CN113406238A - Efficient detection method for volatile components in cigarette smoke - Google Patents
Efficient detection method for volatile components in cigarette smoke Download PDFInfo
- Publication number
- CN113406238A CN113406238A CN202110725537.4A CN202110725537A CN113406238A CN 113406238 A CN113406238 A CN 113406238A CN 202110725537 A CN202110725537 A CN 202110725537A CN 113406238 A CN113406238 A CN 113406238A
- Authority
- CN
- China
- Prior art keywords
- sample
- volatile components
- smoke
- cigarette
- detection
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000779 smoke Substances 0.000 title claims abstract description 92
- 238000001514 detection method Methods 0.000 title claims abstract description 68
- 235000019504 cigarettes Nutrition 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 39
- 239000012634 fragment Substances 0.000 claims abstract description 33
- 238000001319 headspace solid-phase micro-extraction Methods 0.000 claims abstract description 33
- 239000012086 standard solution Substances 0.000 claims abstract description 25
- 238000004458 analytical method Methods 0.000 claims abstract description 22
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 claims abstract description 22
- 238000002470 solid-phase micro-extraction Methods 0.000 claims abstract description 16
- 238000003860 storage Methods 0.000 claims abstract description 16
- 238000005520 cutting process Methods 0.000 claims abstract description 15
- 238000007781 pre-processing Methods 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims description 20
- KWOLFJPFCHCOCG-JGUCLWPXSA-N 2,2,2-trideuterio-1-(2,3,4,5,6-pentadeuteriophenyl)ethanone Chemical compound [2H]C1=C([2H])C([2H])=C(C(=O)C([2H])([2H])[2H])C([2H])=C1[2H] KWOLFJPFCHCOCG-JGUCLWPXSA-N 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 239000012188 paraffin wax Substances 0.000 claims description 3
- 230000007613 environmental effect Effects 0.000 claims description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 17
- 239000003546 flue gas Substances 0.000 abstract description 16
- 239000000126 substance Substances 0.000 description 28
- 238000000605 extraction Methods 0.000 description 19
- 150000001335 aliphatic alkanes Chemical class 0.000 description 16
- 241000208125 Nicotiana Species 0.000 description 12
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 12
- 238000010257 thawing Methods 0.000 description 12
- 230000008569 process Effects 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- 239000012855 volatile organic compound Substances 0.000 description 5
- JHFNJRVFKOQALR-UHFFFAOYSA-N 1-prop-2-enylpyrrole Chemical compound C=CCN1C=CC=C1 JHFNJRVFKOQALR-UHFFFAOYSA-N 0.000 description 4
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 4
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 150000003505 terpenes Chemical class 0.000 description 4
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 3
- GFAZHVHNLUBROE-UHFFFAOYSA-N 1-hydroxybutan-2-one Chemical compound CCC(=O)CO GFAZHVHNLUBROE-UHFFFAOYSA-N 0.000 description 3
- UZLQSPYGTUMKGS-UHFFFAOYSA-N 2,3-dimethylcyclopent-2-en-1-one Chemical compound CC1=C(C)C(=O)CC1 UZLQSPYGTUMKGS-UHFFFAOYSA-N 0.000 description 3
- HPYNZHMRTTWQTB-UHFFFAOYSA-N 2,3-dimethylpyridine Chemical compound CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 description 3
- OJVAMHKKJGICOG-UHFFFAOYSA-N 2,5-hexanedione Chemical compound CC(=O)CCC(C)=O OJVAMHKKJGICOG-UHFFFAOYSA-N 0.000 description 3
- HJFZAYHYIWGLNL-UHFFFAOYSA-N 2,6-Dimethylpyrazine Chemical compound CC1=CN=CC(C)=N1 HJFZAYHYIWGLNL-UHFFFAOYSA-N 0.000 description 3
- VEKIYFGCEAJDDT-UHFFFAOYSA-N 2-pyridin-3-ylpyridine Chemical compound N1=CC=CC=C1C1=CC=CN=C1 VEKIYFGCEAJDDT-UHFFFAOYSA-N 0.000 description 3
- CHCCBPDEADMNCI-UHFFFAOYSA-N 3-Methyl-2-cyclopenten-1-one Chemical compound CC1=CC(=O)CC1 CHCCBPDEADMNCI-UHFFFAOYSA-N 0.000 description 3
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- ANGDWNBGPBMQHW-UHFFFAOYSA-N methyl cyanoacetate Chemical compound COC(=O)CC#N ANGDWNBGPBMQHW-UHFFFAOYSA-N 0.000 description 3
- CAWHJQAVHZEVTJ-UHFFFAOYSA-N methylpyrazine Chemical compound CC1=CN=CC=N1 CAWHJQAVHZEVTJ-UHFFFAOYSA-N 0.000 description 3
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 235000007586 terpenes Nutrition 0.000 description 3
- LABTWGUMFABVFG-ONEGZZNKSA-N (3E)-pent-3-en-2-one Chemical compound C\C=C\C(C)=O LABTWGUMFABVFG-ONEGZZNKSA-N 0.000 description 2
- SZQCPPRPWDXLMM-UHFFFAOYSA-N 1,4-dimethylpyrazole Chemical compound CC=1C=NN(C)C=1 SZQCPPRPWDXLMM-UHFFFAOYSA-N 0.000 description 2
- ZQEXIXXJFSQPNA-UHFFFAOYSA-N 1h-imidazole-5-carbaldehyde Chemical compound O=CC1=CNC=N1 ZQEXIXXJFSQPNA-UHFFFAOYSA-N 0.000 description 2
- OWLVHKAAVQCIEI-UHFFFAOYSA-N 2-(2,5-dihydrofuran-2-yl)-2,5-dihydrofuran Chemical compound C1=CCOC1C1C=CCO1 OWLVHKAAVQCIEI-UHFFFAOYSA-N 0.000 description 2
- PLXBWEPPAAQASG-UHFFFAOYSA-N 2-(Dimethylamino)acetonitrile Chemical compound CN(C)CC#N PLXBWEPPAAQASG-UHFFFAOYSA-N 0.000 description 2
- NRGGMCIBEHEAIL-UHFFFAOYSA-N 2-ethylpyridine Chemical class CCC1=CC=CC=N1 NRGGMCIBEHEAIL-UHFFFAOYSA-N 0.000 description 2
- XWKFPIODWVPXLX-UHFFFAOYSA-N 2-methyl-5-methylpyridine Natural products CC1=CC=C(C)N=C1 XWKFPIODWVPXLX-UHFFFAOYSA-N 0.000 description 2
- WLAMNBDJUVNPJU-UHFFFAOYSA-N 2-methylbutyric acid Chemical compound CCC(C)C(O)=O WLAMNBDJUVNPJU-UHFFFAOYSA-N 0.000 description 2
- ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 2-octanone Chemical compound CCCCCCC(C)=O ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 0.000 description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- BDCFWIDZNLCTMF-UHFFFAOYSA-N 2-phenylpropan-2-ol Chemical compound CC(C)(O)C1=CC=CC=C1 BDCFWIDZNLCTMF-UHFFFAOYSA-N 0.000 description 2
- XSOSLVVAKBKYRV-UHFFFAOYSA-N 3,4-dimethylcyclopent-2-en-1-one Chemical compound CC1CC(=O)C=C1C XSOSLVVAKBKYRV-UHFFFAOYSA-N 0.000 description 2
- BNYKZFOZWZMEJD-UHFFFAOYSA-N 3-methylimidazole-4-carbaldehyde Chemical compound CN1C=NC=C1C=O BNYKZFOZWZMEJD-UHFFFAOYSA-N 0.000 description 2
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical class C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical class O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- SQSPRWMERUQXNE-UHFFFAOYSA-N Guanylurea Chemical compound NC(=N)NC(N)=O SQSPRWMERUQXNE-UHFFFAOYSA-N 0.000 description 2
- -1 Pyridine compound Chemical class 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 125000003897 citraconoyl group Chemical group C(\C(\C)=C/C(=O)*)(=O)* 0.000 description 2
- MCFZBCCYOPSZLG-UHFFFAOYSA-N cyclopent-4-ene-1,3-dione Chemical compound O=C1CC(=O)C=C1 MCFZBCCYOPSZLG-UHFFFAOYSA-N 0.000 description 2
- IMKHDCBNRDRUEB-LLVKDONJSA-N dihydroactinidiolide Chemical compound C1CCC(C)(C)C2=CC(=O)O[C@@]21C IMKHDCBNRDRUEB-LLVKDONJSA-N 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- STJIISDMSMJQQK-UHFFFAOYSA-N furan-3-ylmethanol Chemical compound OCC=1C=COC=1 STJIISDMSMJQQK-UHFFFAOYSA-N 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 239000002207 metabolite Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- VKCYHJWLYTUGCC-UHFFFAOYSA-N nonan-2-one Chemical compound CCCCCCCC(C)=O VKCYHJWLYTUGCC-UHFFFAOYSA-N 0.000 description 2
- 238000010606 normalization Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SNICXCGAKADSCV-JTQLQIEISA-N (-)-Nicotine Chemical compound CN1CCC[C@H]1C1=CC=CN=C1 SNICXCGAKADSCV-JTQLQIEISA-N 0.000 description 1
- NLQMSBJFLQPLIJ-UHFFFAOYSA-N (3-methyloxetan-3-yl)methanol Chemical compound OCC1(C)COC1 NLQMSBJFLQPLIJ-UHFFFAOYSA-N 0.000 description 1
- YYGNTYWPHWGJRM-UHFFFAOYSA-N (6E,10E,14E,18E)-2,6,10,15,19,23-hexamethyltetracosa-2,6,10,14,18,22-hexaene Chemical compound CC(C)=CCCC(C)=CCCC(C)=CCCC=C(C)CCC=C(C)CCC=C(C)C YYGNTYWPHWGJRM-UHFFFAOYSA-N 0.000 description 1
- FEWIGMWODIRUJM-HWKANZROSA-N (E)-4-hexen-3-one Chemical compound CCC(=O)\C=C\C FEWIGMWODIRUJM-HWKANZROSA-N 0.000 description 1
- ZEHYJZXQEQOSON-AATRIKPKSA-N (e)-1-chloro-3-ethylpent-1-en-4-yn-3-ol Chemical compound CCC(O)(C#C)\C=C\Cl ZEHYJZXQEQOSON-AATRIKPKSA-N 0.000 description 1
- MITDXNUXOAYFGC-UHFFFAOYSA-N 1-prop-2-ynylbenzimidazole Chemical compound C1=CC=C2N(CC#C)C=NC2=C1 MITDXNUXOAYFGC-UHFFFAOYSA-N 0.000 description 1
- 239000001934 2,5-dimethylpyrazine Substances 0.000 description 1
- GRZZTYUZNNKOFW-UHFFFAOYSA-N 2-hydroxy-1,3,2-dioxaphospholane Chemical compound OP1OCCO1 GRZZTYUZNNKOFW-UHFFFAOYSA-N 0.000 description 1
- NUKYPUAOHBNCPY-UHFFFAOYSA-N 4-aminopyridine Chemical compound NC1=CC=NC=C1 NUKYPUAOHBNCPY-UHFFFAOYSA-N 0.000 description 1
- VJWJZPNGHLCFNO-UHFFFAOYSA-N 4-ethynyl-6,6-dimethyl-2,5-dihydropyran Chemical compound CC1(C)CC(C#C)=CCO1 VJWJZPNGHLCFNO-UHFFFAOYSA-N 0.000 description 1
- FEWIGMWODIRUJM-UHFFFAOYSA-N 4-hexen-3-one Chemical class CCC(=O)C=CC FEWIGMWODIRUJM-UHFFFAOYSA-N 0.000 description 1
- 150000000530 4H-pyran-4-ones Chemical class 0.000 description 1
- VTNQPKFIQCLBDU-UHFFFAOYSA-N Acetochlor Chemical compound CCOCN(C(=O)CCl)C1=C(C)C=CC=C1CC VTNQPKFIQCLBDU-UHFFFAOYSA-N 0.000 description 1
- 206010006458 Bronchitis chronic Diseases 0.000 description 1
- IMKHDCBNRDRUEB-UHFFFAOYSA-N Dihydroactinidiolide Natural products C1CCC(C)(C)C2=CC(=O)OC21C IMKHDCBNRDRUEB-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 208000001132 Osteoporosis Diseases 0.000 description 1
- BHEOSNUKNHRBNM-UHFFFAOYSA-N Tetramethylsqualene Natural products CC(=C)C(C)CCC(=C)C(C)CCC(C)=CCCC=C(C)CCC(C)C(=C)CCC(C)C(C)=C BHEOSNUKNHRBNM-UHFFFAOYSA-N 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 159000000021 acetate salts Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229940053200 antiepileptics fatty acid derivative Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000004931 azocinyl group Chemical group N1=C(C=CC=CC=C1)* 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 206010006451 bronchitis Diseases 0.000 description 1
- RHDGNLCLDBVESU-UHFFFAOYSA-N but-3-en-4-olide Chemical class O=C1CC=CO1 RHDGNLCLDBVESU-UHFFFAOYSA-N 0.000 description 1
- 235000019282 butylated hydroxyanisole Nutrition 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 238000004177 carbon cycle Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 208000007451 chronic bronchitis Diseases 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 208000029078 coronary artery disease Diseases 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- PRAKJMSDJKAYCZ-UHFFFAOYSA-N dodecahydrosqualene Natural products CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- KKJLGRFVBCOZKZ-UHFFFAOYSA-N ethenyl dihydrogen phosphite Chemical compound OP(O)OC=C KKJLGRFVBCOZKZ-UHFFFAOYSA-N 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- 230000035558 fertility Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 201000010235 heart cancer Diseases 0.000 description 1
- 208000024348 heart neoplasm Diseases 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229930003658 monoterpene Natural products 0.000 description 1
- 150000002773 monoterpene derivatives Chemical class 0.000 description 1
- 235000002577 monoterpenes Nutrition 0.000 description 1
- 229960002715 nicotine Drugs 0.000 description 1
- SNICXCGAKADSCV-UHFFFAOYSA-N nicotine Natural products CN1CCCC1C1=CC=CN=C1 SNICXCGAKADSCV-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229930015704 phenylpropanoid Natural products 0.000 description 1
- 125000001474 phenylpropanoid group Chemical group 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- HUAZGNHGCJGYNP-UHFFFAOYSA-N propyl butyrate Chemical compound CCCOC(=O)CCC HUAZGNHGCJGYNP-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000003860 sleep quality Effects 0.000 description 1
- 230000000391 smoking effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 229940031439 squalene Drugs 0.000 description 1
- TUHBEKDERLKLEC-UHFFFAOYSA-N squalene Natural products CC(=CCCC(=CCCC(=CCCC=C(/C)CCC=C(/C)CC=C(C)C)C)C)C TUHBEKDERLKLEC-UHFFFAOYSA-N 0.000 description 1
- YYGNTYWPHWGJRM-AAJYLUCBSA-N squalene Chemical compound CC(C)=CCC\C(C)=C\CC\C(C)=C\CC\C=C(/C)CC\C=C(/C)CCC=C(C)C YYGNTYWPHWGJRM-AAJYLUCBSA-N 0.000 description 1
- 238000007619 statistical method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000019281 tert-butylhydroquinone Nutrition 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- UAXOELSVPTZZQG-UHFFFAOYSA-N tiglic acid Natural products CC(C)=C(C)C(O)=O UAXOELSVPTZZQG-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/86—Signal analysis
- G01N30/8675—Evaluation, i.e. decoding of the signal into analytical information
-
- 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
- G01N2030/042—Standards
- G01N2030/045—Standards internal
-
- 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
- G01N2030/042—Standards
- G01N2030/047—Standards external
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Library & Information Science (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Sampling And Sample Adjustment (AREA)
Abstract
The invention discloses a high-efficiency detection method of volatile components in cigarette smoke, which comprises the following steps: s1, extracting smoke components, sucking and trapping the smoke of the cigarette, and enabling the mainstream smoke of the cigarette to be detected to pass through a Cambridge filter; s2, preprocessing a sample, cutting the Cambridge filter disc obtained in the step S1 into small fragments, putting the fragments into a headspace bottle, adding an internal standard solution to obtain the sample, and then putting the sample into a refrigerator for storage for later use; s3, performing headspace solid phase microextraction, namely taking out the sample prepared in the step S2, placing the sample into a thermostat, standing and unfreezing, and then extracting by adopting full-automatic headspace solid phase microextraction HS-SPME; and S4, performing GC-MS detection, and performing detection analysis on the sample extracted in the step S3 in a GC-MS detection system. The method can obtain more than 500 volatile components by detecting the flue gas, has wide detection range, and is simple, convenient, rapid and efficient to operate.
Description
Technical Field
The invention relates to the technical field of cigarette component analysis, in particular to a high-efficiency detection method for volatile components in cigarette smoke.
Background
Cigarette combustion is a complex chemical system, except for gas phase substances (such as carbon monoxide, water, methane and other lower hydrocarbon compounds) generated by full combustion and cracking of organic matters, due to insufficient oxygen supply in partial areas, a plurality of complex chemical changes occur in an anoxic state, volatile substances (such as semi-volatile 5-membered ring and 6-membered ring nitrogen-heterocyclic compounds) in tobacco shreds are volatilized into smoke gas flow, and terpenes, saccharides, amino acids, celluloses and other components in tobacco are subjected to thermal decomposition, thermal synthesis, dry distillation, polymerization, condensation, free radical and other reactions to generate volatile and semi-volatile gases. The smoke components generated after the cigarette is burnt are very complex, and comprise carboxylic acids, lipids, aldehydes, ketones, nicotine, alkane and the like, and the specific chemical substances are more than 4000. Wherein the harmful substances affect the sleep quality and fertility of smokers, and cause chronic bronchitis. Osteoporosis and other health problems, and even serious diseases such as coronary heart disease, cancer and the like. Along with the improvement of health consciousness of people, the attention to harmful substances in smoke generated by cigarette combustion is increased, and a plurality of products capable of reducing the harmfulness of cigarettes are designed. For example, the external filter cigarette holder directly blocks substances such as tar in smoke through micropores, but the substances block harmful substances only through an absorption means, and the harm of the cigarette to human bodies cannot be reduced substantially.
Therefore, before the cigarette leaves factory, the analysis and determination of the composition of the components in the smoke has very important significance for improving the quality of the tobacco leaves and promoting the sustainable development of the tobacco leaves. In the prior art, the detection method of cigarette smoke components is mainly a GC-MS method, but most of the methods have the problems of complex operation, small detection range and the like. Therefore, a method for measuring chemical components in smoke with high speed, high efficiency, simple operation and wide detection range is urgently needed.
Chinese patent (CN 106556665A) discloses a method for simultaneously measuring 14 sour ingredients in main stream smoke of cigarettes, which comprises the following steps: 1) after particulate matters of mainstream smoke of the cigarettes are captured by using a Cambridge filter, the Cambridge filter is transferred into an extraction container, an acetone solution is added, an internal standard solution is added for oscillation extraction, and a supernatant is taken, added with a derivatization reagent and heated to obtain a smoke sample; 2) and (3) detecting the flue gas sample by adopting GC-MS (gas chromatography-Mass spectrometer), and detecting the content of 14 sour components by an internal standard quantitative method. The method adopts solvent extraction-gas chromatography-mass spectrometry combined method, can simultaneously determine the content of 14 sour components in cigarette mainstream smoke, and is suitable for determining the content of the sour components in cigarette smoke. However, the method is complicated to operate, an organic solvent is needed as a solvent for back extraction, and in the process, the method of shaking, shaking or heating is adopted, so that volatile substances are easily lost.
Chinese patent (CN 108680694A) discloses a method for measuring volatile chemical components in smoke by using an infrared mirror reflection furnace-headspace gas chromatography-mass spectrometry, which comprises the following steps: (A) placing the tobacco sample and the glass fiber filter disc under constant temperature and humidity for balancing for 48 hours; (B) weighing not less than 0.50g of the tobacco leaf sample obtained in the step A, placing the tobacco leaf sample into a quartz tube, heating by using infrared rays, carrying out temperature rise program heating, introducing air into the quartz tube during heating to simulate the combustion process of the tobacco leaves, stopping infrared ray heating after a period of time, introducing nitrogen into the quartz tube to simulate the smoldering process of the tobacco leaves, trapping chemical components in smoke by using a glass fiber filter disc, and repeatedly carrying out the steps of simulating combustion and simulating smoldering for a plurality of times; (C) and (3) putting the glass fiber filter disc into a headspace bottle, and performing headspace gas chromatography-mass spectrometry combined analysis. The method can make the tobacco shred consumption reach or even exceed 1 cigarette tobacco leaf raw material, and ensure accurate analysis of trace amount of volatile chemical components in tobacco leaf smoke. However, the method adopts an infrared mirror reflection furnace to simulate the combustion process of the flue gas, and only 100 kinds of volatile compounds can be obtained by measurement according to the method, so that the requirement of wide detection of flue gas components cannot be met.
Disclosure of Invention
In order to solve the problems, the invention provides a high-efficiency detection method for volatile components in cigarette smoke, which specifically comprises the steps of smoke component extraction, sample pretreatment, headspace solid phase microextraction, GC-MS detection and the like.
The technical scheme provided by the invention is as follows: a high-efficiency detection method for volatile components in cigarette smoke comprises the following steps:
s1, extracting smoke components, sucking and trapping the smoke of the cigarette, and enabling the mainstream smoke of the cigarette to be detected to pass through a Cambridge filter;
s2, preprocessing a sample, cutting the Cambridge filter disc obtained in the step S1 into small fragments, putting the fragments into a headspace bottle, adding an internal standard solution to obtain the sample, and then putting the sample into a refrigerator for storage for later use;
s3, performing headspace solid phase microextraction, namely taking out the sample prepared in the step S2, placing the sample into a thermostat, standing and unfreezing, and then extracting by adopting full-automatic headspace solid phase microextraction HS-SPME;
and S4, performing GC-MS detection, and enabling the sample to be detected extracted in the step S3 to enter a GC-MS detection system for detection and analysis.
Further, the mass ratio of the fragments to the internal standard solution in the step S2 is 40: (1.3-2.0).
Further, the internal standard solution in the step S2 is [2H8] -acetophenone with the concentration of 10 μ g/mL.
Further, in the step S2, the cambridge filter obtained in the step S1 is cut into small pieces each having a length and a width of 1-2 cm.
Further, the environmental temperature of the sample pretreatment in the step S2 is 0-20 ℃.
Further, in the step S2, the sample is stored in a refrigerator at-20 ℃ for further use.
Further, the heating temperature during the extraction in the step S3 is 50-80 ℃.
Further, in the step S3, the sample prepared in the step S2 is taken out and placed in an incubator for standing at 16-20 ℃.
Further, in the step S3, the sample prepared in the step S2 is taken out and placed in an incubator for standing for 25-35 min.
Further, the step S4 includes the following steps: a normal paraffin mixture solution with a concentration of 10ppm was prepared and subjected to GC-MS analysis as an external standard together with the sample extracted in step S3.
The internal standard solution is a method for accurate quantification in chromatographic analysis, a certain weight of pure substances are added into a certain amount of sample mixture to be analyzed as internal standard substances, and the content of the component to be detected is calculated according to the mass ratio of the sample to be detected to the internal standard substances, the ratio of corresponding chromatographic peak areas and relative correction factors.
The general internal standard solution selection criteria are as follows:
a. the original sample contains no components
b. The retention time of the sample should be close to but not overlapped with that of the sample
c. Is a high purity standard substance, or a substance with a known content
d. Has certain chemical stability under given chromatographic conditions
Therefore, the invention selects the [2H8] -acetophenone as the isotope internal standard substance, and the accuracy is very high.
The invention has the beneficial effects that:
1. the invention provides a high-efficiency detection method of volatile components in cigarette smoke, which specifically comprises the steps of smoke component extraction, sample pretreatment, headspace solid phase microextraction, GC-MS detection and the like, wherein more than 500 volatile components can be obtained by detecting smoke through the method, and the method has the advantages of wide detection range, simple and convenient operation, rapidness and high efficiency. The detection method provided by the invention can detect smoke components more comprehensively, quickly and efficiently, and can judge the quality of cigarettes better.
2. According to the efficient detection method for volatile components in cigarette smoke, provided by the invention, the Cambridge filter fragment after smoke collection is directly subjected to headspace solid phase microextraction, other intermediate treatment steps are not required, smoke components are retained to the maximum extent, the loss of volatile components in the treatment process can be reduced, the detection of more than 500 volatile components in the smoke can be realized, and the detection range of disposable smoke is widest based on the GC-MS technology at present.
Drawings
FIG. 1 is a flow chart of a method for efficiently detecting volatile components in cigarette smoke according to an embodiment of the present invention.
Detailed Description
In order to more clearly illustrate the embodiments of the present invention and the technical solutions in the prior art, the following will describe the specific embodiments of the present invention with reference to the accompanying drawings.
It is obvious that the drawings in the following description are only some examples of the invention, and it is obvious to a person skilled in the art that other drawings and other embodiments can be obtained from these drawings without inventive effort, and the invention is not limited to this example.
In the embodiment of the invention, SPME sample injection parameters are as follows: aging temperature: 250 ℃; aging time: 5 min; heating temperature: 60 ℃; heating time: 10 min; adsorption time: 20 min; analysis time: 5 min; aging time after sample introduction: and 5 min.
The chromatographic collection conditions were: shunting mode: no flow diversion; carrier gas: he; a chromatographic column: DB-5MS (30m x 0.25mm x 0.25 μm); column flow rate: 1.0 mL/min; column box temperature program: the temperature was maintained at 40 ℃ for 5 minutes, and then the temperature was raised to 280 ℃ (6 ℃/min) for 5 minutes. The mass spectrum acquisition conditions are as follows: temperature of a front sample inlet: 250 ℃; transmission line temperature: 280 ℃; ion source temperature: 230 ℃; quadrupole temperature: 150 ℃; ionization voltage: 70 eV; solvent retardation: and 5 min. See table 1 for details.
Table 1: collecting conditions of chromatographic mass spectrum
Item | Parameter(s) |
Sample volume | - |
Shunting Mode (Front Inlet Mode) | splitless |
Carrier Gas (Carrier Gas) | Helium |
Chromatographic Column (Column) | DB-5MS (30m x 0.25mm x 0.25μm) |
Column Flow rate (Column Flow) | 1.0mL/min |
Column box Temperature program (Oven Temperature Ramp) | 40°C hold on 5 min, raised to 280°C at a rate of 6 °C/min, hold for 5 min |
Front Injection Temperature (Front Injection Temperature) | 250°C |
Transmission Line Temperature (Transfer Line Temperature) | 280°C |
Ion Source Temperature (Ion Source Temperature) | 230°C |
Four-lever Temperature (Quad Temperature) | 150°C |
Ionization voltage (Electron Energy) | 70 eV |
Solvent Delay (Solvent Delay) | 5 min |
In the embodiment of the invention, the specific steps of smoking and trapping of smoke are carried out according to the method specified in GB/T19609-2004, so that the mainstream smoke of the cigarette to be detected completely passes through the Cambridge filter disc, the Cambridge filter disc is used for trapping volatile components in the smoke, then the Cambridge filter disc collecting the smoke is detected, and classification numbering is carried out according to the difference of the smoke.
In the present example, 12 samples were prepared in total and the metabolic studies were performed in 4 groups, wherein each group had 3 biological replicates. The grouping of each sample and the corresponding information are shown in table 2. The 12 samples were subjected to the component detection using the method provided by the present invention, and the 12 samples corresponded to examples 1 to 12, respectively.
Table 2: sample number information
Examples | Sample grouping | Sample name | Sample description |
Example 1 | CZGZ | CZGZ-1 | Flue gas |
Example 2 | CZGZ | CZGZ-2 | Flue gas |
Example 3 | CZGZ | CZGZ-3 | Flue gas |
Example 4 | CZG4 | CZG4-1 | Flue gas |
Example 5 | CZG4 | CZG4-2 | Flue gas |
Example 6 | CZG4 | CZG4-3 | Flue gas |
Example 7 | CZGZ7 | CZGZ7-1 | Flue gas |
Example 8 | CZGZ7 | CZGZ7-2 | Flue gas |
Example 9 | CZGZ7 | CZGZ7-3 | Flue gas |
Example 10 | CZGZ9 | CZGZ9-1 | Flue gas |
Example 11 | CZGZ9 | CZGZ9-2 | Flue gas |
Example 12 | CZGZ9 | CZGZ9-3 | Flue gas |
The specific embodiment of the invention is as follows:
example 1
S1, extracting smoke components, namely collecting the smoke CZGZ-1, and enabling the mainstream smoke of the cigarette to be detected to pass through a Cambridge filter disc;
s2, preprocessing a sample, cutting the Cambridge filter disc obtained in the step S1 into small fragments with the length and width of 1cm on an ice block, taking 0.4g of the fragments into a headspace bottle, quickly adding 20 mu L of internal standard solution to obtain a sample to be detected, screwing a bottle cap, and then placing the sample to be detected into a refrigerator for storage at-20 ℃ for later use, wherein the internal standard solution is [2H8] -acetophenone with the concentration of 10 mu g/mL;
s3, performing headspace solid-phase microextraction, namely taking out the sample to be detected prepared in the step S2, placing the sample into a thermostat, standing for 25min for thawing, and then extracting by adopting full-automatic headspace solid-phase microextraction HS-SPME, wherein the heating temperature is 50 ℃ during extraction;
and S4, performing GC-MS detection, and performing detection analysis on the sample extracted in the step S3 in a GC-MS detection system. And preparing normal alkane mixed liquor with the concentration of 10ppm as an external standard and carrying out GC-MS analysis together with a sample.
Example 2
S1, extracting smoke components, namely collecting the smoke CZGZ-2, and enabling the mainstream smoke of the cigarette to be detected to pass through a Cambridge filter disc;
s2, preprocessing a sample, cutting the Cambridge filter disc obtained in the step S1 into small fragments with the length and width of 1.5cm on an ice block, taking 0.4g of the fragments into a headspace bottle, quickly adding 25 mu L of internal standard liquid to obtain a sample to be detected, screwing a bottle cap, and then placing the sample to be detected into a refrigerator for storage at-20 ℃ for later use, wherein the internal standard liquid is [2H8] -acetophenone with the concentration of 10 mu g/mL;
s3, performing headspace solid-phase microextraction, namely taking out the sample to be detected prepared in the step S2, placing the sample into a thermostat, standing for 30min for thawing, and then extracting by adopting full-automatic headspace solid-phase microextraction HS-SPME, wherein the heating temperature is 65 ℃ during extraction;
and S4, performing GC-MS detection, and performing detection analysis on the sample extracted in the step S3 in a GC-MS detection system. And preparing normal alkane mixed liquor with the concentration of 10ppm as an external standard and carrying out GC-MS analysis together with a sample.
Example 3
S1, extracting smoke components, namely collecting the smoke CZGZ-3, and enabling the mainstream smoke of the cigarette to be detected to pass through a Cambridge filter disc;
s2, preprocessing a sample, cutting the Cambridge filter disc obtained in the step S1 into small fragments with the length and width of 2cm on an ice block, taking 0.4g of the fragments into a headspace bottle, quickly adding 30 mu L of internal standard solution to obtain a sample to be detected, screwing a bottle cap, and then placing the sample to be detected into a refrigerator for storage at-20 ℃ for later use, wherein the internal standard solution is [2H8] -acetophenone with the concentration of 10 mu g/mL;
s3, performing headspace solid-phase microextraction, namely taking out the sample to be detected prepared in the step S2, placing the sample into a thermostat, standing for 35min for thawing, and then extracting by adopting full-automatic headspace solid-phase microextraction HS-SPME, wherein the heating temperature is 80 ℃ during extraction;
and S4, performing GC-MS detection, and performing detection analysis on the sample extracted in the step S3 in a GC-MS detection system. And preparing normal alkane mixed liquor with the concentration of 10ppm as an external standard and carrying out GC-MS analysis together with a sample.
Example 4
S1, extracting smoke components, namely collecting the smoke CZG4-1, and enabling the mainstream smoke of the cigarette to be detected to pass through a Cambridge filter disc;
s2, preprocessing a sample, cutting the Cambridge filter disc obtained in the step S1 into small fragments with the length and width of 1cm on an ice block, taking 0.4g of the fragments into a headspace bottle, quickly adding 20 mu L of internal standard solution to obtain a sample to be detected, screwing a bottle cap, and then placing the sample to be detected into a refrigerator for storage at-20 ℃ for later use, wherein the internal standard solution is [2H8] -acetophenone with the concentration of 10 mu g/mL;
s3, performing headspace solid-phase microextraction, namely taking out the sample to be detected prepared in the step S2, placing the sample into a thermostat, standing for 25min for thawing, and then extracting by adopting full-automatic headspace solid-phase microextraction HS-SPME, wherein the heating temperature is 50 ℃ during extraction;
and S4, performing GC-MS detection, and performing detection analysis on the sample extracted in the step S3 in a GC-MS detection system. And preparing normal alkane mixed liquor with the concentration of 10ppm as an external standard and carrying out GC-MS analysis together with a sample.
Example 5
S1, extracting smoke components, namely collecting the smoke CZG4-2, and enabling the mainstream smoke of the cigarette to be detected to pass through a Cambridge filter disc;
s2, preprocessing a sample, cutting the Cambridge filter disc obtained in the step S1 into small fragments with the length and width of 1.5cm on an ice block, taking 0.4g of the fragments into a headspace bottle, quickly adding 25 mu L of internal standard liquid to obtain a sample to be detected, screwing a bottle cap, and then placing the sample to be detected into a refrigerator for storage at-20 ℃ for later use, wherein the internal standard liquid is [2H8] -acetophenone with the concentration of 10 mu g/mL;
s3, performing headspace solid-phase microextraction, namely taking out the sample to be detected prepared in the step S2, placing the sample into a thermostat, standing for 30min for thawing, and then extracting by adopting full-automatic headspace solid-phase microextraction HS-SPME, wherein the heating temperature is 65 ℃ during extraction;
and S4, performing GC-MS detection, and performing detection analysis on the sample extracted in the step S3 in a GC-MS detection system. And preparing normal alkane mixed liquor with the concentration of 10ppm as an external standard and carrying out GC-MS analysis together with a sample.
Example 6
S1, extracting smoke components, namely collecting the smoke CZG4-3, and enabling the mainstream smoke of the cigarette to be detected to pass through a Cambridge filter disc;
s2, preprocessing a sample, cutting the Cambridge filter disc obtained in the step S1 into small fragments with the length and width of 2cm on an ice block, taking 0.4g of the fragments into a headspace bottle, quickly adding 30 mu L of internal standard solution to obtain a sample to be detected, screwing a bottle cap, and then placing the sample to be detected into a refrigerator for storage at-20 ℃ for later use, wherein the internal standard solution is [2H8] -acetophenone with the concentration of 10 mu g/mL;
s3, performing headspace solid-phase microextraction, namely taking out the sample to be detected prepared in the step S2, placing the sample into a thermostat, standing for 35min for thawing, and then extracting by adopting full-automatic headspace solid-phase microextraction HS-SPME, wherein the heating temperature is 80 ℃ during extraction;
and S4, performing GC-MS detection, and performing detection analysis on the sample extracted in the step S3 in a GC-MS detection system. And preparing normal alkane mixed liquor with the concentration of 10ppm as an external standard and carrying out GC-MS analysis together with a sample.
Example 7
S1, extracting smoke components, namely collecting the smoke CZGZ7-1, and enabling the mainstream smoke of the cigarette to be detected to pass through a Cambridge filter disc;
s2, preprocessing a sample, cutting the Cambridge filter disc obtained in the step S1 into small fragments with the length and width of 1cm on an ice block, taking 0.4g of the fragments into a headspace bottle, quickly adding 20 mu L of internal standard solution to obtain a sample to be detected, screwing a bottle cap, and then placing the sample to be detected into a refrigerator for storage at-20 ℃ for later use, wherein the internal standard solution is [2H8] -acetophenone with the concentration of 10 mu g/mL;
s3, performing headspace solid-phase microextraction, namely taking out the sample to be detected prepared in the step S2, placing the sample into a thermostat, standing for 25min for thawing, and then extracting by adopting full-automatic headspace solid-phase microextraction HS-SPME, wherein the heating temperature is 50 ℃ during extraction;
and S4, performing GC-MS detection, and performing detection analysis on the sample extracted in the step S3 in a GC-MS detection system. And preparing normal alkane mixed liquor with the concentration of 10ppm as an external standard and carrying out GC-MS analysis together with a sample.
Example 8
S1, extracting smoke components, namely collecting the smoke CZGZ7-2, and enabling the mainstream smoke of the cigarette to be detected to pass through a Cambridge filter disc;
s2, preprocessing a sample, cutting the Cambridge filter disc obtained in the step S1 into small fragments with the length and width of 1.5cm on an ice block, taking 0.4g of the fragments into a headspace bottle, quickly adding 25 mu L of internal standard liquid to obtain a sample to be detected, screwing a bottle cap, and then placing the sample to be detected into a refrigerator for storage at-20 ℃ for later use, wherein the internal standard liquid is [2H8] -acetophenone with the concentration of 10 mu g/mL;
s3, performing headspace solid-phase microextraction, namely taking out the sample to be detected prepared in the step S2, placing the sample into a thermostat, standing for 30min for thawing, and then extracting by adopting full-automatic headspace solid-phase microextraction HS-SPME, wherein the heating temperature is 65 ℃ during extraction;
and S4, performing GC-MS detection, and performing detection analysis on the sample extracted in the step S3 in a GC-MS detection system. And preparing normal alkane mixed liquor with the concentration of 10ppm as an external standard and carrying out GC-MS analysis together with a sample.
Example 9
S1, extracting smoke components, namely collecting the smoke CZGZ7-3, and enabling the mainstream smoke of the cigarette to be detected to pass through a Cambridge filter disc;
s2, preprocessing a sample, cutting the Cambridge filter disc obtained in the step S1 into small fragments with the length and width of 2cm on an ice block, taking 0.4g of the fragments into a headspace bottle, quickly adding 30 mu L of internal standard solution to obtain a sample to be detected, screwing a bottle cap, and then placing the sample to be detected into a refrigerator for storage at-20 ℃ for later use, wherein the internal standard solution is [2H8] -acetophenone with the concentration of 10 mu g/mL;
s3, performing headspace solid-phase microextraction, namely taking out the sample to be detected prepared in the step S2, placing the sample into a thermostat, standing for 35min for thawing, and then extracting by adopting full-automatic headspace solid-phase microextraction HS-SPME, wherein the heating temperature is 80 ℃ during extraction;
and S4, performing GC-MS detection, and performing detection analysis on the sample extracted in the step S3 in a GC-MS detection system. And preparing normal alkane mixed liquor with the concentration of 10ppm as an external standard and carrying out GC-MS analysis together with a sample.
Example 10
S1, extracting smoke components, namely collecting the smoke CZGZ9-1, and enabling the mainstream smoke of the cigarette to be detected to pass through a Cambridge filter disc;
s2, preprocessing a sample, cutting the Cambridge filter disc obtained in the step S1 into small fragments with the length and width of 1cm on an ice block, taking 0.4g of the fragments into a headspace bottle, quickly adding 20 mu L of internal standard solution to obtain a sample to be detected, screwing a bottle cap, and then placing the sample to be detected into a refrigerator for storage at-20 ℃ for later use, wherein the internal standard solution is [2H8] -acetophenone with the concentration of 10 mu g/mL;
s3, performing headspace solid-phase microextraction, namely taking out the sample to be detected prepared in the step S2, placing the sample into a thermostat, standing for 25min for thawing, and then extracting by adopting full-automatic headspace solid-phase microextraction HS-SPME, wherein the heating temperature is 50 ℃ during extraction;
and S4, performing GC-MS detection, and performing detection analysis on the sample extracted in the step S3 in a GC-MS detection system. And preparing normal alkane mixed liquor with the concentration of 10ppm as an external standard and carrying out GC-MS analysis together with a sample.
Example 11
S1, extracting smoke components, namely collecting the smoke CZGZ9-2, and enabling the mainstream smoke of the cigarette to be detected to pass through a Cambridge filter disc;
s2, preprocessing a sample, cutting the Cambridge filter disc obtained in the step S1 into small fragments with the length and width of 1.5cm on an ice block, taking 0.4g of the fragments into a headspace bottle, quickly adding 25 mu L of internal standard liquid to obtain a sample to be detected, screwing a bottle cap, and then placing the sample to be detected into a refrigerator for storage at-20 ℃ for later use, wherein the internal standard liquid is [2H8] -acetophenone with the concentration of 10 mu g/mL;
s3, performing headspace solid-phase microextraction, namely taking out the sample to be detected prepared in the step S2, placing the sample into a thermostat, standing for 30min for thawing, and then extracting by adopting full-automatic headspace solid-phase microextraction HS-SPME, wherein the heating temperature is 65 ℃ during extraction;
and S4, performing GC-MS detection, and performing detection analysis on the sample extracted in the step S3 in a GC-MS detection system. And preparing normal alkane mixed liquor with the concentration of 10ppm as an external standard and carrying out GC-MS analysis together with a sample.
Example 12
S1, extracting smoke components, namely collecting the smoke CZGZ9-3, and enabling the mainstream smoke of the cigarette to be detected to pass through a Cambridge filter disc;
s2, preprocessing a sample, cutting the Cambridge filter disc obtained in the step S1 into small fragments with the length and width of 2cm on an ice block, taking 0.4g of the fragments into a headspace bottle, quickly adding 30 mu L of internal standard solution to obtain a sample to be detected, screwing a bottle cap, and then placing the sample to be detected into a refrigerator for storage at-20 ℃ for later use, wherein the internal standard solution is [2H8] -acetophenone with the concentration of 10 mu g/mL;
s3, performing headspace solid-phase microextraction, namely taking out the sample to be detected prepared in the step S2, placing the sample into a thermostat, standing for 35min for thawing, and then extracting by adopting full-automatic headspace solid-phase microextraction HS-SPME, wherein the heating temperature is 80 ℃ during extraction;
and S4, performing GC-MS detection, and performing detection analysis on the sample extracted in the step S3 in a GC-MS detection system. And preparing normal alkane mixed liquor with the concentration of 10ppm as an external standard and carrying out GC-MS analysis together with a sample.
Data processing method
The original data files obtained from the GC-MS analysis in examples 1-12 were first subjected to peak extraction by MassHunter software (Agilent) to obtain information on mass-to-charge ratio, retention time, and peak area of characteristic peaks, and then the data were subjected to statistical analysis. To better analyze the data, embodiments of the present invention perform a series of preparations and arrangements on the raw data. The method mainly comprises the following steps:
(1) calculating a retention index;
(2) filtering the single Peak, and only retaining Peak area data with a single null value of no more than 50% or with null values of no more than 50% in all groups;
(3) data normalization (normalization) using an internal standard.
Method for analyzing results
Volatile Organic Compounds (VOCs) are generally understood to be various organic compounds having a boiling point of from 50 ℃ to 260 ℃ at atmospheric pressure. VOCs can be further classified into alkanes, aromatic hydrocarbons, esters, aldehydes, and others according to their chemical structures. Benzene, toluene, xylene, styrene, phenethyl alcohol, chloroform, propyl butyrate, 2-nonanone, 2-octanone, etc. are common. Plants release a large amount of volatile organic compounds, mainly isoprenoids and monoterpenes, to the atmosphere in physiological processes. Plant-derived volatile organic compounds (BVOCs) have an extremely important ecological function. BVOCs are bio-signal substances that can transmit signals or information between plant tissues-organs, plant-plants and plant-animals to warn other organisms in the vicinity, resist environmental stress, prevent plant diseases and insect pests, etc. Moreover BVOCs affect the carbon cycle of the terrestrial ecosystem and the atmospheric photochemical processes. The MEIWEI volatile metabolism group adopts NIST database to detect terpenes, benzenoids, phenylpropanoids, alcohols, fatty acid derivatives, alkanes, ketones, esters, aldehydes, etc.
Therefore, the experimental data of the samples to be tested obtained in examples 1 to 12 are collated and analyzed based on the NIST database and in combination with the data processing method.
And (4) reporting the identified compound with the matching degree of more than 80% by NIST spectral library retrieval, normal paraffin retention time analysis and artificial analysis of experimental data. Opening a machine profile file under a sample to be detected by MassHunter quantitative software, integrating and correcting chromatographic peaks, wherein the peak Area (Area) of each chromatographic peak represents the relative content of a corresponding substance, and finally exporting integral data of all chromatographic peak areas for storage. 533 volatile substances are obtained by the co-detection in the embodiment of the invention, wherein the first five substances with the largest variety are 168 heterocyclic compounds, 86 aromatic hydrocarbons, 50 esters, 46 ketones, 32 alkanes, and other olefins, terpenes, amines, alcohols, phenols, sulfides, etc. Table 3 lists the major metabolites detected:
table 3: statistical table of metabolite quantities
Substance(s) | CAS | Molecular formula | Precise molecular mass |
1, 3-dioxolan-2-ones | 96-49-1 | C3H4O3 | 88.016 |
(E) -3-penten-2-one | 3102-33-8 | C5H8O | 84.058 |
(dimethylamino) acetonitrile | 926-64-7 | C4H8N2 | 84.069 |
Pyridine compound | 110-86-1 | C5H5N | 79.042 |
1-hydroxy-2-butanone | 5077-67-8 | C4H8O2 | 88.052 |
Dihydro-2-methyl-3 (2H) -furanones | 3188-00-9 | C5H8O2 | 100.052 |
2-methyl radicalPyridine compound | 109-06-8 | C6H7N | 93.058 |
Methylpyrazine | 109-08-0 | C5H6N2 | 94.053 |
1, 4-dimethylpyrazole | 1072-68-0 | C5H8N2 | 96.069 |
3-Furanylmethanol | 4412-91-3 | C5H6O2 | 98.037 |
3-methylpyridine | 108-99-6 | C6H7N | 93.058 |
(Aminoiminomethyl) -urea | 141-83-3 | C2H6N4O | 102.054 |
4-cyclopentene-1, 3-dione | 930-60-9 | C5H4O2 | 96.021 |
2, 6-lutidine | 108-48-5 | C7H9N | 107.073 |
2-methyl butyric acid | 116-53-0 | C5H10O2 | 102.068 |
3-methyl-2-cyclopenten-1-one | 2758-18-1 | C6H8O | 96.058 |
2-ethylpyridines | 100-71-0 | C7H9N | 107.073 |
2, 6-dimethylpyrazine | 108-50-9 | C6H8N2 | 108.069 |
2-butenoic acid, 3-methyl-2-methylene-3-butenyl ester | 76003-38-8 | C10H14O2 | 166.099 |
2, 5-hexanedione | 110-13-4 | C6H10O2 | 114.068 |
2, 5-dimethylpyridine | 589-93-5 | C7H9N | 107.073 |
2, 3-dimethyl-2-cyclopenten-1-one | 1121-05-7 | C7H10O | 110.073 |
3, 4-dimethyl-2-cyclopenten-1-one | 30434-64-1 | C7H10O | 110.073 |
2, 3-dimethylpyridine | 583-61-9 | C7H9N | 107.073 |
N, N-diethyl-3-butan-2-amine | 37969-64-5 | C8H17N | 127.136 |
Propyl benzene | 103-65-1 | C9H12 | 120.094 |
Cyanoacetic acid methyl ester | 105-34-0 | C4H5NO2 | 99.032 |
2, 2-dimethyl-4-ethynyl-3, 6-dihydro-2H-pyran | 42491-40-7 | C9H12O | 136.089 |
1H-imidazole-4-carbaldehyde | 3034-50-2 | C4H4N2O | 96.032 |
4-vinylpyridines | 100-43-6 | C7H7N | 105.058 |
4-hexen-3-ones | 2497-21-4 | C6H10O | 98.073 |
4H-pyran-4-ones | 108-97-4 | C5H4O2 | 96.021 |
Alpha, alpha-dimethyl benzyl alcohol | 617-94-7 | C9H12O | 136.089 |
Benzonitrile | 100-47-0 | C7H5N | 103.042 |
6-methyl-5-hept-2-one | 110-93-0 | C8H14O | 126.104 |
1-methylimidazole-5-carbaldehyde | 39021-62-0 | C5H6N2O | 110.048 |
2,2', 5,5' -tetrahydro-2, 2' -bifuran | 98869-92-2 | C8H10O2 | 138.068 |
2-Furanylmethanol, acetate salt | 623-17-6 | C7H8O3 | 140.047 |
1,2, 3-trimethylbenzene | 526-73-8 | C9H12 | 120.094 |
Phosphorous acid vinyl ester | 58402-90-7 | C2H5O3P | 107.998 |
Acetochlor alcohol | 113-18-8 | C7H9ClO | 144.034 |
Squalene | 111-02-4 | C30H50 | 410.391 |
2,3' -bipyridine | 581-50-0 | C10H8N2 | 156.069 |
Dihydroactinidiolide | 17092-92-1 | C11H16O2 | 180.115 |
The above-described aspects may be implemented individually or in various combinations, and such variations are within the scope of the present invention.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the specific embodiments of the invention be limited to these descriptions. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (10)
1. A high-efficiency detection method for volatile components in cigarette smoke is characterized by comprising the following steps:
s1, extracting smoke components, sucking and trapping the smoke of the cigarette, and enabling the mainstream smoke of the cigarette to be detected to pass through a Cambridge filter;
s2, preprocessing a sample, cutting the Cambridge filter disc obtained in the step S1 into small fragments, putting the fragments into a headspace bottle, adding an internal standard solution to obtain the sample, and then putting the sample into a refrigerator for storage for later use;
s3, performing headspace solid phase microextraction, namely taking out the sample prepared in the step S2, placing the sample into a thermostat, standing and unfreezing, and then extracting by adopting full-automatic headspace solid phase microextraction HS-SPME;
and S4, performing GC-MS detection, and enabling the sample to be detected extracted in the step S3 to enter a GC-MS detection system for detection and analysis.
2. The efficient detection method for the volatile components in the cigarette smoke according to claim 1, wherein the mass ratio of the fragments to the internal standard liquid in the step S2 is 40: (1.3-2.0).
3. The method for efficiently detecting the volatile components in the cigarette smoke according to claim 1, wherein the internal standard solution in the step S2 is [2H8] -acetophenone with a concentration of 10 μ g/mL.
4. The method for efficiently detecting the volatile components in the cigarette smoke according to claim 1, wherein in the step S2, the Cambridge filter obtained in the step S1 is cut into small pieces with the length and the width of 1-2 cm.
5. The method for efficiently detecting the volatile components in the cigarette smoke according to claim 1, wherein the environmental temperature for sample pretreatment in the step S2 is 0-20 ℃.
6. The method for efficiently detecting the volatile components in the cigarette smoke according to claim 1, wherein the sample is stored in a refrigerator at-20 ℃ for later use in step S2.
7. The method for efficiently detecting the volatile components in the cigarette smoke according to claim 1, wherein the heating temperature in the step S3 is 50-80 ℃.
8. The method for efficiently detecting the volatile components in the cigarette smoke according to claim 1, wherein the sample prepared in the step S2 is taken out from the step S3 and is placed in a constant temperature box for standing at 16-20 ℃.
9. The method for efficiently detecting the volatile components in the cigarette smoke according to claim 8, wherein the sample prepared in the step S2 is taken out and placed in an incubator for standing for 25-35min in the step S3.
10. The method for efficiently detecting the volatile components in the cigarette smoke according to claim 1, wherein the step S4 further comprises the following steps: a normal paraffin mixture solution with a concentration of 10ppm was prepared and subjected to GC-MS analysis as an external standard together with the sample extracted in step S3.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110725537.4A CN113406238A (en) | 2021-06-29 | 2021-06-29 | Efficient detection method for volatile components in cigarette smoke |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110725537.4A CN113406238A (en) | 2021-06-29 | 2021-06-29 | Efficient detection method for volatile components in cigarette smoke |
Publications (1)
Publication Number | Publication Date |
---|---|
CN113406238A true CN113406238A (en) | 2021-09-17 |
Family
ID=77680058
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110725537.4A Pending CN113406238A (en) | 2021-06-29 | 2021-06-29 | Efficient detection method for volatile components in cigarette smoke |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113406238A (en) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101140268A (en) * | 2007-08-21 | 2008-03-12 | 中国烟草总公司郑州烟草研究院 | Analysis method for semi-volatility component in cigarette main stream flue gas |
CN103439443A (en) * | 2013-08-29 | 2013-12-11 | 中国烟草总公司郑州烟草研究院 | Method for simultaneously measuring 16 polyaromatic hydrocarbons in mainstream smoke of cigarettes |
CN109342632A (en) * | 2018-12-07 | 2019-02-15 | 上海市环境科学研究院 | The method that microwave abstracting-Solid Phase Extraction pre-treatment combination LC-MS technology detects 15 kinds of antibiotic in aquaculture bed mud simultaneously |
CN111929120A (en) * | 2020-09-16 | 2020-11-13 | 云南中烟工业有限责任公司 | Device and method for trapping cigarette smoke through mouth-to-mouth suction |
-
2021
- 2021-06-29 CN CN202110725537.4A patent/CN113406238A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101140268A (en) * | 2007-08-21 | 2008-03-12 | 中国烟草总公司郑州烟草研究院 | Analysis method for semi-volatility component in cigarette main stream flue gas |
CN103439443A (en) * | 2013-08-29 | 2013-12-11 | 中国烟草总公司郑州烟草研究院 | Method for simultaneously measuring 16 polyaromatic hydrocarbons in mainstream smoke of cigarettes |
CN109342632A (en) * | 2018-12-07 | 2019-02-15 | 上海市环境科学研究院 | The method that microwave abstracting-Solid Phase Extraction pre-treatment combination LC-MS technology detects 15 kinds of antibiotic in aquaculture bed mud simultaneously |
CN111929120A (en) * | 2020-09-16 | 2020-11-13 | 云南中烟工业有限责任公司 | Device and method for trapping cigarette smoke through mouth-to-mouth suction |
Non-Patent Citations (1)
Title |
---|
刘嘉莉等: "HS-SPME-GC/MS法测定主流烟气中8种香味成分的逐口释放量", 《烟草科技》 * |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102004132B (en) | Method for measuring alkaloid in tobacco and tobacco product | |
Torikaiu et al. | Study on tobacco components involved in the pyrolytic generation of selected smoke constituents | |
CN102565233B (en) | Method for determining volatile and semi-volatile secondary metabolite in fresh tobacco leaves | |
CN103226139B (en) | Process for analyzing gas-phase total components in cigarette mainstream smoke through airbag-thermal desorption-gas chromatography/mass spectrometry method | |
CN101329232A (en) | Method for screening fragrant raw material for cigarette based on thermal cracking - gas chromatograph mass spectrogram multiple techniques | |
CN101871922A (en) | Method for pyrolyzing tobacco additive and trapping and analyzing pyrolysis product | |
CN110412183B (en) | Rose fragrance component analysis method by needle capture-gas chromatography-mass spectrometry | |
CN102353741A (en) | Method for measuring contents of four kinds of tobacco-specific nitrosamines in cigarette mainstream smoke | |
CN113109483B (en) | Analysis method of pyrolysis aroma components of latent aroma type aroma raw materials for cigarettes | |
CN104931613A (en) | Method for detecting volatile components in tobacco leaves | |
Mitsui et al. | LC fractionation followed by pyrolysis GC–MS for the in-depth study of aroma compounds formed during tobacco combustion | |
CN106770707A (en) | The screening method of volatile organic matter in a kind of quick-fried pearl of cigarette filter | |
CN105527356B (en) | The peculiar N nitrosamine of tobacco and assay method while polycyclic aromatic hydrocarbon in a kind of cigarette mainstream flue gas based on suction nozzle micro-extraction | |
CN106053653A (en) | Analytical method for identifying flavor characteristic index compound of chilli oil | |
CN110763794B (en) | Method for measuring volatile organic compounds in tobacco material | |
CN113406238A (en) | Efficient detection method for volatile components in cigarette smoke | |
CN108760921B (en) | Analysis method for volatile chemical components of agilawood smoke for cigarettes | |
CN116183786B (en) | Identification method for trace glutinous rice aroma characteristic key aroma compound in tobacco | |
CN112213429B (en) | Analysis method for characteristic aroma components of heated non-combustible cigarettes | |
CN111208310A (en) | GC-QTOF (gas chromatography-quantitative trait loci) detection method for aldehyde ketone flavor components in tobacco and tobacco products | |
CN113109472B (en) | Novel method for simultaneously measuring main chemical components and phenolic harmful components in smoke exhaled by tobacco products | |
Chen et al. | The generation of carbon monoxide and carbonyl compounds in reconstituted tobacco sheet | |
CN111579664B (en) | Method for identifying processing quality of platycladus orientalis charcoal based on odor identification and application | |
CN103063759A (en) | Method for determining maleic hydrazide content in cigarette sidestream smoke | |
CN109975445B (en) | Method for detecting aldehydes in gas phase substances of cigarette smoke generated by heating and non-combustion |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210917 |