CN103698456A - Online detection method for pyrolysis gas-phase components of tobacco additive or tobacco material - Google Patents
Online detection method for pyrolysis gas-phase components of tobacco additive or tobacco material Download PDFInfo
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- CN103698456A CN103698456A CN201310724029.XA CN201310724029A CN103698456A CN 103698456 A CN103698456 A CN 103698456A CN 201310724029 A CN201310724029 A CN 201310724029A CN 103698456 A CN103698456 A CN 103698456A
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Abstract
The invention provides an online detection method for pyrolysis gas-phase components of a tobacco additive or a tobacco material. The method comprises the following steps: filtering the pyrolysis product of the tobacco additive or the tobacco material through a Cambridge filter device, trapping and injecting the sample, adopting a gas chromatography-mass spectrometry method to measure the content of the gas-phase components generated after the tobacco additive or tobacco material is pyrolyzed. Compared to the conventional method, the online detection method adopts a stepped-heating pyrolysis condition, different trapping and injection conditions and gas chromatography-mass spectrometry detection conditions, saves time, and can effectively and comprehensively detect low-molecular-weight gas-phase components in the pyrolysis product of the tobacco additive and the tobacco material. The method is of great significance for improving tobacco safety and reducing harm of the tobacco to human health.
Description
Technical field
The invention belongs to the technical field of the gas phase composition assay method that the cracking of a kind of on-line determination organic substance discharges, be specifically related to the assay method of the gas phase composition that the online cracking of a kind of tobacco additive agent or smoking material discharges.
Background technology
Improve safety cigarette, reducing cigarette is the World tobacco industry main development direction in future to the harm of health.Wherein, required cigarette additive or the smoking material of preparation tobacco, as an important component part of cigarette, himself security with and at cigarette, burn and suck the security of pyrolysis product in process, for the security that improves cigarette, will play vital effect.
The people such as Richard R.Baker have carried out Study on Cleavage (The pyrolysis of tobacco ingredients to the adjuvant using in tobacco, J.Anal.Appl.Pyrolysis 71 (2004) 223-311), but the method can only be measured formed half volatile component in adjuvant cracking process, especially Huffman analyte, can not measure many low-molecular-weight gas phase objectionable constituent (MW is less than 29g/mol) in pyrolysis product, that is to say and can not measure the gas phase composition producing in cigarette additive or smoking material cracking process.
Analytical approach and the analytic system (CN201110193135.0) of the gas phase combustion product of cigarette of Wang Ye, Liu Baizhan, Zheng Saijing invention, adopt the method for a kind of off-line cracking-thermal desorption-gas phase/mass spectrum (Py-ATD-GC/MSD) to measure the gaseous component that result of combustion of tobacco discharges.The method, by adopting off-line cracking process by cigarette or tobacco leaf pyrolytic, is collected decomposition product, and then puts into thermal desorption-gas chromatograph-mass spectrometer and measure the gas phase composition that cigarette or tobacco leaf cracking discharge.But the method is a kind of determined off-line method, and selected cracking temperature is steady temperature, has larger otherness with cigarette burning temperature, can not react truly the actual conditions of tobacco additive agent cracking.Meanwhile, owing to being determined off-line method, during off-line cracking, the gas phase composition that produces can not obtain detecting timely analysis, and gaseous component may produce ageing and produce certain subsidiary reaction, thereby produces distortion phenomenon.In addition, adsorbent can not have to all gas phase compositions same absorption property, can not all adsorb all gaseous substances, and the temperature when desorb may also can produce certain subsidiary reaction to gas phase composition, and testing result can produce inaccurate.
Therefore, setting up a kind of analytical approach of measuring the harmful or stimulating component of the gas phase that discharges in tobacco additive agent or the online cracking process of smoking material, is the ingredient of evaluating tobacco security interwoveness.
Summary of the invention
The shortcoming of prior art in view of the above, the object of the present invention is to provide a kind of method of on-line determination tobacco additive agent or smoking material pyrolysis gas phase constituent, solve and adopt the minute existing in off-line cracking-thermal desorption-gas phase/mass spectrum (Py-ATD-GC/MSD) assay method long, efficiency is low, the problems such as poor accuracy, for supplementing and improve existing tobacco additive agent or smoking material method for evaluating safety in the world, overcome prior art simultaneously and can not measure the defect of many low-molecular-weight gas phase objectionable constituent in pyrolysis product, conscientiously improve cigarette product quality and safety.
For achieving the above object and other relevant objects, the invention provides a kind of method of on-line determination tobacco additive agent or smoking material pyrolysis gas phase constituent, by the pyrolysis product of tobacco additive agent or smoking material, by cambridge filter device, filter, trapping sample introduction, then adopt combined gas chromatography mass spectrometry to measure the content of the gas phase composition producing after tobacco additive agent or smoking material cracking.
The method of described a kind of on-line determination tobacco additive agent or smoking material pyrolysis gas phase constituent, specifically includes following steps:
Described on-line determination specifically refers to: by sample by be connected to the cracking instrument, cambridge filter device of sealing one by pipeline, device and the gas chromatograph-mass spectrometer of trapping sample introduction are analyzed mensuration.
1) cracking: tobacco additive agent or smoking material are carried out to temperature programme cracking;
Preferably, as described in step 1), temperature programme cracking specifically refers to: take the sample of tobacco additive agent or smoking material, use silica wool that sample is fixed in cracking silica tube, put into again cracking instrument, under oxygen-containing gas atmosphere, temperature programme is stage by stage carried out in platinum filament heating, thus heating pyrolyze.
Preferably, the cracking condition of described cracking instrument is: pyrolysis gas: 10%O
2and 90%N
2combination gas; Gas flow rate: 70～276ml/min; Cracking room temperature: 250～300 ℃; Heating schedule: initial temperature is 300 ℃, keeps 5s, with 10～50 ℃/s, is warmed up to 900 ℃, keeps 5s.
Preferably, described cracking instrument is CDS 2000 cracking instrument or CDS 5250T cracking instrument.
More preferably, described sample fixed form in the cracking silica tube of CDS 2000 cracking instrument is: first at the middle part of cracking silica tube, load silica wool, then take the sample of tobacco additive agent or smoking material, be seated on this silica wool, then the silica wool beyond the Great Wall again in sample upper end, then cracking silica tube is put into cracking instrument.
More preferably, described sample fixed form in the cracking silica tube of CDS 5250T cracking instrument is: first in cracking silica tube, insert a quartz rod, and fill out silica wool in quartz rod upper end, take the sample of tobacco additive agent or smoking material, be seated on this silica wool, then the silica wool beyond the Great Wall again in sample upper end, then cracking silica tube is put into cracking instrument.
More preferably, the cracking condition of described CDS 2000 cracking instrument is: pyrolysis gas: 10%O
2and 90%N
2combination gas; Gas flow rate: 276ml/min; Cracking room temperature: 250 ℃; Heating schedule: initial temperature is 300 ℃, keeps 5s, with 30 ℃/s, is warmed up to 900 ℃, keeps 5s.
More preferably, the cracking condition of described CDS 5250T cracking instrument is: pyrolysis gas: 10%O
2/ and 90%N
2combination gas; Gas flow rate: 70ml/min; Cracking room temperature: 300 ℃; Heating schedule: initial temperature is 300 ℃, keeps 5s, with 30 ℃/s, is warmed up to 900 ℃, keeps 5s.
2) filter: the composition by tobacco additive agent described in step 1) or smoking material cracking generation, filters by cambridge filter device;
Preferably, as step 2) as described in cambridge filter device filter specifically finger: the pyrolysis product of tobacco additive agent or smoking material is filtered by cambridge filter device, cambridge filter device is the grain phase constituent interception in pyrolysis product, and gas phase composition in pyrolysis product is through cambridge filter.
Preferably, as step 2) as described in cambridge filter device utilize deactivation stainless steel to process, built-in O-ring seal keeps impermeability, cambridge filter diameter is 1cm, is connected respectively with the pipeline of cracking instrument, sampling device, and pipeline connects closely and without dead angle, more than withstand voltage 40psi, air tight.
3) trapping sample introduction: will be as step 2), gained gas phase composition is after trapping, then carries out desorption sample introduction;
Preferably, as described in step 3), gas phase composition is through trapping concrete finger: use cold-trap and bushing pipe, and/or adsorbent is to step 2) in gained gas phase composition trap.Preferably, the bushing pipe that uses cold-trap and be filled with adsorbent is to step 2) in gained gas phase composition trap.
Preferably, the low-temperature receiver of described cold-trap is liquid nitrogen or other low-temperature receiver.
Preferably, in described bushing pipe, filling out adsorbent is a kind of adsorbent, also can be and in bushing pipe, loads the compound adsorbent that multiple adsorbent combines.
Preferably, described adsorbent is any in Carbotrap B, Carbotrap C, TENAX.More preferably, described Carbotrap B, Carbotrap C are compound adsorbent.
Preferably, described to step 2) in gained gas phase composition through trapping actual conditions be: condenser temperature :-196～30 ℃; Adsorbent in bushing pipe: Carbotrap B or Carbotrap C or TENAX; The filling material of non-adsorbent: glass wool.
The principle of described trapping is: by being coated on, can filling out adsorbent trap in the cold-trap of bushing pipe outside and bushing pipe, wherein, by adsorbent, adsorb required gas phase composition, can jointly use to adsorb more required gas phase composition by multiple adsorbent; Meanwhile, when trapping, can utilize different condenser temperatures, trap required gas phase composition, improve arresting efficiency.Which kind of Trapping ways of choice for use, determine according to the physical property of the character of lysate and cracking generation.Use separately cold trap trapping gas phase composition, only filling glass is cotton in bushing pipe, not fill adsorbent, needs the condenser temperature of use lower; Use separately Capture by Sorbents, cold-trap is inoperative, and trapping temperature is 30 ℃ of room temperatures, and programmed temperature sampling initial temperature is also 30 ℃ of room temperatures, can be weaker to the little molecule gas phase composition trapping effect below six carbon; Cold-trap and adsorbent trap jointly, and trapping effect is best, and the little molecule gas phase composition that can substantially all cracking be produced traps (except carbon monoxide etc.).
Preferably, as described in step 3), the actual conditions of desorption sample introduction is: at 200～330 ℃, keep 1～5min.
Preferably, when carrying out desorption sample introduction by programmed temperature sampling device, the actual conditions of described programmed temperature sampling device temperature programme is :-196～30 ℃ keep 1min, then with 12 ℃/s, are warmed up to 200～330 ℃, at 200～330 ℃, keep 1～5min.
Any in the PTV programmed temperature sampling device of the CIS4 programmed temperature sampling device that more preferably, described programmed temperature sampling device is Gerstel company, CIS3 programmed temperature sampling device, Agilent company.Optimally, the CIS4 programmed temperature sampling device that described programmed temperature sampling device is Gerstel company.
Preferably, when carrying out desorption sample introduction by thermal desorption device, the actual conditions of described thermal desorption device desorb is: 200～330 ℃ of desorption temperatures, desorption time: 1～5min.
More preferably, described thermal desorption device is for being provided with cold-trap and bushing pipe, has the thermal desorption device that be automatically rapidly heated function and heating rate are greater than 30 ℃/s.
4) measure: by gas chromatograph-mass spectrometer, sample introduction sample is carried out to quantitative and qualitative analysis detection.
Preferably, as described in step 4), qualitative detection is by spectrum data library searching, determines the constituent of gas phase composition after cracking; Described quantitative detection is to adopt peak area normalization method to determine the relative content of gas phase composition after cracking.
Preferably, the spectrum data storehouse of described qualitative detection is wiley7n and Nist98 spectrum data storehouse, and pyrolysis gas phase constituent basis for estimation is selected matching degree >=80.
Preferably, described peak area normalization method refers to: after GC/MS analyzes, the chromatographic peak area of the pyrolysis gas phase constituent calculating respectively, and calculate the chromatographic peak area sum of pyrolysis gas phase constituent, obtain total chromatographic peak area, then, by the chromatographic peak area of pyrolysis gas phase constituent respectively divided by total chromatographic peak area, the chromatographic peak area that obtains respectively pyrolysis gas phase constituent accounts for the percent of total chromatographic peak area, is the relative content of pyrolysis gas phase constituent.
Preferably, as described in step 4), combined gas chromatography mass spectrometry condition is:
GC conditions is: chromatographic column: 60m * 0.32mm id * 1.8 μ m nominal(Supelco VOCOL); Injector temperature during thermal desorption sample introduction: 250～280 ℃; Carrier gas: high-purity helium, purity >=99.999%; Flow velocity: 1.0～1.2mL/min; Split ratio: 20～50:1; Heating schedule: 30～35 ℃ of initial temperatures keep 10min, rises to 180～240 ℃ with the speed of 3.5～10 ℃/min, then rises to 210 ℃～280 ℃ with the speed of 10～20 ℃/min, keeps 5～10min;
Mass spectrum condition is: ion source temperature: 230 ℃; Quadrupole rod temperature: 150 ℃, transmission line temperature: 230～280 ℃; Solvent delay: 3～5min; Ionization mode: EI source; Ionizing energy: 70eV; Scan mode: full scan (scan), mass scanning scope (m/z): 10～300amu.
The gas phase composition producing after described tobacco additive agent or smoking material cracking includes ammonia, hydrogen cyanide, sulfuretted hydrogen, aliphatic compound (volatilization alkane, volatilization alkene, isoprene, butadiene, acetylene), compound fragrant hydrocarbon (benzene, toluene, ethylbenzene, styrene, other aromatic hydrocarbon), acid compounds (formic acid, acetic acid, propionic acid, other volatile acid), ester type compound (methyl formate), aldehyde compound (formaldehyde, acetaldehyde, acryl aldehyde, other Volatile Aldehydes), ketone compounds (acetone, other volatility ketone), alcohol compound (methyl alcohol, other alcohol that volatilizees), nitrile compounds (acetonitrile, other nitrile that volatilizees), furfuran compound (furans, other volatility furans), pyridine compounds and their (pyridine, picoline class material, vinylpyridine, other volatility pyridine), azoles (pyrroles, pyrrolidine, N-crassitude), aminated compounds (methyl amine, other fatty amine) and amides compound (acetamide), other compound.
Off-line cracking-thermal desorption-gas phase/mass spectrum (Py-ATD-GC/MSD) Method And Principle is: adopt micro-stove formula cracker as cracking instrument, tobacco leaf powder is placed under oxygen-containing gas atmosphere, carry out the isothermal cracking of steady temperature, pyrolysis product filters by cambridge filter, cambridge filter is by the part trapping mutually of the grain in pyrolysis product, gas phase in pyrolysis product is partly passed, then gaseous component enters adsorption sampling pipe, be adsorbed sampling pipe absorption, last adsorption sampling pipe enters the analysis of gas chromatography mass spectrometry spectrometer after thermal desorption.Because sample adopts oxygen-containing gas, carry out cracking, and common capillary chromatographic column can not contact oxygen-containing atmosphere in temperature-rise period, therefore, the cigarette in the method or the cracking of tobacco ingredient, grain filter mutually, Gas Phase Adsorption agent is captured under off-line and carries out.Sample reusable heat desorption sample introduction sample desorb after trapping, gas chromatograph-mass spectrometer analysis, belong to off-line cracking.Due to micro-stove cracking instrument principle of heating restriction, off-line cracking-thermal desorption-gas phase/mass spectrometry method, selected cracking temperature is the cracking of sectional type isothermal, has larger otherness with cigarette burning temperature, can not react truly the actual conditions of tobacco additive agent cracking.Meanwhile, during off-line cracking, the gas phase composition that produces can not obtain detecting timely analysis, and gaseous component may produce ageing and produce certain subsidiary reaction, thereby produces distortion phenomenon.In addition, the gas phase composition that off-line cracking adopts adsorbent to produce cracking traps, and adsorbent can not have to all gas phase compositions same absorption property, can not all adsorb all gaseous substances.
As mentioned above, the method for a kind of on-line determination tobacco additive agent of the present invention or smoking material pyrolysis gas phase constituent, has following beneficial effect:
1. the method that the present invention applies for is by transforming the gas circuit of cracking instrument, add cambridge filter device, change the mode of original detection method determined off-line, compare the sample below of determined off-line just can measure possibly for 20 hours after cracking, on-line determination is saved time, and within after sample dissociation 5 minutes, with interior, just can be measured, and efficiency is high, avoid the ageing of determined off-line appearance and the distortion phenomenon that other subsidiary reaction produces, detection accuracy is higher.
2. the method that the present invention applies for, the temperature programme cracking condition of employing ladder-elevating temperature formula, the cracking temperature that is different from conventional method selection is steady temperature, can react truly the actual conditions of tobacco additive agent cracking.
3. the method that the present invention applies for, except employing adsorbent traps, also adopts cold-trap to trap, and has improved the arresting efficiency of gas phase composition.
4. the method that the present invention applies for, by selecting different sampling conditions and gas chromatography mass spectrometry condition determination, can be effectively, composition in complete detection tobacco additive agent and smoking material pyrolysis product.Can not only measure formed half volatile component in adjuvant cracking process, can also measure many low-molecular-weight gas phase objectionable constituent in pyrolysis product, can evaluate all sidedly the harmfulness of tobacco additive agent and smoking material lysate.
5. the method that the present invention applies for, a kind ofly can set up the method for testing integrating with the world or national standard and meet industry actual conditions, it is the ingredient of evaluating tobacco security interwoveness, it is the precondition that conscientiously improves cigarette product quality safety, for improving safety cigarette, reduce cigarette the harm tool of health is had very great significance.
Accompanying drawing explanation
Fig. 1 is shown as online CDS 2000 cracking-cambridge filter filtration-cold-trap of the present invention and Capture by Sorbents, sample introduction are analyzed schematic diagram, wherein, and I: cambridge filter device; II: cold-trap; III: bushing pipe and in the adsorbent filled out; LOAD: show trapping state; RUN: show sample introduction state; 1～8: eight logical valve interfaces
Fig. 2 is shown as online CDS 5250T cracking-cambridge filter filtration-cold-trap of the present invention and Capture by Sorbents, sample introduction are analyzed schematic diagram 2A, 2B, wherein, and 2A: show trapping state; 2B: show sample introduction state; I: cambridge filter device; II: cold-trap; III: bushing pipe and in the adsorbent filled out; 1～8: eight logical valve interfaces
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention, should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.
In the present embodiment, the selection of material comprises that instrument, sample and reagent are as follows:
1 material
1.1 instrument
CDS 2000 cracking instrument (U.S. CDS Analytical company); CDS 5250T cracking instrument (U.S. CDS Analytical company); Cracking silica tube, quartz rod (U.S. CDS Analytical company); Cambridge filter device (Shanghai Tobacco Group Co., Ltd.'s design, the processing of Puffma company); CIS4 programmed temperature sampling device and C506 controller (German Gerstel company); CDS adsorption trap (thermal desorption device, U.S. CDS Analytical company); GC7890 gas chromatograph (U.S. Agilent company); MS5973 mass spectrometer (U.S. Agilent company); VOCOL gas chromatographic column (60m * 0.32mm id * 1.8 μ m nominal) (Supelco company); XP603S type analysis balance (Switzerland METTLER TOLEDO company); Adsorbent: Carbotrap B, Carbotrap C, TENAX(Germany Gerstel company); The filling material of non-adsorbent: glass wool (German Gerstel company).
1.2 samples and reagent
Cured tobacco leaf powder (Shanghai Tobacco Group Co., Ltd.); D (+) – sucrose (99.9%, lark prestige Science and Technology Ltd.); Cigarette paper (CU60, French Mauduit company); Glutamine (99.5%, U.S. Sigma-Aldrich company); Oxalic acid (99.0%, German Dr.Ehrenstorfer GmbH company); Xenthophylls (98.5%, German Dr.Ehrenstorfer GmbH company); Liquid nitrogen (99%, chemical refrigeration gas company limited can be covered in Shanghai); Silica wool (the residual level of agriculture, U.S. CDS Analytical company); 10%O
2and 90%N
2mixed pyrolysis gas (chemical refrigeration gas company limited can be covered in Shanghai); Carrier gas: high-purity helium (99.999%, chemical refrigeration gas company limited can be covered in Shanghai).
1 method
1.1 cracking: first fill out silica wool at the middle part of cracking silica tube, then take 1 ± 0.05mg tobacco leaf powder, be contained on this silica wool, then silica wool in sample upper end plug, put into CDS 2000 cracking instrument, under oxygen-containing gas atmosphere, temperature programme cracking is stage by stage carried out in platinum filament heating again; The cracking condition of described CDS 2000 cracking instrument is: pyrolysis gas: 10%O
2and 90%N
2combination gas; Gas flow rate: 276ml/min; Cracking room temperature: 250 ℃; Heating rate: initial temperature is 300 ℃, keeps 5s, with 30 ℃/s, is warmed up to 900 ℃, keeps 5s.
1.2 filter: the composition that cracking is produced, by the cambridge filter device being connected with cracking instrument, filter online, and described cambridge filter diameter is 1cm;
1.3 trapping sample introductions: the adsorbent that the gas phase composition after filtering is carried out to fill in cold-trap (liquid nitrogen) and bushing pipe traps jointly, CIS4 programmed temperature sampling.Trapping sampling condition is: condenser temperature :-60 ℃; Bushing pipe adsorbent: Carbotrap B; Temperature programme curve :-60 ℃ keep 1min, are then warmed up to 250 ℃ with 12 ℃/s, keep 5min at 250 ℃.
1.4 measure: the gas phase composition after trapping sample introduction is carried out to quantitative and qualitative analysis detection by combined gas chromatography mass spectrometry; Described qualitative detection is by wiley7n and Nist98 spectrum data library searching, and composition basis for estimation is selected matching degree >=80; Described quantitative detection is to adopt peak area normalization method to determine the relative content of gas phase composition after cracking.
Described peak area normalization method refers to: after GC/MS analyzes, the chromatographic peak area of the pyrolysis gas phase constituent calculating respectively, and calculate the chromatographic peak area sum of pyrolysis gas phase constituent, obtain total chromatographic peak area, then, by the chromatographic peak area of pyrolysis gas phase constituent, respectively divided by total chromatographic peak area, the chromatographic peak area that obtains respectively pyrolysis gas phase constituent accounts for the percent of total chromatographic peak area, is the relative content of pyrolysis gas phase constituent.
Described combined gas chromatography mass spectrometry condition is:
GC conditions is: chromatographic column: 60m * 0.32mm id * 1.8 μ m nominal(Supelco VOCOL); Carrier gas: high-purity helium, purity >=99.999%; Flow velocity: 1.2mL/min; Split ratio: 50:1; Heating schedule: 35 ℃ of initial temperatures keep 10min, rises to 180 ℃ with the speed of 3.5 ℃/min, then rises to 250 ℃ with the speed of 10 ℃/min, keeps 5min;
Mass spectrum condition is: ion source temperature: 230 ℃; Quadrupole rod temperature: 150 ℃; Transmission line temperature: 260 ℃; Solvent delay: 5min; Ionization mode: EI source; Ionizing energy: 70eV; Scan mode: full scan (scan), mass scanning scope (m/z): 10-300amu.
2 results and discussion
Utilize this method to do to analyze to the pyrolysis gas phase constituent of tobacco leaf powder and measure, detailed process is shown in Fig. 1, and analysis result details are in Table 1.Result shows, by wiley7n and Nist98 collection of illustrative plates, retrieves, and identifies altogether 129 kinds of pyrolysis gas phase constituents, and adopts peak area normalization method to determine the relative content of each composition.Wherein, many low-molecular-weight gas phase objectionable constituent can both detect, thereby can evaluate all sidedly the harmfulness of tobacco leaf lysate.
Pyrolysis gas phase constituent in the tobacco leaf powder that table 1 GC-MS detects
1 method
1.1 cracking: first put into a quartz rod in cracking silica tube, and in quartz rod upper end, fill out the silica wool of about 1mg, compacting, take 1 ± 0.05mg sucrose on this silica wool, then in sample upper end, fill out about 1mg silica wool, put into CDS 5250T cracking instrument, under oxygen-containing gas atmosphere, temperature programme cracking is stage by stage carried out in platinum filament heating again; The cracking condition of described CDS 5250T cracking instrument is: pyrolysis gas: 10%O
2and 90%N
2combination gas; Gas flow rate: 70ml/min; Cracking room temperature: 300 ℃; Heating rate: initial temperature is 300 ℃, keeps 5s, with 30 ℃/s, is warmed up to 900 ℃, keeps 5s.
1.2 filter: the composition that cracking is produced, by the cambridge filter device being connected with cracking instrument, filter online, and described cambridge filter diameter is 1cm;
1.3 trapping sample introductions: the adsorbent TENAX that the gas phase composition after filtering is carried out filling in cold-trap (liquid nitrogen) and bushing pipe traps jointly, thermal desorption desorb sample introduction.Trapping sampling condition is: condenser temperature :-196 ℃; Bushing pipe adsorbent: TENAX; Thermal desorption desorb sampling condition: 330 ℃ of desorption temperatures, desorption time: 1min.
1.4 measure: the gas phase composition after trapping sample introduction is carried out to quantitative and qualitative analysis detection by combined gas chromatography mass spectrometry; Described qualitative detection is by wiley7n and Nist98 spectrum data library searching, and composition basis for estimation is selected matching degree >=80; Described quantitative detection is to adopt peak area normalization method as described in Example 1 to determine the relative content of gas phase composition after cracking.
Described combined gas chromatography mass spectrometry condition is:
GC conditions is: chromatographic column: 60m * 0.32mm id * 1.8 μ m nominal(Supelco VOCOL); Injector temperature: 250 ℃; Carrier gas: high-purity helium, purity >=99.999%; Flow velocity: 1mL/min; Split ratio: 20:1; Heating schedule: 30 ℃ of initial temperatures keep 10min, rises to 240 ℃ with the speed of 10 ℃/min, then rises to 280 ℃ with the speed of 20 ℃/min, keeps 5min;
Mass spectrum condition is: ion source temperature: 230 ℃; Quadrupole rod temperature: 150 ℃; Transmission line temperature: 280 ℃; Solvent delay: 3min; Ionization mode: EI source; Ionizing energy: 70eV; Scan mode: full scan (scan), mass scanning scope (m/z): 10-300amu.
2 results and discussion
Utilize this method to measure the pyrolysis gas phase constituent of sucrose, detailed process is shown in Fig. 2 A, 2B, and analysis result details are in Table 2.Result shows, by wiley7n and Nist98 collection of illustrative plates, retrieves, and identifies altogether 36 kinds of pyrolysis gas phase constituents, and adopts peak area normalization method to determine the relative content of each composition.Wherein, many low-molecular-weight gas phase objectionable constituent can both detect, thereby can evaluate all sidedly the harmfulness of sucrose lysate.
Pyrolysis gas phase constituent in the sucrose that table 2 GC-MS detects
| Sequence number | Retention time (min) | The compound of identifying | Matching degree | Relative peak area (%) |
| 1 | 4.044 | Formaldehyde | 98 | 4.361 |
| 2 | 4.142 | Water | 99 | 7.074 |
| 3 | 4.8 | 2-methyl-1-propylene | 99 | 6.603 |
| 4 | 5.019 | 1,3-butadiene | 99 | 12.973 |
| 5 | 5.308 | Acetaldehyde | 98 | 13.268 |
| 6 | 5.441 | 1-butine | 96 | 2.523 |
| 7 | 5.563 | (Z)-1,2-butadiene | 95 | 0.487 |
| 8 | 5.987 | 3-methyl-1-butene | 96 | 0.792 |
| 9 | 6.127 | (E)-1,2-butadiene | 92 | 1.474 |
| 10 | 6.896 | (Z)-1,3-pentadiene | 95 | 0.087 |
| 11 | 7.008 | 1-amylene | 90 | 0.555 |
| 12 | 7.304 | 1,1-dimethylcyclopropane | 82 | 0.26 |
| 13 | 7.749 | (Z)-1,2-dimethylcyclopropane | 80 | 1.47 |
| 14 | 8.24 | 1,3-pentadiene | 96 | 4.535 |
| 15 | 8.599 | Furans | 98 | 5.77 |
| 16 | 8.912 | 2-acryl aldehyde | 98 | 5.943 |
| 17 | 9.205 | Acetone | 96 | 8.819 |
| 18 | 10.329 | Isosorbide-5-Nitrae-pentadiene | 95 | 0.802 |
| 19 | 10.535 | (E)-3-methyl-2-amylene | 86 | 0.135 |
| 20 | 11.068 | 1,3-cyclopentadiene | 90 | 4.676 |
| 21 | 14.717 | (E)-pirylene | 92 | 0.86 |
| 22 | 15.702 | Trans-2-methyl isophthalic acid, 3-pentadiene | 80 | 0.185 |
| 23 | 16.461 | 2-methylfuran | 95 | 1.177 |
| 24 | 16.764 | 3-butene-2-one | 96 | 2.516 |
| 25 | 17.245 | 2-butanone | 98 | 1.822 |
| 26 | 19.097 | 1-methyl isophthalic acid, 3-cyclopentadiene | 91 | 0.352 |
| 27 | 19.564 | 1,3-cyclohexadiene | 85 | 0.535 |
| 28 | 22.154 | Benzene | 98 | 5.345 |
| 29 | 22.617 | 2-crotonaldehyde | 92 | 0.291 |
| 30 | 24.7 | Trans-2-hexene | 83 | 0.275 |
| 31 | 24.978 | 2,5-dimethyl furan | 82 | 0.08 |
| 32 | 30.326 | Toluene | 98 | 2.029 |
| 33 | 37.054 | Ethylbenzene | 96 | 0.249 |
| 34 | 37.308 | Furfural | 98 | 1.114 |
| 35 | 38.008 | 2-cyclopentene-1-one | 88 | 0.184 |
| 36 | 39.564 | 1,3,5,7-cyclo-octatetraene | 82 | 0.301 |
1 method
1.1 cracking: first fill out silica wool at the middle part of cracking silica tube, then take 1 ± 0.05mg cigarette paper, be contained on this silica wool, then silica wool in cigarette paper upper end plug, put into CDS 2000 cracking instrument, under oxygen-containing gas atmosphere, temperature programme cracking is stage by stage carried out in platinum filament heating again.The cracking condition of described CDS 2000 cracking instrument is: pyrolysis gas: 10%O
2and 90%N
2combination gas; Gas flow rate: 276ml/min; Cracking room temperature: 250 ℃; Heating rate: initial temperature is 300 ℃, keeps 5s, with 30 ℃/s, is warmed up to 900 ℃, keeps 5s.
1.2 filter: the composition that cracking is produced, by the cambridge filter device being connected with cracking instrument, filter online, and described cambridge filter diameter is 1cm;
1.3 trapping sample introductions: the gas phase composition after filtering is trapped separately through cold-trap, fill out glass wool in bushing pipe, CIS4 programmed temperature sampling; Trapping sampling condition is: condenser temperature :-60 ℃; Bushing pipe: glass wool; Temperature programme curve :-60 ℃ keep 1min, are then warmed up to 200 ℃ with 12 ℃/s, keep 5min at 200 ℃.
1.4 measure: the gas phase composition after trapping sample introduction is carried out to quantitative and qualitative analysis detection by combined gas chromatography mass spectrometry; Described qualitative detection is by wiley7n and Nist98 spectrum data library searching, and composition basis for estimation is selected matching degree >=80; Described quantitative detection is to adopt peak area normalization method as described in Example 1 to determine the relative content of gas phase composition after cracking.
Described combined gas chromatography mass spectrometry condition is:
GC conditions is: chromatographic column: 60m * 0.32mm id * 1.8 μ m nominal(Supelco VOCOL); Carrier gas: high-purity helium, purity >=99.999%; Flow velocity: 1.2mL/min; Split ratio: 20:1; Heating schedule: 30 ℃ of initial temperatures keep 10min, rises to 180 ℃ with the speed of 3.5 ℃/min, then rises to 210 ℃ with the speed of 10 ℃/min, keeps 5min;
Mass spectrum condition is: ion source temperature: 230 ℃; Quadrupole rod temperature: 150 ℃; Transmission line temperature: 230 ℃; Solvent delay: 3.5min; Ionization mode: EI source; Ionizing energy: 70eV; Scan mode: full scan (scan), mass scanning scope (m/z): 10-300amu.
2 results and discussion
Utilize this method to measure the pyrolysis gas phase constituent of cigarette paper, detailed process is shown in Fig. 1, and analysis result details are in Table 3.Result shows, by wiley7n and Nist98 collection of illustrative plates, retrieves, and identifies altogether 41 kinds of pyrolysis gas phase constituents, and adopts peak area normalization method to determine the relative content of each composition.Wherein, many low-molecular-weight gas phase objectionable constituent can both detect, thus the harmfulness of evaluating cigarette paper lysate all sidedly.
Pyrolysis gas phase constituent in the cigarette paper that table 3 GC-MS detects
| Sequence number | Retention time (min) | The compound of identifying | Matching degree | Relative peak area (%) |
| 1 | 3.947 | Trimethylene | 88 | 0.141 |
| 2 | 4.044 | Formaldehyde | 98 | 0.552 |
| 3 | 4.163 | Water | 98 | 6.567 |
| 4 | 4.814 | 2-methyl-1-propylene | 86 | 8.48 |
| 5 | 5.033 | 1,3-butadiene | 95 | 10.76 |
| 6 | 5.329 | Acetaldehyde | 98 | 6.594 |
| 7 | 5.569 | 1-butine | 89 | 0.449 |
| 8 | 6.008 | 2-methyl-2-butene | 85 | 0.713 |
| 9 | 6.137 | 1,2-butadiene | 94 | 0.548 |
| 10 | 6.764 | Ethanol | 92 | 0.351 |
| 11 | 7.032 | 1-amylene | 97 | 1.707 |
| 12 | 7.324 | 2-methyl-1-butene alkene | 90 | 0.955 |
| 13 | 7.76 | Trans-1,2-dimethylcyclopropane | 83 | 1.153 |
| 14 | 7.986 | 2-butine | 86 | 0.611 |
| 15 | 8.264 | 1,3-pentadiene | 96 | 13.989 |
| 16 | 8.616 | Furans | 98 | 4.943 |
| 17 | 8.933 | 2-acryl aldehyde | 92 | 5.031 |
| 18 | 9.232 | Acetone | 97 | 6.08 |
| 19 | 10.343 | (Z)-1,3-pentadiene | 86 | 0.899 |
| 20 | 10.563 | Acetonitrile | 89 | 0.286 |
| 21 | 11.067 | 1,3-cyclopentadiene | 92 | 2.902 |
| 22 | 12.669 | 2-vinyl cyanide | 95 | 0.485 |
| 23 | 13.118 | 1-hexene | 96 | 1.69 |
| 24 | 14.744 | 2-methyl-2-acryl aldehyde | 92 | 1.671 |
| 25 | 16.461 | 2-methylfuran | 95 | 1.17 |
| 26 | 16.795 | 3-butene-2-one | 96 | 1.358 |
| 27 | 17.269 | 2-butanone | 96 | 1.16 |
| 28 | 17.721 | Propionitrile | 98 | 0.359 |
| 29 | 18.488 | Cyclopropylniitrile | 81 | 0.373 |
| 30 | 19.588 | Methyl isophthalic acid, 3-cyclopentadiene | 84 | 0.448 |
| 32 | 21.343 | 1-heptene | 85 | 0.171 |
| 33 | 22.154 | Benzene | 98 | 10.341 |
| 34 | 29.02 | Octene | 88 | 0.216 |
| 35 | 30.316 | Toluene | 96 | 3.929 |
| 36 | 37.026 | Ethylbenzene | 96 | 0.498 |
| 37 | 37.342 | 1,3-dimethyl benzene | 98 | 0.387 |
| 38 | 39.331 | Isosorbide-5-Nitrae-dimethyl benzene | 98 | 0.109 |
| 39 | 39.543 | Styrene | 99 | 0.702 |
| 40 | 41.897 | 1-decene | 83 | 0.145 |
| 41 | 47.196 | Coumarone | 91 | 0.219 |
1 method
1.1 cracking: first fill out silica wool at the middle part of cracking silica tube, then take 1 ± 0.05mg glutamine, be contained on this silica wool, then silica wool in glutamine upper end plug, put into again CDS 2000 cracking instrument, under oxygen-containing gas atmosphere, temperature programme cracking is stage by stage carried out in platinum filament heating; The cracking condition of described CDS 2000 cracking instrument is: pyrolysis gas: 10%O
2and 90%N
2combination gas; Gas flow rate: 276ml/min; Cracking room temperature: 250 ℃; Heating rate: initial temperature is 300 ℃, keeps 5s, with 30 ℃/s, is warmed up to 900 ℃, keeps 5s.
1.2 filter: the composition that cracking is produced, by the cambridge filter device being connected with cracking instrument, filter online, and described cambridge filter diameter is 1cm;
1.3 trapping sample introductions: the adsorbent Carbotrap B that the gas phase composition after filtering is carried out filling in bushing pipe traps separately, and cold-trap is not used, CIS4 programmed temperature sampling; Trapping sampling condition is: condenser temperature: 30 ℃; Bushing pipe: Carbotrap B; Temperature programme curve: 30 ℃ keep 1min, are then warmed up to 250 ℃ with 12 ℃/s, keep 5min at 250 ℃.
1.4 measure: the gas phase composition after trapping sample introduction is carried out to quantitative and qualitative analysis detection by combined gas chromatography mass spectrometry; Described qualitative detection is by wiley7n and Nist98 spectrum data library searching, and composition basis for estimation is selected matching degree >=80; Described quantitative detection is to adopt peak area normalization method as described in Example 1 to determine the relative content of gas phase composition after cracking.
Described combined gas chromatography mass spectrometry condition is:
GC conditions is: chromatographic column: 60m * 0.32mm id * 1.8 μ m nominal(Supelco VOCOL); Carrier gas: high-purity helium, purity >=99.999%; Flow velocity: 1.2mL/min; Split ratio: 50:1; Heating schedule: 30 ℃ of initial temperatures keep 10min, rises to 180 ℃ with the speed of 3.5 ℃/min, then rises to 250 ℃ with the speed of 10 ℃/min, keeps 10min;
Mass spectrum condition is: ion source temperature: 230 ℃; Quadrupole rod temperature: 150 ℃; Transmission line temperature: 260 ℃; Solvent delay: 5min; Ionization mode: EI source; Ionizing energy: 70eV; Scan mode: full scan (scan), mass scanning scope m/z:10-300amu.
2 results and discussion
Utilize this method to measure the pyrolysis gas phase constituent of glutamine, detailed process is shown in Fig. 1, and analysis result details are in Table 4.Result shows, by collection of illustrative plates, retrieves, and identifies altogether 54 kinds of pyrolysis gas phase constituents, and adopts peak area normalization method to determine the relative content of each composition.Wherein, many low-molecular-weight gas phase objectionable constituent can both detect, thereby can evaluate all sidedly the harmfulness of glutamine lysate.
Pyrolysis gas phase constituent in the glutamine that table 4 GC-MS detects
| Sequence number | Retention time (min) | The compound of identifying | Matching degree | Relative peak area (%) |
| 1 | 6.089 | Ammonia | 90 | 1.475 |
| 2 | 6.919 | Water | 92 | 45.646 |
| 3 | 8.108 | Acetaldehyde | 95 | 0.264 |
| 4 | 9.686 | Different hydrogen cyanide | 90 | 0.734 |
| 5 | 9.908 | |
56 | 5.430 |
| 6 | 12.918 | Acetone | 98 | 0.537 |
| 7 | 15.966 | 2-vinyl cyanide | 98 | 5.825 |
| 8 | 17.579 | Acetic acid | 99 | 0.440 |
| 9 | 19.953 | 2-butanone | 98 | 0.207 |
| 10 | 20.307 | Propionitrile | 99 | 2.191 |
| 11 | 20.996 | 2-methyl-2-vinyl cyanide | 95 | 0.221 |
| 12 | 23.171 | Isobutyronotrile | 96 | 0.195 |
| 13 | 24.252 | Benzene | 98 | 0.378 |
| 14 | 24.548 | Propionic acid | 94 | 0.225 |
| 15 | 24.756 | 2-acrylic acid | 95 | 0.099 |
| 16 | 24.986 | 2-butene nitrile | 92 | 2.043 |
| 17 | 26.814 | Butyronitrile | 92 | 0.953 |
| 18 | 29.292 | Formamide | 98 | 0.216 |
| 19 | 31.353 | 1,3,5-cycloheptatriene | 86 | 0.087 |
| 20 | 31.593 | Pyridine | 98 | 0.205 |
| 21 | 31.739 | Pyrroles | 99 | 6.695 |
| 22 | 32.183 | 2,3,4,5-tetrahydropyridine | 91 | 0.144 |
| 23 | 33.657 | Acetaldehyde cyanhydrin | 83 | 0.341 |
| 24 | 33.779 | Acetamide | 90 | 0.682 |
| 25 | 34.776 | Cyclopentanone | 84 | 0.398 |
| 26 | 35.586 | 2-picoline | 91 | 0.528 |
| 27 | 37.001 | 2-methylpyrrole | 96 | 1.608 |
| 28 | 37.209 | (Z)-2-maleonitrile | 87 | 0.095 |
| 29 | 37.4 | 3-methylpyrrole | 95 | 0.430 |
| 30 | 38.148 | 2-cyclopentene-1-one | 98 | 0.183 |
| 31 | 38.992 | Propionamide | 90 | 0.442 |
| 32 | 39.364 | 2-acrylamide | 85 | 0.319 |
| 33 | 40.591 | 2-ethylpyridine | 92 | 0.180 |
| 34 | 41.724 | 2,5-dimethyl pyrrole | 90 | 0.377 |
| 35 | 41.936 | 2-N-ethyl pyrrole N- | 91 | 0.653 |
| 36 | 42.124 | 3,5-lutidines | 88 | 0.190 |
| 37 | 42.541 | 2,3-dimethyl pyrrole | 92 | 0.131 |
| 38 | 42.933 | 3-N-ethyl pyrrole N- | 98 | 0.345 |
| 39 | 43.416 | (E)-2-maleonitrile | 82 | 0.203 |
| 40 | 43.834 | Butyramide | 89 | 0.086 |
| 41 | 44.112 | Butyrolactone | 96 | 0.223 |
| 42 | 46.03 | 2-ethyl-4-methylpyrrole | 80 | 0.477 |
| 43 | 46.183 | Pyrazine | 82 | 0.268 |
| 44 | 46.489 | 2,3,5-trimethyl pyrroles | 82 | 0.324 |
| 45 | 46.763 | Cyanophenyl | 95 | 0.500 |
| 46 | 47.413 | Unknown material 2 | 62 | 0.594 |
| 47 | 47.775 | Unknown material 3 | 71 | 0.410 |
| 48 | 48.609 | 4-methylaniline | 83 | 0.407 |
| 49 | 50.722 | 4-methyl-2-pyridine amine | 80 | 0.158 |
| 50 | 51.271 | 4-aminopyrimidine | 85 | 1.890 |
| 51 | 52.071 | 2-pyrrolidine | 82 | 10.562 |
| 52 | 52.283 | 2,4-dimethyl oxazoline | 88 | 0.325 |
| 53 | 52.849 | 5-piperidines-2-pyrrolidine | 86 | 1.133 |
| 54 | 53.311 | 4-methyl oxazole | 81 | 1.329 |
Embodiment 5
1 method
1.1 cracking: first put into a quartz rod in cracking tube quartz, in quartz rod upper end, fill out the silica wool of 1mg left and right, compacting, taking 1 ± 0.05mg oxalic acid is contained on this silica wool, then in sample upper end, fill out the silica wool of 1mg left and right, put into CDS 5250T cracking instrument, under oxygen-containing gas atmosphere, temperature programme cracking is stage by stage carried out in platinum filament heating again; The cracking condition of described CDS 5250T cracking instrument is: pyrolysis gas: 10%O
2and 90%N
2combination gas; Gas flow rate: 70ml/min; Cracking room temperature: 300 ℃; Heating rate: initial temperature is 300 ℃, keeps 5s, with 30 ℃/s, is warmed up to 900 ℃, keeps 5s.
1.2 filter: the composition that cracking is produced, by the cambridge filter device being connected with cracking instrument, filter online, and described cambridge filter diameter is 1cm;
1.3 trapping sample introductions: the adsorbent TENAX that the gas phase composition after filtering is carried out filling in bushing pipe traps separately, and cold-trap is not used, thermal desorption desorb sample introduction.Trapping sampling condition is: condenser temperature: 30 ℃; Bushing pipe adsorbent: Carbotrap C; Thermal desorption desorb sampling condition: 200 ℃ of desorption temperatures, desorption time: 5min.
1.4 measure: the gas phase composition after trapping sample introduction is carried out to quantitative and qualitative analysis detection by combined gas chromatography mass spectrometry; Described qualitative detection is by wiley7n and Nist98 spectrum data library searching, and composition basis for estimation is selected matching degree >=80; Described quantitative detection is to adopt peak area normalization method as described in Example 1 to determine the relative content of gas phase composition after cracking.
Described combined gas chromatography mass spectrometry condition is:
GC conditions is: chromatographic column: 60m * 0.32mm id * 1.8 μ m nominal(Supelco VOCOL); Injector temperature: 280 ℃; Carrier gas: high-purity helium, purity >=99.999%; Flow velocity: 1.2mL/min; Split ratio: 20:1; Heating schedule: 30 ℃ of initial temperatures keep 10min, rises to 240 ℃ with the speed of 10 ℃/min, then rises to 280 ℃ with the speed of 20 ℃/min, keeps 5min.
Mass spectrum condition is: ion source temperature: 230 ℃; Quadrupole rod temperature: 150 ℃, transmission line temperature: 280 ℃; Solvent delay: 3min; Ionization mode: EI source; Ionizing energy: 70eV; Scan mode: full scan (scan), mass scanning scope (m/z): 10-300amu.
2 results and discussion
Utilize this method to measure the pyrolysis gas phase constituent of oxalic acid, detailed process is shown in Fig. 2 A, 2B, and analysis result details are in Table 5.Result shows, by wiley7n and Nist98 collection of illustrative plates, retrieves, and identifies altogether 22 kinds of pyrolysis gas phase constituents, and adopts peak area normalization method to determine the relative content of each composition.Wherein, many low-molecular-weight gas phase objectionable constituent can both detect, thereby can evaluate all sidedly the harmfulness of oxalic acid lysate.
The oxalic acid pyrolysis gas phase constituent that table 5 GC-MS detects
| Sequence number | Retention time (min) | The compound of identifying | Matching degree | Relative peak area (%) |
| 1 | 6.402 | Formaldehyde | 90 | 0.124 |
| 2 | 6.871 | Water | 99 | 12.150 |
| 3 | 7.615 | 1,3-butadiene | 95 | 0.182 |
| 4 | 8.004 | Acetaldehyde | 92 | 0.097 |
| 5 | 12.237 | Formic acid | 98 | 0.097 |
| 6 | 12.484 | 2-acryl aldehyde | 98 | 0.180 |
| 7 | 12.797 | 1-propylene-2-alcohol | 95 | 0.120 |
| 8 | 14.548 | 1,3-cyclopentadiene | 96 | 0.177 |
| 9 | 17.76 | Acetic acid | 99 | 2.173 |
| 10 | 19.435 | 3-butene-2-one | 90 | 0.157 |
| 11 | 23.196 | Unknown material | 60 | 0.088 |
| 12 | 24.165 | Benzene | 94 | 2.103 |
| 13 | 24.44 | (E)-2-crotonaldehyde | 96 | 0.363 |
| 14 | 24.808 | 2-acrylic acid | 95 | 0.589 |
| 15 | 31.301 | Toluene | 96 | 0.503 |
| 16 | 33.622 | (Z)-2-butenoic acid | 88 | 1.541 |
| 17 | 34.279 | (E)-2-butenoic acid | 86 | 0.106 |
| 18 | 38.102 | 2-cyclopentene-1-one | 97 | 0.212 |
| 19 | 39.541 | Styrene | 98 | 0.251 |
| 20 | 40.41 | Maleic anhydride | 96 | 78.042 |
| 21 | 55.915 | Naphthalene | 98 | 0.602 |
| 22 | 60.096 | 2-methylnaphthalene | 94 | 0.142 |
Embodiment 6
1 method
1.1 cracking: first fill out silica wool at the middle part of cracking silica tube, take 1 ± 0.05mg xenthophylls, be contained on this silica wool, then silica wool in xenthophylls upper end plug, put into CDS 2000 cracking instrument, under oxygen-containing gas atmosphere, temperature programme cracking is stage by stage carried out in platinum filament heating again; The cracking condition of described CDS 2000 cracking instrument is: pyrolysis gas: 10%O
2and 90%N
2combination gas; Gas flow rate: 276ml/min; Cracking room temperature: 250 ℃; Heating rate: initial temperature is 300 ℃, keeps 5s, with 30 ℃/s, is warmed up to 900 ℃, keeps 5s.
1.2 filter: the composition that cracking is produced, by the cambridge filter device being connected with cracking instrument, filter online, and described cambridge filter diameter is 1cm;
1.3 trapping sample introductions: the adsorbent Carbotrap B that the gas phase composition after filtering is carried out to fill in cold-trap (liquid nitrogen) and bushing pipe traps jointly, CIS4 programmed temperature sampling; Trapping sampling condition is: condenser temperature :-196 ℃; Bushing pipe: Carbotrap B; Temperature programme curve :-196 ℃ keep 1min, are then warmed up to 330 ℃ with 12 ℃/s, keep 1min at 330 ℃.
1.4 measure: the gas phase composition after trapping sample introduction is carried out to quantitative and qualitative analysis detection by combined gas chromatography mass spectrometry; Described qualitative detection is by wiley7n and Nist98 spectrum data library searching, and composition basis for estimation is selected matching degree >=80; Described quantitative detection is to adopt peak area normalization method as described in Example 1 to determine the relative content of gas phase composition after cracking.
Described combined gas chromatography mass spectrometry condition is:
GC conditions is: chromatographic column: 60m * 0.32mm id * 1.8 μ m nominal(Supelco VOCOL); Carrier gas: high-purity helium, purity >=99.999%; Flow velocity: 1.2mL/min; Split ratio: 50:1; Heating schedule: 30 ℃ of initial temperatures keep 10min, rises to 180 ℃ with the speed of 3.5 ℃/min, then rises to 250 ℃ with the speed of 10 ℃/min, keeps 10min;
Mass spectrum condition is: ion source temperature: 230 ℃; Quadrupole rod temperature: 150 ℃, transmission line temperature: 280 ℃.Solvent delay: 3.5min; Ionization mode: EI source; Ionizing energy: 70eV; Scan mode: full scan (scan), mass scanning scope m/z:10-300amu.
2 results and discussion
Utilize this method to measure the pyrolysis gas phase constituent of xenthophylls, detailed process is shown in Fig. 1, and analysis result details are in Table 6.Result shows, by collection of illustrative plates, retrieves, and detects altogether 107 kinds of pyrolysis gas phase constituents, and adopts peak area normalization method to determine the relative content of each composition.Wherein, many low-molecular-weight gas phase objectionable constituent can both detect, thereby can evaluate all sidedly the harmfulness of xenthophylls lysate.
The xenthophylls pyrolysis gas phase constituent that table 6 GC-MS detects
| Sequence number | Retention time (min) | The compound of identifying | Matching degree | Relative peak area (%) |
| 1 | 4.41 | Unknown material | 55 | 2.321 |
| 2 | 8.612 | Ethyl formate | 87 | 0.184 |
| 3 | 11.605 | Unknown material | 59 | 0.162 |
| 4 | 11.99 | 3-methyl-1-butene | 89 | 0.220 |
| 5 | 12.578 | Unknown material | 49 | 0.074 |
| 6 | 13.134 | Unknown material | 65 | 0.624 |
| 7 | 13.287 | Unknown material | 74 | 0.289 |
| 8 | 13.975 | Acetone | 93 | 0.480 |
| 9 | 14.194 | (Z)-1,3-pentadiene | 87 | 0.168 |
| 10 | 15.028 | (E)-1,3-pentadiene | 90 | 0.066 |
| 11 | 15.668 | 1,3-cyclopentadiene | 92 | 0.159 |
| 12 | 17.329 | 1-hexene | 94 | 0.286 |
| 13 | 17.736 | 2 methyl propanal | 93 | 0.067 |
| 14 | 18.021 | Acetic acid | 80 | 0.102 |
| 15 | 18.566 | Methacrolein | 96 | 0.256 |
| 16 | 19.977 | 2-methylfuran | 95 | 0.190 |
| 17 | 20.151 | Methyl vinyl ketone | 91 | 0.322 |
| 18 | 20.533 | 2-butanone | 98 | 0.301 |
| 19 | 21.267 | (Z, Z)-2,4-hexadiene | 93 | 0.074 |
| 20 | 21.635 | C, t-1,3-hexadiene | 87 | 0.100 |
| 21 | 22.146 | 3-methylene cyclopentene | 87 | 0.511 |
| 22 | 22.521 | 1,3-cyclohexene | 91 | 0.415 |
| 23 | 23.008 | Unknown material | 70 | 0.059 |
| 24 | 23.95 | 1-heptene | 64 | 0.099 |
| 25 | 24.162 | 3-methyl butyraldehyde | 90 | 0.241 |
| 26 | 24.648 | Benzene | 87 | 1.652 |
| 27 | 24.864 | Unknown material | 58 | 0.115 |
| 28 | 26.219 | 3,3-dimethyl-2,4-pentanedione | 93 | 0.075 |
| 29 | 26.237 | 3-ethyl-2 pentanone | 81 | 0.042 |
| 30 | 28.691 | (Z)-3-methyl isophthalic acid, 3,5-hexatriene | 93 | 0.191 |
| 31 | 28.916 | 1-methyl isophthalic acid, 4-cyclohexadiene | 76 | 0.017 |
| 32 | 29.483 | Unknown material | 70 | 0.149 |
| 33 | 30.355 | 1-octene | 90 | 0.054 |
| 34 | 30.863 | 2-methyl isophthalic acid, 3,5-hexatriene | 95 | 0.062 |
| 35 | 31.29 | 3-methyl isophthalic acid, 3,5-hexatriene | 94 | 0.019 |
| 36 | 31.502 | Toluene | 94 | 14.986 |
| 37 | 33.633 | 3-methyl-2-butene aldehyde | 94 | 0.221 |
| 38 | 34.165 | 1,2,5,5-tetramethyl-1,3-cyclopentadiene | 84 | 0.801 |
| 39 | 34.842 | 1,2,5,5-tetramethyl-1,3-cyclopentadiene | 80 | 0.867 |
| 40 | 35.384 | Unknown material | 80 | 0.249 |
| 41 | 36.226 | 1-tridecylene | 91 | 0.074 |
| 42 | 36.577 | Unknown material | 76 | 0.548 |
| 43 | 37.317 | Ethylbenzene | 95 | 0.206 |
| 44 | 37.616 | P-toluene | 87 | 11.871 |
| 45 | 38.134 | Unknown material | 64 | 0.161 |
| 46 | 39.128 | Unknown material | 64 | 0.073 |
| 47 | 39.225 | DHF | 92 | 0.037 |
| 48 | 39.357 | O-toluene | 94 | 0.404 |
| 49 | 39.534 | Styrene | 91 | 0.227 |
| 50 | 40.74 | 1-ethyl-2-toluene | 88 | 0.016 |
| 51 | 41.634 | 1-decene | 90 | 0.226 |
| 52 | 42.791 | 1-ethyl-3-toluene | 91 | 0.788 |
| 53 | 43.013 | Unknown material | 62 | 0.373 |
| 54 | 43.281 | 2-ethyl-Isosorbide-5-Nitrae-dimethylbenzene | 86 | 0.686 |
| 55 | 44.091 | 2,6-dimethyl-2,4,6-sarohornene | 92 | 0.177 |
| 56 | 44.341 | Phenol | 90 | 0.267 |
| 57 | 44.633 | 1,2,3-trimethylbenzene | 97 | 1.063 |
| 58 | 45.005 | 1-vinyl-3-toluene | 84 | 0.747 |
| 59 | 45.2 | 1-vinyl-4--toluene | 81 | 0.488 |
| 60 | 45.446 | 3-methyl-2-cyclopentene-1-one | 87 | 0.042 |
| 61 | 45.707 | Unknown material | 60 | 0.047 |
| 62 | 45.877 | Unknown material | 52 | 0.153 |
| 63 | 46.326 | Coumarone | 95 | 0.062 |
| 64 | 46.624 | 1,3,5-trimethylbenzene | 97 | 1.383 |
| 65 | 47.257 | 1-methyl-3-propyl benzene | 96 | 0.122 |
| 66 | 47.452 | Unknown material | 60 | 0.047 |
| 67 | 47.594 | 3,5,5-trimethyl-3-cyclohexene-1-ketone | 95 | 2.210 |
| 68 | 47.89 | 2-ethyl-phenol | 95 | 6.060 |
| 69 | 48.407 | 3,5,5-trimethyl-2-cyclohexene-1-alcohol | 95 | 0.430 |
| 70 | 48.546 | Unknown material | 55 | 0.611 |
| 71 | 48.863 | Indenes | 92 | 0.337 |
| 72 | 49.221 | 3-methylphenol | 86 | 0.945 |
| 73 | 49.589 | 1-methyl-4-(1-isopropyl)-benzene | 97 | 0.494 |
| 74 | 49.881 | 1-ethyl-2,3-dimethyl benzene | 95 | 0.347 |
| 75 | 50.076 | 2-vinyl-Isosorbide-5-Nitrae-dimethyl benzene | 95 | 0.035 |
| 76 | 50.288 | 3-tolyl aldehyde | 80 | 0.604 |
| 77 | 50.649 | (3-methyl-2-butene base)-benzene | 87 | 0.098 |
| 78 | 51.021 | 2-tolyl aldehyde | 81 | 0.468 |
| 79 | 51.181 | Unknown material | 74 | 0.207 |
| 80 | 51.522 | Unknown material | 78 | 0.339 |
| 81 | 51.636 | 1-methyl-4-(2-propenyl)-benzene | 81 | 0.166 |
| 82 | 51.807 | Unknown material | 55 | 0.271 |
| 83 | 52.491 | Unknown material | 70 | 1.504 |
| 84 | 52.682 | Unknown material | 65 | 0.037 |
| 85 | 52.773 | 2,4-xylenol | 94 | 0.096 |
| 86 | 52.978 | 1,2,4,5-tetramethylbenzene | 90 | 0.443 |
| 87 | 53.235 | 1,2,3,4-tetramethylbenzene | 85 | 0.119 |
| 88 | 53.44 | Unknown material | 71 | 2.200 |
| 89 | 53.583 | Unknown material | 64 | 0.421 |
| 90 | 53.697 | Unknown material | 66 | 0.133 |
| 91 | 53.916 | 1-methyl indenes | 96 | 1.494 |
| 92 | 54.462 | Unknown material | 60 | 2.630 |
| 93 | 54.601 | Unknown material | 43 | 0.261 |
| 94 | 54.733 | 3,5-dimethylbenzaldehyde | 96 | 0.162 |
| 95 | 54.855 | (2-methyl-1-butene thiazolinyl)-benzene | 90 | 0.237 |
| 96 | 55.112 | 2-methyl acetophenone | 96 | 1.421 |
| 97 | 55.664 | Naphthalene | 92 | 1.462 |
| 98 | 56.453 | Unknown material | 55 | 0.974 |
| 99 | 57.284 | 1,3-dimethyl indenes | 95 | 3.528 |
| 100 | 57.698 | Unknown material | 50 | 1.633 |
| 101 | 59.342 | Unknown material | 54 | 1.398 |
| 102 | 59.769 | 2-methylnaphthalene | 96 | 2.018 |
| 103 | 60.238 | 1,2,3-trimethyl indenes | 95 | 0.100 |
| 104 | 60.895 | Unknown material | 62 | 1.314 |
| 105 | 61.211 | 1,2-dihydro-1,1,6-trimethylnaphthalene | 80 | 5.975 |
| 106 | 62.091 | 1,1,3-trimethyl indenes | 95 | 1.003 |
| 107 | 64.663 | 2,7-dimethylnaphthalene | 95 | 7.735 |
Embodiment 7
1 method
1.1 cracking: the silica wool of first filling out 1mg left and right at the middle part of cracking silica tube, take 1 ± 0.05mg1,2-propylene glycol is on silica wool, then in sample upper end, fill out again about 1mg silica wool, then the cracking silica tube that sample is housed is put into the cracking room of CDS 2000 cracking instrument, under oxygen-containing gas atmosphere, temperature programme cracking is stage by stage carried out in platinum filament heating; The cracking condition of described CDS 2000 cracking instrument is: pyrolysis gas: 10%O
2and 90%N
2combination gas; Gas flow rate: 276ml/min; Cracking room temperature: 250 ℃; Heating rate: initial temperature is 300 ℃, keeps 5s, with 30 ℃/s, is warmed up to 900 ℃, keeps 5s.
1.2 filter: the composition that cracking is produced, by the cambridge filter device being connected with cracking instrument, filter online, and described cambridge filter diameter is 1cm;
1.3 trapping sample introductions: the adsorbent Carbotrap C that the gas phase composition after filtering is carried out filling in cold-trap (liquid nitrogen) and bushing pipe traps jointly, thermal desorption desorb sample introduction.Trapping sampling condition is: condenser temperature :-80 ℃; Bushing pipe adsorbent: Carbotrap C; Thermal desorption desorb sampling condition: 300 ℃ of desorption temperatures, desorption time: 2min.
1.4 measure: the gas phase composition after trapping sample introduction is carried out to quantitative and qualitative analysis detection by combined gas chromatography mass spectrometry; Described qualitative detection is by wiley7n and Nist98 spectrum data library searching, and composition basis for estimation is selected matching degree >=80; Described quantitative detection is to adopt peak area normalization method as described in Example 1 to determine the relative content of gas phase composition after cracking.
Described combined gas chromatography mass spectrometry condition is:
GC conditions is: chromatographic column: 60m * 0.32mm id * 1.8 μ m nominal(Supelco VOCOL); Injector temperature: 280 ℃; Carrier gas: high-purity helium, purity >=99.999%; Flow velocity: 1.2mL/min; Split ratio: 50:1; Heating schedule: 30 ℃ of initial temperatures keep 10min, rises to 180 ℃ with the speed of 10 ℃/min, then rises to 280 ℃ with the speed of 10 ℃/min, keeps 10min;
Mass spectrum condition is: ion source temperature: 230 ℃; Quadrupole rod temperature: 150 ℃; Transmission line temperature: 280 ℃; Solvent delay: 5min; Ionization mode: EI source; Ionizing energy: 70eV; Scan mode: full scan (scan), mass scanning scope m/z:10-300amu.
2 results and discussion
Utilize this method to measure the pyrolysis gas phase constituent of 1,2-PD, detailed process is shown in Fig. 1, and analysis result details are in Table 7.Result shows, by collection of illustrative plates, retrieves, and identifies altogether 8 kinds of pyrolysis gas phase constituents, and adopts peak area normalization method to determine the relative content of each composition.Wherein, the low-molecular-weight gas phase objectionable constituent such as formaldehyde, acetone can both be detected, thereby can evaluate all sidedly the harmfulness of 1,2-PD lysate.
The 1,2-PD pyrolysis gas phase constituent that table 7 GC-MS detects
| Sequence number | Retention time (min) | The compound of identifying | Matching degree | Relative peak area (%) |
| 1 | 6.457 | Formaldehyde | 92 | 0.102 |
| 3 | 12.807 | Acetone | 98 | 0.400 |
| 5 | 13.395 | 2-butanone | 98 | 1.326 |
| 6 | 21.607 | 2-propyl alcohol | 90 | 0.387 |
| 7 | 26.004 | 1-hydroxyl-2-acetone | 98 | 2.498 |
| 8 | 31.766 | 1,2-PD | 98 | 95.286 |
1 method
1.1 cracking: first put into a quartz rod in cracking silica tube, in quartz rod upper end, fill out the silica wool of 1mg left and right, compacting, take 1 ± 0.05mg eugenol on silica wool, then in sample upper end, fill out again about 1mg silica wool, then the cracking silica tube that sample is housed is put into the cracking room of CDS 5250T cracking instrument, under oxygen-containing gas atmosphere, temperature programme cracking is stage by stage carried out in platinum filament heating; The cracking condition of described CDS 5250T cracking instrument is: pyrolysis gas: 10%O
2and 90%N
2combination gas; Gas flow rate: 70ml/min; Cracking room temperature: 300 ℃; Heating rate: initial temperature is 300 ℃, keeps 5s, with 30 ℃/s, is warmed up to 900 ℃, keeps 5s.
1.2 filter: the composition that cracking is produced, by the cambridge filter device being connected with cracking instrument, filter online, and described cambridge filter diameter is 1cm;
1.3 trapping sample introductions: the adsorbent that the gas phase composition after filtering is carried out to fill in cold-trap (liquid nitrogen) and bushing pipe traps jointly, CIS4 programmed temperature sampling.Trapping sampling condition is: condenser temperature :-60 ℃; Bushing pipe adsorbent: TENAX; Temperature programme curve :-60 ℃ keep 1min, are then warmed up to 250 ℃ with 12 ℃/s, keep 5min at 250 ℃.
1.4 measure: the gas phase composition after trapping sample introduction is carried out to quantitative and qualitative analysis detection by combined gas chromatography mass spectrometry; Described qualitative detection is by wiley7n and Nist98 spectrum data library searching, and composition basis for estimation is selected matching degree >=80; Described quantitative detection is to adopt peak area normalization method as described in Example 1 to determine the relative content of gas phase composition after cracking.
Described combined gas chromatography mass spectrometry condition is:
GC conditions is: chromatographic column: 60m * 0.32mm id * 1.8 μ m nominal(Supelco VOCOL); Carrier gas: high-purity helium, purity >=99.999%; Flow velocity: 1.2mL/min; Split ratio: 50:1; Heating schedule: 30 ℃ of initial temperatures keep 10min, rises to 240 ℃ with the speed of 3.5 ℃/min, then rises to 280 ℃ with the speed of 20 ℃/min, keeps 10min.
Mass spectrum condition is: ion source temperature: 230 ℃; Quadrupole rod temperature: 150 ℃, transmission line temperature: 280 ℃; Solvent delay: 3min; Ionization mode: EI source; Ionizing energy: 70eV; Scan mode: full scan (scan), mass scanning scope (m/z): 10-300amu.
2 results and discussion
Utilize this method to measure the pyrolysis gas phase constituent of eugenol, detailed process is shown in Fig. 2 A, 2B, and analysis result details are in Table 8.Result shows, by wiley7n and Nist98 collection of illustrative plates, retrieves, and identifies altogether 12 kinds of pyrolysis gas phase constituents, and adopts peak area normalization method to determine the relative content of each composition.Wherein, many low-molecular-weight gas phase objectionable constituent can both detect, thereby can evaluate all sidedly the harmfulness of eugenol lysate.
The eugenol pyrolysis gas phase constituent that table 8 GC-MS detects
| Sequence number | Retention time (min) | The compound of identifying | Matching degree | Relative peak area (%) |
| 1 | 12.467 | 2-acryl aldehyde | 92 | 0.090 |
| 2 | 14.521 | Valylene | 86 | 0.111 |
| 3 | 16.126 | 1,5-hexadiene | 90 | 0.102 |
| 4 | 24.148 | Benzene | 96 | 0.838 |
| 5 | 28.51 | 2 Methylpropionic acid | 87 | 1.641 |
| 6 | 31.28 | Toluene | 95 | 0.778 |
| 7 | 37.254 | 1,3-dimethylbenzene | 92 | 0.110 |
| 8 | 37.546 | To toluene | 96 | 0.153 |
| 9 | 39.524 | Styrene | 98 | 0.417 |
| 10 | 61.01 | P-(1-ethyl vinyl)-anisole | 90 | 1.801 |
| 11 | 61.941 | Eugenol | 98 | 78.530 |
| 12 | 63.405 | 1,2-dimethoxy-4 '-(2-propenyl)-benzene | 90 | 15.428 |
In sum, the method of a kind of on-line determination tobacco additive agent provided by the invention or smoking material pyrolysis gas phase constituent, compare conventional method, adopt the cracking condition of ladder-elevating temperature formula, different trapping, sampling condition and gas chromatography mass spectrometry condition determinations, can not only measure formed half volatile component in adjuvant cracking process, can also measure many low-molecular-weight gas phase objectionable constituent in pyrolysis product, save time, can be effectively, low-molecular-weight gas phase composition in complete detection tobacco additive agent and smoking material pyrolysis product, detection accuracy is higher.Meanwhile, overcome the problem existing in existing method, for improving safety cigarette, reduce cigarette the harm tool of health is had very great significance, be worth very much promoting in actual applications.
Above-described embodiment is illustrative principle of the present invention and effect thereof only, but not for limiting the present invention.Any person skilled in the art scholar all can, under spirit of the present invention and category, modify or change above-described embodiment.Therefore, such as in affiliated technical field, have and conventionally know that the knowledgeable, not departing from all equivalence modifications that complete under disclosed spirit and technological thought or changing, must be contained by claim of the present invention.
Claims (10)
1. a method for on-line determination tobacco additive agent or smoking material pyrolysis gas phase constituent, specifically includes following steps:
1) cracking: tobacco additive agent or smoking material are carried out to temperature programme cracking;
2) filter: will, as tobacco additive agent described in step 1) or smoking material pyrolysis product, by cambridge filter device, filter;
3) trapping sample introduction: will be as step 2), gained gas phase composition is after trapping, then carries out desorption sample introduction;
4) measure: by gas chromatograph-mass spectrometer, sample introduction sample is carried out to quantitative and qualitative analysis detection.
2. the method for a kind of on-line determination tobacco additive agent according to claim 1 or smoking material pyrolysis gas phase constituent, it is characterized in that, described on-line determination specifically refers to: by sample by be connected to the cracking instrument, cambridge filter device of sealing one by pipeline, device and the gas chromatograph-mass spectrometer of trapping sample introduction are analyzed mensuration.
3. the method for a kind of on-line determination tobacco additive agent according to claim 1 or smoking material pyrolysis gas phase constituent, it is characterized in that, as described in step 1), temperature programme cracking specifically refers to: the sample that takes tobacco additive agent or smoking material, use silica wool that sample is fixed in cracking silica tube, put into again cracking instrument, under oxygen-containing gas atmosphere, temperature programme is stage by stage carried out in platinum filament heating, thus heating pyrolyze.
4. the method for a kind of on-line determination tobacco additive agent according to claim 3 or smoking material pyrolysis gas phase constituent, is characterized in that, the cracking condition of described cracking instrument is: pyrolysis gas: 10%O
2and 90%N
2combination gas; Gas flow rate: 70～276ml/min; Cracking room temperature: 250～300 ℃; Heating schedule: initial temperature is 300 ℃, keeps 5s, with 10～50 ℃/s, is warmed up to 900 ℃, keeps 5s.
5. the method for a kind of on-line determination tobacco additive agent according to claim 1 or smoking material pyrolysis gas phase constituent, it is characterized in that, as step 2) as described in cambridge filter device filter specifically finger: the pyrolysis product of tobacco additive agent or smoking material is filtered by cambridge filter device, cambridge filter device is the grain phase constituent interception in pyrolysis product, and gas phase composition in pyrolysis product is through cambridge filter.
6. the method for a kind of on-line determination tobacco additive agent according to claim 1 or smoking material pyrolysis gas phase constituent, it is characterized in that, as described in step 3), gas phase composition is through trapping concrete finger: use cold-trap and bushing pipe, and/or adsorbent is to step 2) in gained gas phase composition trap.
7. the method for a kind of on-line determination tobacco additive agent according to claim 6 or smoking material pyrolysis gas phase constituent, is characterized in that, the bushing pipe that uses cold-trap and be filled with adsorbent is to step 2) in gained gas phase composition trap.
8. the method for a kind of on-line determination tobacco additive agent according to claim 6 or smoking material pyrolysis gas phase constituent, is characterized in that, described to step 2) in gained gas phase composition through trapping actual conditions be: condenser temperature :-196～30 ℃; Adsorbent in bushing pipe: Carbotrap B or Carbotrap C or TENAX; The filling material of non-adsorbent: glass wool.
9. the method for a kind of on-line determination tobacco additive agent according to claim 1 or smoking material pyrolysis gas phase constituent, is characterized in that, as described in step 3), the actual conditions of desorption sample introduction is: at 200～330 ℃, keep 1～5min.
10. the method for a kind of on-line determination tobacco additive agent according to claim 1 or smoking material pyrolysis gas phase constituent, is characterized in that, as described in step 4), qualitative detection is by spectrum data library searching, determines the constituent of gas phase composition after cracking; Described quantitative detection is to adopt peak area normalization method to determine the relative content of gas phase composition after cracking.
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