosamines 91.8%~
Between 111%, relative standard deviation can satisfy quantitative needs less than 10%.
Table 3
Claims (10)
1. the measuring method of Alkaloid and nitrosamine in a kind of cigarette mainstream flue gas, which comprises the following steps:
A) smoking cigarette, and collect the total granules in cigarette mainstream flue gas, deuterated Isotopic Internal Standard is added and accelerate molten
Agent extraction, collects extract liquor；
B) by the extract liquor and QuECHERS reagent whirlpool mixing 0.5min~10min, with the speed of 9000rpm~11000rpm
Degree 3~7min of centrifugation, obtains supernatant；
C) using UPLC-HR-MS in the supernatant Alkaloid and tobacco-specific nitrosamine carry out quantitative analysis.
2. measuring method according to claim 1, which is characterized in that the step a) extractant is methanol and/or second
Nitrile, addition volume are 10~100mL.
3. measuring method according to claim 1, which is characterized in that step a) the deuterated Isotopic Internal Standard is false scouring rush
One of alkali-D4, nornicotine-D4, myosmine-D4, cotinine-D3 and nicotelline-D9 or a variety of.
4. measuring method according to claim 1, which is characterized in that the step a) extraction is accelerated solvent extraction, extraction
Taking the time is 5~20min.
5. measuring method according to claim 1, which is characterized in that the mobile phase of the UPLC-HR-MS includes mobile phase
A and Mobile phase B, the mobile phase A are ammonium acetate solution, and the Mobile phase B is methanol；
The setting of its gradient elution program are as follows: 0~0.5min:2%B, 0.5~4min:2% → 98%B, 4~7min:98%B, 7
~8min:98% → 2%B balances 2min.
6. measuring method according to claim 1, which is characterized in that the chromatogram column temperature of the UPLC-HR-MS is 25 DEG C
~60 DEG C.
7. measuring method according to claim 1, which is characterized in that the flow velocity of the mobile phase is 0.1~0.5mL/
min。
8. measuring method according to claim 1, which is characterized in that the ion source of the UPLC-HR-MS is electric heating spray
Mist ion source, spray voltage are 2.5~4.0KV, and ion source temperature is 250 DEG C~350 DEG C, and auxiliary gas heating temperature is 250
DEG C~350 DEG C, sheath gas is 25~40mL/min, and secondary air speed is 5~20mL/min.
9. measuring method according to claim 1, which is characterized in that step b) is described after centrifugation further include: purification, institute
Stating purification is that Solid phase extraction or dispersive solid-phase extraction purify.
10. measuring method according to claim 1, which is characterized in that the condition of the suction are as follows: 20~24 DEG C of temperature,
Relative humidity 55%~65%, puff interval 60s, each duration 2s, pumping volume 35mL.
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