Analytical Chemistry

Transcript

1 In silico modelling of hundred thousand experiments for effective selection of ionic liquid phase combinations in comprehensive twodimensional gas chromatography Analytical Chemistry Supporting Information Yada Nolvachai, Chadin Kulsing and Philip J. Marriott* Australian Centre for Research on Separation Science, School of Chemistry, Monash University, Wellington Road, Clayton, VIC 3800, Australia S1

2 Table of Contents 1. Additional tables 1.1 Table S1... S3 1.2 Table S2... S9 Compound Set A (Kerosene)... S9 Compound Set B (Polychlorinated biphenyls, PCB)... S16 Compound Set C (Gasoline)... S21 Compound Set D (Analytes from ref 1 )... S23 Compound Set E (Diesel)... S25 Compound Set F (Essential oil)... S34 Compound Set G (FAME & esters)... S36 Compound Set H (Food contaminants)... S39 Compound Set I (Polychlorinated naphthalenes, PCN)... S41 2. Normalized retention time from calculated retention factor... S43 3. Calculation of retention based on the dispersion/cavity formation for liquid to liquid phase... S44 4. Calculation of experiment numbers... S45 5. Additional figures... S47 6. References... S48 S2

3 Table S1. List of the stationary phases with the corresponding descriptors obtained/approximated at 100 C. (Commercially available phases are listed in blue) Phase Name e s a b l Ref Squalene a SPB-Octyl DB DB-VRX SPB DB PTE OV HP HP-5TA Rtx DB HP HP DB-WAXetr Rtx DB ,7b Rtx DB DB ,7b SLB-5ms DB-17ms Stabilwax DB DB HP-20M AT-WAX DB-FFAP SP HP-INNOWax SLB-IL SLB-IL SLB-IL SLB-IL SLB-IL SLB-IL IL1 (Structure referred to original article) IL2 (Structure referred to original article) IL3 (Structure referred to original article) IL4 (Structure referred to original article) S3

4 IL5 (Structure referred to original article) (2-hydroxyethyl)-1-methylpyrrolidinium (2-hydroxyethyl)-1-methylpyrrolidinium tri(pentafluoroethyl)trifluorophosphate (2-hydroxyethyl)-3-methylimidazolium (2-hydroxyethyl)-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate (4-methoxyphenyl)-3-methylimidazolium trifluoromethanesulfonate (6-aminohexyl)-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate ,-di(3-[2-hydroxyethyl])-2,6,9-trioxaundecane ,-di(3-[2-hydroxyethyl])-2,6,9-trioxaundecane trifluoromethanesulfonate ,-di(3-benzylimidazolium)-3,6,9-trioxaundecane ,-di(3-methylimidazolium)-3,6,9- trioxaundecane ,-di(3-methylimidazolium)-3,6,9- trioxaundecane trifluoromethanesulfonate ,12-di(3-benzylimidazolium)dodecane ,14-di(3-[2-hydroxyethyl]imidazolium)-3,6,9,12- tetraoxapentadecane trifluoromethanesulfonate ,14-di(3-benzylimidazolium)-3,6,9,12- tetraoxapentadecane ,14-di(3-methylimidazolium)-3,6,9,12- tetraoxapentadecane ,17-di(3-[2-hydroxyethyl]imidazolium)- 3,6,9,12,15-pentaoxanonadecane ,17-di(3-benzylylimidazolium)-3,6,9,12,15- pentaoxnonadecane ,17-di(3-methylimidazolium)-3,6,9,12,15- pentaoxnonadecane ,4-di(3-methylimidazolium)butane bis(triflioromethylsulfonyl)imide ,9-di(1-methylpyrrolidinium)nonane ,9-di(3-[2-hydroxyethy]limidazolium)nonane ,9-di(3-methylimidazolium)nonane benzyl-3-hexylimidazolium hexafluorophosphate benzyl-3-methylimidazolium S4

5 trifluoromethylsulfonate 1-butyl-1-methylpyrrolidinium bis(oxalato)borate butyl-1-methylpyrrolidinium tetracyanoborate butyl-1-methylpyrrolidinium thiocyanate butyl-1-methylpyrrolidinium tricyanomethide butyl-1-methylpyrrolidinium butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate butyl-2,3-dimethylimidazolium butyl-3-(2-acetylcyclohexyl)imidazolium tetrafluoroborate butyl-3-(2-hydroxycyclohexyl)imidazolium tetrafluoroborate butyl-3-methylimidazolium tetrachloroferrate butyl-3-methylimidazolium butyl-3-methylimidazolium hexafluorophosphate butyl-3-methylimidazolium trifluoromethanesulfonate ethoxycarbonylmethyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate ethyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate hexyl-2,3,4,5-tetramethylimidazolium hexyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate methoxyethyl-1-methylmorpholinium tris(pentafluoroethyl)trifluorophosphate methoxyethyl-1-methylpiperidinium tris(pentafluoroethyl)trifluorophosphate methoxyethyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate methoxypropyl-1-methylpiperidinium tris(pentafluoroethyl)trifluorophosphate nonyl-3-methylimidazolium octyl-2,3,4,5-tetramethylimidazolium propyl-1-methylpiperidinium benzene 3-benzylimidazolium bis[trifluoromethylsulfonyl]imides benzene 3-butylimidazolium bis[trifluoromethylsulfonyl]imides benzene 3-methylimidazolium bis[trifluoromethylsulfonyl]imides hexyl(trimethyl)ammonium S5

6 mesitylene 3-benzyl-1-imidazolium bis[trifluoromethylsulfonyl]imides methoxyethyl(dimethyl)ethylammonium tris(pentafluoroethyl)trifluorophosphate N,N,N,N -tetrahexyl-n,n -dimethylguanadinium N,N,N,N -tetramethyl-n,n -dioctylguanadinium N,N,N,N -tetraoctyl-n,n -dimethylguanadinium N-hexyl-4-(N',N'-dimethylamino)pyridinium tris(pentafluoroethyl)trifluorophosphate N-hexylpyridinium tris(pentafluoroethyl)trifluorophosphate N-hydroxypropylpyridinium tris(pentafluoroethyl)trifluorophosphate poly(1-[4-vinylbenzyl]-3-[2- hydroxycyclohexyl]imidazolium) poly(1-allyl-3-[2-hydroxycyclohexyl]imidazolium) poly(1-butene-3-[2- hydroxycyclohexyl]imidazolium) poly(1-butene-3-[2- hydroxycyclohexyl]imidazolium) bromide poly(1-butene-3-[2- hydroxycyclohexyl]imidazolium) tetrafluoroborate poly(1-butene-3-[2- hydroxycyclohexyl]imidazolium) thiocyanate poly(1-octene-3-[2- hydroxycyclohexyl]imidazolium) poly(1-vinyl-3-hexadecylimidazolium) poly(1-vinyl-3-hexyl)imidazolium poly(1-vinyl-3-nonylimidazolium-co-di-1,9-[3- vinylimidazolium]nonane) poly(1-vinyl-3-octylimidazolium) bis(trifluoroethylsulfonyl)imide poly(1-vinyl-3-octylimidazolium) poly(1-vinyl-3-propylphenylimidazolium) poly(crotyltributyl)phosphonium poly(dimethylsiloxane-comethyl[ethylimidazolium-3-hexy])siloxane) poly(dimethylsiloxane-comethyl[ethylimidazolium-3-hexy])siloxane) S6

7 hexafluorophosphate poly(dimethylsiloxane-comethyl[propylimidazolium-3-methyl)siloxane) (10% imidazolium monomer) poly(dimethylsiloxane-comethyl[propylimidazolium-3-methyl)siloxane) (30% imidazolium monomer) poly(dimethylsiloxane-comethyl[propylimidazolium-3-methyl)siloxane) chloride (30% imidazolium monomer) poly(tributylvinylphosphonium) tetrakis(3,5- bis[trifluoromethyl]phenyl)borate triethylamine 3-(2-hydroxyethyl)imidazolium bis[trifluoromethylsulfonyl]imides triethylamine 3-benzylimidazolium bis[trifluoromethylsulfonyl]imides triethylamine 3-butylimidazolium bis[trifluoromethylsulfonyl]imides triethylamine 3-methylimidazolium bis[trifluoromethylsulfonyl]imides trihexyl(tetradecyl)phosphonium tetrachloroferrate trihexyl(tetradecyl)phosphonium tris(pentafluoroethyl)trifluorophosphate tris(2-hexanamido)ethylamine 3-benzylimidazolium bis[trifluoromethylsulfonyl]imides tris(2-hexanamido)ethylamine 3-butylimidazolium bis[trifluoromethylsulfonyl]imides tris(2-hexanamido)ethylamine 3- methylimidazolium bis[trifluoromethylsulfonyl]imides tris(2-hexanamido)ethylamine tri(npropyl)phosphonium bis[trifluoromethylsulfonyl]imides [(Mim) 2 C 12 ] 2+ 2[FeCl 3 Br] [(C 16 im) 2 C 4 ] 2+ 2[FeCl 3 Br] [(C 16 BnIM) 2 C 12 ] 2+ [NTf 2, FeCl 3 Br] [(C 10 im) 2 C 4 ] 2+ 2[FeCl 3 Br] [(C 10 im) 2 C 4 ] 2+ 2[NTf 2 ] [(C 10 im) 2 C 4 ] 2+ [NTf 2, FeCl 3 Br] [(C 10 im) 2 C 10 ] 2+ 2[FeCl 4 ] [(C 10 im) 2 C 10 ] 2+ 2[FeCl 3 Br] [(C 10 im) 2 C 10 ] 2+ 2[NTf 2 ] [(C 10 im) 2 C 10 ] 2+ [NTf 2, FeCl 3 Br] a LSER descriptor values at C; b average LSER descriptors between 2 literatures. S7

8 Table S2. List of analytes investigated in this study with the corresponding LSER descriptor values. Various combinations of these compounds were selected as virtual test mixtures for simulated GC GC results. Compound set A (Model compounds available in LSER database 16, which may be observed in kerosene according E S A B V L to 17,18 ) hexyne cyclopentene isohexene ,5-hexadiene ,4-hexadiene isohexane ,3-hexadiene hexene n-hexane heptyne benzene methylcyclopentene cyclohexene cyclohexane isoheptene isooctene isoheptane ,6-heptadiene ,3-heptadiene ,4-heptadiene heptene ,5-heptadiene n-heptane octyne ,2,4-trimethylpentane ,2,4-trimethylpentene methylbenzene methylcyclohexane ethylcyclopentene ,2,4-trimethylpentane ,2,4-trimethylpentene isooctane octene ,5-octadiene ,6-octadiene ,4-octadiene S8

9 cycloheptene ,2,3-trimethylpentane ,2,3-trimethylpentene ,7-octadiene ,3-octadiene methyl-4-methylcyclohexane cycloheptane n-octane nonyne methyl-3-methylcyclohexane methyl-2-methylcyclohexane methyl-1-methylcyclohexane p-xylene m-xylene propylcyclopentene ethylbenzene ethylcyclohexane o-xylene methylcycloheptane ,2,4-trimethylhexane isononane ,5-nonadiene cyclooctene ,2,3-trimethylhexane ,6-nonadiene ,2,3-trimethylhexene ,4-nonadiene ,2,4-trimethylhexane ,3-nonadiene ,2,4-trimethylhexene nonene cyclooctane n-nonane decyne isopropylbenzene ,1,2-trimethylcyclohexane ethyl-4-methylcyclohexane isopropylcyclohexane isopropylcycloheptane propylbenzene ethyl-1-methylcyclohexane methyl-4-ethylbenzene ethyl-3-methylcyclohexane S9

10 1-methyl-3-ethylbenzene dimethylcycloheptane ,2,4-trimethylcyclohexane propylcyclohexane butylcyclopentene ,2,3-trimethylcyclohexane ethyl-2-methylcyclohexane propylcyclohexene methyl-2-ethylbenzene ,3,5-trimethylcyclohexane ethylcycloheptane ,2,4-trimethylbenzene ethylcycloheptene ,2,4-trimethylheptane ,2,3-trimethylbenzene methylcyclooctane methylcyclooctene ,5-decadiene ,6-decadiene ,3-decadiene ,4-decadiene indan decene isodecane ,2,3-trimethylheptane ,2,3-trimethylheptene isopentylcyclopentene ,2,4-trimethylheptane n-decane undecyne ,2-dimethyl-4-ethylbenzene methyl-4-propylcyclohexane cyclononene ,4-diethylbenzene ,2-dimethyl-3-ethylbenzene cyclononane methyl-1-propylcyclohexane methyl-2-propylbenzene butylcyclohexane methyl-2-propylcyclohexane methyl-3-propylcyclohexane ,2,4,5-tetramethylbenzene isobutylcyclohexane S10

11 1,2,3,4-tetramethylbenzene ,3-diethylbenzene butylcyclohexene ,2,4-trimethyloctane ,2-diethylbenzene propylcycloheptene decalin ethylcyclooctane ethylcyclooctene ,6-undecadiene ,5-undecadiene ,4-undecadiene ,3-undecadiene isoundecane undecene ,2,4-trimethyloctene ,2,3-trimethyl-5-ethylbenzene n-undecane dodecyne ,2,3-trimethyl-4-ethylbenzene methylcyclononane methylcyclononene cyclodecane methyl-2-butylbenzene methyl-2-butylcyclohexane cyclodecene pentylbenzene isopentylcyclohexane pentylcyclohexene ethyl-4-propylcyclohexane pentamethylbenzene ethyl-2-propylbenzene methylbutylcyclohexane hexylcyclopentene pentylcyclohexane methylnaphthalene butylcycloheptene ethyl-2-propylcyclohexane ,5-dodecadiene ,6-dodecadiene ,4-dodecadiene butylcycloheptane ,3-dodecadiene S

12 dodecene isododecane methylcyclodecane n-dodecane tridecyne cycloundecene propylcyclooctene cycloundecane heptylcyclopentene hexylcyclohexane methyl-2-pentylbenzene hexylcyclohexene isohexylcyclohexane ,6-tridecadiene ,4-tridecadiene ,3-tridecadiene ,5-tridecadiene methyldecalin isotridecane tridecene methyl-3-pentylcyclohexane cyclohexylbenzene cyclododecene methyl-1-pentylcyclohexane propyl-2-propylbenzene ethyl-2-butylbenzene cyclododecane methyl-2-pentylcyclohexane n-tridecane tetradecyne ,2,4-triethylbenzene ethyl-3-butylcyclohexane ethylbutylcyclohexane ,2,4-triethylcyclohexane butylcyclooctane ,2,3-triethylbenzene ethylcyclodecane ,3-tetradecadiene ,4-tetradecadiene ,6-tetradecadiene ,5-tetradecadiene octylcyclopentene tetradecene S12

13 isotetradecane heptylcyclohexene heptylcyclohexane n-tetradecane pentadecyne ,5-pentadecadiene ,6-pentadecadiene ,2,3-triethylcyclohexane methyl-4-hexylcyclohexane ethyl-2-pentylbenzene propyl-2-butylbenzene cyclotridecane cyclotridecene methylhexylcyclohexane ethyldecalin hexamethylbenzene nonylcyclopentene ethylpentylcyclohexane ,4-pentadecadiene ,3-pentadecadiene propylbutylcyclohexane octylcyclohexane pentadecene isopentadecane propyldecalin octylcyclohexene ethyl-2-hexylbenzene n-pentadecane hexadecyne propyl-2-pentylbenzene butyl-2-butylbenzene cyclotetradecene methylheptylcyclohexane decylcyclopentene ,2,4,5-tetraethylbenzene ,2,3,4-tetraethylbenzene hexylcyclooctene cyclotetradecane hexadecene isohexadecane cyclopentadecene n-hexadecane heptadecyne S13

14 nonylcyclohexene cyclopentadecane octylcycloheptane S14

15 Compound set B (Model compounds available in LSER database 16, which were observed in polychlorinated E S A B V L biphenyls, PCB, according to 19 ) 2,4,6-trichlorobiphenyl ,2,3,5-tetrachlorobiphenyl ,3,3,4-tetrachlorobiphenyl ,3,3,5 -tetrachlorobiphenyl ,3,4,5-tetrachlorobiphenyl ,3,3,4,6-pentachlorobiphenyl ,3,3,5,6-pentachlorobiphenyl ,3,4,5,5 -pentachlorobiphenyl ,3,3,4,5,5 -hexachlorobiphenyl ,2,3,4,5,6,6 -heptachlorobiphenyl ,3,3,4,5,5,6-heptachlorobiphenyl ,2,3,3,4,5,5,6-octachlorobiphenyl ,3,5-trichlorobiphenyl ,3,5,5 -tetrachlorobiphenyl ,3,4,5-tetrachlorobiphenyl ,3,4,5 -tetrachlorobiphenyl ,2,3,4,6 -pentachlorobiphenyl ,2,3,6,6 -pentachlorobiphenyl ,2,3,4,6-pentachlorobiphenyl ,3,3,4,5-pentachlorobiphenyl ,3,3,4,5 -pentachlorobiphenyl ,2,3,5,6,6 -hexachlorobiphenyl ,3,4,4,5,6-hexachlorobiphenyl ,2,3,4,4,5,6 -heptachlorobiphenyl ,2,3,4,4,6,6 -heptachlorobiphenyl ,2,3,4,4,5,6,6 -octachlorobiphenyl ,3 -dichlorobiphenyl ,3,4-trichlorobiphenyl ,4,5-trichlorobiphenyl ,2,4,6-tetrachlorobiphenyl ,3,3,5-tetrachlorobiphenyl ,3,4,5-tetrachlorobiphenyl ,3,5,6-tetrachlorobiphenyl ,2,3,4,5-pentachlorobiphenyl ,2,4,5,6 -pentachlorobiphenyl ,3,3,5,6-pentachlorobiphenyl ,3,4,4,5-pentachlorobiphenyl ,3,4,5,5 -pentachlorobiphenyl ,2,3,3,5,5 -hexachlorobiphenyl S15

16 2,2,3,4,4,6-hexachlorobiphenyl ,2,3,4,6,6 -hexachlorobiphenyl ,3,3,4,5,6-hexachlorobiphenyl ,3,4,4,5,5 -hexachlorobiphenyl ,2,3,4,4,5,6-heptachlorobiphenyl ,4-dichlorobiphenyl ,3,4-trichlorobiphenyl ,2,4,5 -tetrachlorobiphenyl ,3,3,6-tetrachlorobiphenyl ,3,4,5-tetrachlorobiphenyl ,3,4,6-tetrachlorobiphenyl ,3,4,4 -tetrachlorobiphenyl ,2,3,4,4 -pentachlorobiphenyl ,2,3,4,6-pentachlorobiphenyl ,2,3,4,5-pentachlorobiphenyl ,2,4,6,6 -pentachlorobiphenyl ,3,4,4,5-pentachlorobiphenyl ,3,4,4,5-pentachlorobiphenyl ,2,3,3,4,5-hexachlorobiphenyl ,2,3,4,4,5-hexachlorobiphenyl ,3,3,4,4,5-hexachlorobiphenyl ,3,4,4,5,5 -hexachlorobiphenyl ,2,3,3,4,6,6 -heptachlorobiphenyl ,2,3,4,5,5,6-heptachlorobiphenyl ,3,3,4,4,5,5 -heptachlorobiphenyl ,3,5-trichlorobiphenyl ,4,5-trichlorobiphenyl ,3,4,6-tetrachlorobiphenyl ,3,4,5 -tetrachlorobiphenyl ,3,5,5 -tetrachlorobiphenyl ,2,3,4,6-pentachlorobiphenyl ,2,3,5,6 -pentachlorobiphenyl ,3,3,5,5 -pentachlorobiphenyl ,3,4,5,6-pentachlorobiphenyl ,3,4,5,6-pentachlorobiphenyl ,3,4,5,6 -pentachlorobiphenyl ,2,3,4,4,6 -hexachlorobiphenyl ,2,3,4,5,6-hexachlorobiphenyl ,2,3,4,5,6 -hexachlorobiphenyl ,2,3,4,5,6 -hexachlorobiphenyl ,2,3,4,6,6 -hexachlorobiphenyl ,2,4,4,6,6 -hexachlorobiphenyl ,3,3,4,5,6-hexachlorobiphenyl S16

17 2,3,3,4,5,5 -hexachlorobiphenyl ,3,4,4,5,6-hexachlorobiphenyl ,2,3,4,5,6,6 -heptachlorobiphenyl ,4 -dichlorobiphenyl ,5-dichlorobiphenyl ,3,4-trichlorobiphenyl ,2,4,6 -tetrachlorobiphenyl ,2,5,6 -tetrachlorobiphenyl ,2,6,6 -tetrachlorobiphenyl ,3,5,6-tetrachlorobiphenyl ,4,4,6-tetrachlorobiphenyl ,4,4,5-tetrachlorobiphenyl ,2,3,4,5-pentachlorobiphenyl ,2,4,4,6-pentachlorobiphenyl ,3,4,5,6-pentachlorobiphenyl ,3,3,4,5-pentachlorobiphenyl ,3,4,5,5 -pentachlorobiphenyl ,2,3,3,4,5 -hexachlorobiphenyl ,2,4,4,5,6 -hexachlorobiphenyl ,3,3,4,5,6-hexachlorobiphenyl ,3,3,5,5,6-hexachlorobiphenyl ,2,3,3,4,5,6-heptachlorobiphenyl ,2,3,3,4,5,6,6 -octachlorobiphenyl ,2,3,3,4,5,6,6 -octachlorobiphenyl ,2,3,3,5,5,6,6 -octachlorobiphenyl ,4 -dichlorobiphenyl ,3,3 -trichlorobiphenyl ,3,6-trichlorobiphenyl ,4,5-trichlorobiphenyl ,3,5-trichlorobiphenyl ,2,3,3 -tetrachlorobiphenyl ,2,3,4 -tetrachlorobiphenyl ,2,4,4 -tetrachlorobiphenyl ,3,4,6-tetrachlorobiphenyl ,2,3,5,5 -pentachlorobiphenyl ,2,3,5,6-pentachlorobiphenyl ,2,4,5,5 -pentachlorobiphenyl ,3,3,4,4 -pentachlorobiphenyl ,3,4,4,5-pentachlorobiphenyl ,3,4,4,6-pentachlorobiphenyl ,2,3,3,4,4 -hexachlorobiphenyl ,2,3,3,5,6-hexachlorobiphenyl ,2,3,3,6,6 -hexachlorobiphenyl S17

18 2,2,3,4,5,6-hexachlorobiphenyl ,2,3,5,5,6-hexachlorobiphenyl ,3,3,4,4,5 -hexachlorobiphenyl ,3,3,4,4,6-hexachlorobiphenyl ,3,3,4,4,5,6-heptachlorobiphenyl ,3,3,4,4,5,6-heptachlorobiphenyl ,2,3,3,4,4,5,6,6 -nonachlorobiphenyl ,2,3,3,4,5,5,6,6 -nonachlorobiphenyl ,2,3,3,4,4,5,5,6,6 -decachlorobiphenyl ,3-dichlorobiphenyl ,4-dichlorobiphenyl ,6-dichlorobiphenyl ,2,4-trichlorobiphenyl ,3,6-trichlorobiphenyl ,3,5-trichlorobiphenyl ,4,5-trichlorobiphenyl ,4,6-trichlorobiphenyl ,4,4 -trichlorobiphenyl ,2,3,4-tetrachlorobiphenyl ,2,3,6-tetrachlorobiphenyl ,2,3,6 -tetrachlorobiphenyl ,2,4,5-tetrachlorobiphenyl ,3,4,4 -tetrachlorobiphenyl ,3,4,5-tetrachlorobiphenyl ,2,3,3,5-pentachlorobiphenyl ,2,3,3,6-pentachlorobiphenyl ,2,3,5,6-pentachlorobiphenyl ,2,4,5,6-pentachlorobiphenyl ,3,3,4,5-pentachlorobiphenyl ,3,4,4,6-pentachlorobiphenyl ,2,3,3,4,6-hexachlorobiphenyl ,2,3,3,4,6 -hexachlorobiphenyl ,2,3,3,5,6 -hexachlorobiphenyl ,2,3,4,5,5 -hexachlorobiphenyl ,2,3,4,5,6-hexachlorobiphenyl ,3,3,4,5,6-hexachlorobiphenyl ,2,3,3,4,4,5-heptachlorobiphenyl ,2,3,3,4,4,6-heptachlorobiphenyl ,2,3,3,4,5,5 -heptachlorobiphenyl ,2,3,3,5,5,6-heptachlorobiphenyl ,2,3,4,4,5,6-heptachlorobiphenyl ,3,3,4,5,5,6-heptachlorobiphenyl ,2',3,3',4,4',5,6'-octachlorobiphenyl S18

19 2,2,3,3,4,4,6,6 -octachlorobiphenyl ,3,3,4,4,5,5,6-octachlorobiphenyl chlorobiphenyl chlorobiphenyl chlorobiphenyl ,2 -dichlorobiphenyl ,3 -dichlorobiphenyl ,4 -dichlorobiphenyl ,5-dichlorobiphenyl ,2,3-trichlorobiphenyl ,2,5-trichlorobiphenyl ,2,6-trichlorobiphenyl ,3,4 -trichlorobiphenyl ,3,4-trichlorobiphenyl ,4,4 -trichlorobiphenyl ,2,3,5 -tetrachlorobiphenyl ,2,5,5 -tetrachlorobiphenyl ,3,3,4 -tetrachlorobiphenyl ,3,4,4 -tetrachlorobiphenyl ,3,4,5-tetrachlorobiphenyl ,3,4,6-tetrachlorobiphenyl ,4,4,5-tetrachlorobiphenyl ,2,3,3,4-pentachlorobiphenyl ,2,3,4,5 -pentachlorobiphenyl ,2,4,4,5-pentachlorobiphenyl ,3,3,4,6-pentachlorobiphenyl ,2,3,4,4,5 -hexachlorobiphenyl ,2,3,4,5,5 -hexachlorobiphenyl ,2,3,4,5,6-hexachlorobiphenyl ,2,4,4,5,5 -hexachlorobiphenyl ,2,3,3,4,5,6-heptachlorobiphenyl ,2,3,3,4,5,6 -heptachlorobiphenyl ,2,3,3,4,5,6-heptachlorobiphenyl ,2,3,3,5,6,6 -heptachlorobiphenyl ,2,3,4,4,5,5 -heptachlorobiphenyl ,2,3,4,5,5,6-heptachlorobiphenyl ,2,3,3,4,4,5,5 -octachlorobiphenyl ,2,3,3,4,4,5,6-octachlorobiphenyl ,2,3,3,4,5,5,6 -octachlorobiphenyl ,2,3,4,4,5,5,6-octachlorobiphenyl ,2,3,3,4,4,5,5,6-nonachlorobiphenyl S19

20 Compound set C (Model compounds available in LSER database 16, which were observed in gasoline according to 20 ) E S A B V L benzene toluene ethylbenzene p-xylene m-xylene o-xylene methylethylbenzene propylbenzene ethyl-3-methylbenzene ethyl-4-methylbenzene ,3,5-trimethylbenzene ethyl-2-methylbenzene ,2,4-trimethylbenzene ,2,3-trimethylbenzene indane sec-butylbenzene isobutylbenzene methyl-3-(1-methylethyl)benzene methyl-4-(1-methylethyl)benzene ,3-diethylbenzene ,4-diethylbenzene methyl-4-propylbenzene butylbenzene ethyl-2,4-dimethylbenzene ,2-diethylbenzene methyl-2-propylbenzene ethyl-1,2-dimethylbenzene ethyl-1,4-dimethylbenzene (E)-(1-methyl-1-propenyl)benzene ethenyl-4-ethylbenzene ethyl-1,3-dimethylbenzene ,2,3,5-tetramethylbenzene ,2,3,4-tetramethylbenzene ,3-dihydro-4-methyl-1H-indene ,3-dihydro-5-methyl-1H-indene ,2,4,5-tetramethylbenzene ,3-diethyl-5-methylbenzene methyl-4-(2-methylpropyl)benzene ,1-dimethylpropylbenzene S20

21 1,4-diethyl-2-methylbenzene methyl-4-(1-methylpropyl)benzene methylbutylbenzene ethyl-3-(1-methylethyl)-benzene ethylpropylbenzene pentylbenzene ,3-dihydro-2,2-dimethyl-1H-indene, ,3-dihydro-1,6-dimethyl-1H-indene ethyl-2,4,5-trimethylbenzene ,4-dimethyl-1-(1-methylethyl)-benzene ,3-dihydro-4,7-dimethyl-1H-indene ,3-dihydro-1,2-dimethyl-1H-indene ethyl-2,3-dihydro-1H-indene ,3-dihydro-1,3-dimethyl-1H-indene pentamethylbenzene ethynyl-4-methylbenzene methyl-1H-indene naphthalene methylnaphthalene methylnaphthalene S21

22 Compound set D (Analytes from ref 1 ) E S A B V L n-hexane n-heptane n-octane n-nonane n-decane n-undecane n-dodecane n-tridecane octene nonene decene undecene dodecene tridecene tetradecene pentadecene cyclohexane methylcyclohexane ethylcyclohexane propylcyclohexane butylcyclohexane benzene methylbenzene ethylbenzene propylbenzene isopropylbenzene butylbenzene pentylbenzene fluoropentane fluorohexane fluoroheptane fluorooctane fluorodecane chlorobutane chloropentane chlorohexane chloroheptane methylethanoate ethylethanoate propylethanoate butylethanoate pentylethanoate S22

23 hexylethanoate octylethanoate propylethanone butylethanone pentylethanone hexylethanone propanol butanol pentanol hexanol heptanol octanol nonanol methanol ethanol propanol butanol pentanol hexanol heptanol octanol S23

24 Compound set E (Model compounds available in LSER database 16, which may be observed in E S A B L diesel according to 17,18 ) tetradecene isotetradecane ,2-dimethyltetralin heptylcyclohexene ,2,3,4-tetramethyl-5-ethylbenzene ,2-dimethyl-3-pentylbenzene acenaphthylene heptylcyclohexane ,5-dimethyl-1,2,3,4-tetrahydronaphthalene methyl-1-ethylindan ,8-dimethyl-1,2,3,4-tetrahydronaphthalene n-tetradecane pentadecyne ,5-pentadecadiene ,6-pentadecadiene ,1-dimethyltetralin ,2,3-triethylcyclohexane (1Z)-1,2,3-octatrien-1-ylbenzene methylbiphenyl methyl-2-hexylbenzene butylindan methyl-4-hexylcyclohexane ethyl-2-pentylbenzene methylbiphenyl methylbiphenyl propyl-2-butylbenzene cyclotridecane fluorene cyclotridecene methylhexylcyclohexane ethyldecalin (3-buten-1-yl)-1h-indene propylnaphthalene methyl-7-phenylhepta-1,3,4-triene octylbenzene (1E)-1-octen-1-ylbenzene propylnaphthalene ethyl-7-methylnaphthalene isopropylnaphthalene hexamethylbenzene S24

25 2-ethyl-3-methylnaphthalene (1E)-1-(2-propen-1-ylidene)-1,2,3,4- tetrahydronaphthalene [(1E)-1-propen-1-yl]-1,2-dihydronaphthalene allyl-1,2-dihydronaphthalene ethyl-6-methylnaphthalene (2-methyl-propenyl)-1h-indene allyl-3-methyl-1h-indene [(1E,3E)-6-methyl-1,3,5-heptatrien-1-yl]benzene (3-buten-2-yl)-1h-indene isopropylnaphthalene ,6,7-trimethylnaphthalene ,1'-(1,2-ethanediyl)dibenzene (4-vinyl-3,5-hexadien-1-yl)benzene ,2,6-trimethylnaphthalene ,2,7-trimethylnaphthalene ethyl-8-methylnaphthalene ,3,6-trimethylnaphthalene nonylcyclopentene (3E)-1,3,7-octatrien-2-ylbenzene ,2-dimethyl-3-hexylbenzene benzyl-3-methylbenzene benzyl-2-methylbenzene ,1'-(1,1-ethanediyl)dibenzene benzyl-4-methylbenzene ,2'-dimethylbiphenyl ethylpentylcyclohexane (2-allyl-1,4-pentadien-1-yl)benzene ,6-dimethylbiphenyl pentylindan ,4-pentadecadiene ,4-dimethylbiphenyl methyl-1-propylindan ,3-pentadecadiene [(3E)-1,3,6-heptatrien-4-yl]-2-methylbenzene ,3'-dimethylbiphenyl ,5-dimethylbiphenyl propylbutylcyclohexane ethylbiphenyl ,4-dimethylbiphenyl ,2,3-trimethylnaphthalene ,3-dimethylbiphenyl ,2,5-trimethylnaphthalene S25