Metabolic Profiling of Lignan Variability in Linum species of Section Syllinum native to Bulgaria

1 Supporting Information to: Metabolic Profiling of Lignan Variability in Linum species of Section Syllinum native to Bulgaria Nikolay Vasilev1 Rainer Ebel2 RuAngelie Edrada3 Elisabeth Fuss4 A. Wilhelm Alfermann5 Iliana Ionkova1 Ana Petrova6 Miriam Repplinger7 Thomas J. Schmidt8 Affiliation 1 Faculty of Pharmacy, Medical University of Sofia, Sofia, Bulgaria 2 Department of Chemistry, University of Aberdeen, Aberdeen, Scotland, UK 3 Institut für Pharmazeutische Biologie und Biotechnologie, Heinrich-Heine-Universität Düsseldorf, Düsseldorf, Germany 4 Interfakultäres Institut für Biochemie, Eberhard-Karls-Universität Tübingen, Tübingen, Germany 5 Institut für Entwicklungs- und Molekularbiologie der Pflanzen, Heinrich-Heine-Universität Düsseldorf, Düsseldorf, Germany 6 Institute of Botany, Bulgarian Academy of Sciences, Sofia, Bulgaria 7 Institut für Spezielle Botanik und Botanischer Garten, Johannes Gutenberg-Universität Mainz, Mainz, Germany 8 Institut für Pharmazeutische Biologie und Phytochemie, Westfälische Wilhelms-Universität Münster, Münster, Germany © Georg Thieme Verlag KG · DOI 10.1055/s-2008-1034298 · Planta Med 2008; 74: e68–e90 · Vasilev N et al. 2 Correspondence Prof. Dr. Thomas J. Schmidt Institut für Pharmazeutische Biologie und Phytochemie Westfälische Wilhelms-Universität Münster Hittorfstraße 56 48149 Münster Germany Phone: +49-251-83-33378 Fax: +49-251-83-38341 E-mail: thomschm@uni-muenster.de © Georg Thieme Verlag KG · DOI 10.1055/s-2008-1034298 · Planta Med 2008; 74: e68–e90 · Vasilev N et al. 3 [A+H]+ [A+H-OCH3]+ or [A+H-CH3OH]+ [B+H]+ [B+H -(X-H)]+ [B+H-XOH]+ [B+H-CO2]+ [B+H-(X-H) -CO2]+ [B+H-XOH-CO2]+ [B+H-CH2COO]+ [B+H-(X-H) - CH2COO]+ [M+H-XOH]+ [M+H-(X-H)]+ [M+H]+ [M+NH4]+ [M+Na]+ [2M+H-2XOH]+ [2M+H-XOH]+ [2M+H-2 (X-H)]+ [2M+H-(X-H)]+ [2M+H]+ X= [2M+NH4]+ No. Mol. mass [2M+Na]+ © Georg Thieme Verlag KG · DOI 10.1055/s-2008-1034298 · Planta Med 2008; 74: e68–e90 · Vasilev N et al. Table 1S (Supporting Information) ESI/MS fragmentation of aryltetralins; for fragment definition and details on fragmentation pathways see Fig. 1S (Supporting Information). 343c 343b 343c 343c 343c 343b 329c 329c 329b 313c 313b 313c 313d 313d 299b 299d 299b 312b 312b 312b 312b 312b 312b 297b 297b 297b 282b 282a 282b 282b 282c 267b 267c 267b 277b # # # # # 277b # # 277c # 247d # 409b 247b 289b 409a ip 277a 277b 277b 277b 277a ip # 277a ip 277a ip 247a 247c ip 247b 247b 259b 259b 259b 259b 259b 259b 259c 259a 259c 259d 259c 229b 229b # 229b 229d 229d # # # # # # # # # 233a # # # # # 245b 365b # # # # # # # # # # # # # 203a # 203a # 215b 215b 215c 215b 215b 215b 215c 215a 215b 215d 215c 185b 185b # 185b 185b 185b # # # # # # # # # 219b # 189a # # 189a # # # # # # # # # # # # # ip 189a # ip 189b # # # # # # # # # 247g 409d 247g 409e ip 247e ip 247g 229b # 229b # 203c # 203c # ip 203b ip 203b # # # # 189b # 189b # ip 189b ip 189b 7-hydroxy aryltetralins and derivatives b c 1a 1b 1c 1d 1e 1f 2a 2b 2f 3a 3f 4a 4b 4f 5a 5b 5f 444 486 500 514 542 606 430 472 592 414 576 414 456 576 400 442 562 H CH3CO C2H5CO C3H7CO C5H11CO C6H11O5 H CH3CO C6H11O5 H C6H11O5 H CH3CO C6H11O5 H CH3CO C6H11O5 911 995b nd nd nd nd 883b 967b nd 851b nd 851b 935b nd 823b 907a nd 906 990e nd nd nd nd 878c 962c nd 846b nd 846c 930d nd 818c 902b nd # # nd nd nd nd # # nd # nd # # nd # # nd # # # # # nd # # nd # # # # # # # 963a # # # # # # # # # # # # # # # # # 6a 6f 7a 7f 414 576 400 562 H C6H11O5 H C6H11O5 851b nd 823a nd 846b nd 818b nd 829d nd 801c nd ip 991b ip 963d ip 829e ip 801f b 871 853b 467a 462c 445b ip 427g c d a d a b 913 853 509 504 487 445 427g a # 853 523b 518b 501a 445b 427g # 853b 537b 532c 515a 445b 427g b c 969 853 565a 560d 543a 445b 427g d nd 853 629a 624b 607a 445a 427g 843b 825b 453a 448c 431b ip 413g b a c a a # 825 495 490 473 431 413g d nd 825 615b 610c # 431b 413g d b # # # 432 415 ip 397g b c b c a 973 793 599 594 577 # 397g b d a c d 811 793 437 432 415 ip 397g b c b d d a 853 793 479 474 457 415 397g 973b 793b 599b 594d 577b # 397g b c c c 783 765 # 418 401 ip 383g b d # 765 # 460 # # 383g 945c 765d 585b 580c 563a 401b 383g 6-hydroxy, 7-deoxy arlytetralins and derivatives # # 437a 432b 415e ip # # # 599a 594c 577g 415e # c d # # # 418 401 ip # # # # 580d 563d 401e # The relative intensities of ions are shown as: adetectable, <1%; b1-10%; c11-20%, d21-50%, e51-80%, f81-99%, g100% (base peak, bold). #: not present.; ip = identical with previous column ([M+H]+); nd: not detected ions at m/z > 1000 Da. © Georg Thieme Verlag KG · DOI 10.1055/s-2008-1034298 · Planta Med 2008; 74: e68–e90 · Vasilev N et al. 4 X 7-oxygenated aryltetralins H+ O H+ OH 7 if X = glycosyl or acyl O R X= H or acyl or glycosyl O R - (X - H) O H OX R' - - H2O H R' R' + [M + H]+ H generally base peak [M + H - (X - H)]+ = [M' + H]+ H H - R' OX(H) O R H R' + H+ R O - XOH R' H+ H+ O R H - CH3O or -CH3OH [A + H - CH3O]+ or [A + H - CH3OH]+ R O + [B + H] O H O H + [B + H - (X-H)] = [B'+ H]+ + H - [A + H]+ H+ if X = glycosyl [or acyl] - (X - H) O [B + H] / [B' + H] [M + H - XOH]+ R' R' OH OX H+ O R - R' + O rearrangement O O X= H or glycosyl [M + H - (X - H)] = [M' + H] - XOH O R - (X - H) + [M + H] H+ OH if X = glycosyl [or acyl] O O + + 6 R R' R 7-deoxyaryltetralins - CO2 - CH2CO2 [B + H - CO2]+ [B + H - CH2COO]+ - CO2 [B' + H - CO2]+ - CH2CO2 [B' + H - CH2COO]+ O [B + H - XOH]+ - CO2 [B + H - XOH - CO2]+ - CH2CO2 [B + H - XOH - CH2COO]+ Fig. 1S (Supporting Information) ESI/MS fragmentation (positive ion mode) of aryltetralin lignans and their acyl- and glycosyl derivatives; compare table 1S (Supporting Information). 5 Fig. 2S-1 L. tauricum ssp. tauricum (aerial parts, accession 1) RT: 3.00 - 50.00 SM: 5B NL: 1.49E6 Channel E UV Thomas242 10.62 100 19.77 50 7.45 14.13 3.30 27.04 NL: 3.02E9 Base Peak F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas242 19.77 100 10.58 50 27.10 14.11 7.41 15.45 19.77 1a 100 1b 1f 27.10 10.58 50 * 9.54 NL: 1.09E9 2a 7.41 50 * Isomers of 1f and 1a 14.11 2f 100 1c * 15.45 12.66 * Isomers of 2f and 2a 20.88 NL: 2.45E8 9.92 100 m/z= 412.5-413.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas242 2b * * NL: 3.02E9 m/z= 426.5-427.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas242 3f 3a m/z= 396.5-397.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas242 19.16 50 4a 15.45 100 5.12 NL: 1.95E7 14.79 7.58 19.67 50 9.24 9.63 50 14.20 6f 100 7.50 3.53 8.35 7f 24.91 27.00 27.59 30.98 34.54 39.62 NL: 4.25E7 m/z= 414.5-415.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas242 6a 16.91 12.57 0 100 20.17 15.45 m/z= 382.5-383.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas242 5a and derivatives not unambiguously detectable 20.88 NL: 1.87E7 m/z= 400.5-401.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas242 5.91 4.75 * 50 * 6.78 9.05 12.84 * Isomers of 7f and 7a 35.98 14.89 17.75 0 5 10 15 20 25 Time (min) 30 35 40 © Georg Thieme Verlag KG · DOI 10.1055/s-2008-1034298 · Planta Med 2008; 74: e68–e90 · Vasilev N et al. 45 50 6 Fig. 2S-2 L. tauricum ssp. tauricum (aerial parts, accession 2) RT: 3.00 - 50.00 SM: 5B 5.00 100 50 NL: 3.02E5 Channel E UV Thomas243 6.19 8.67 11.65 100 12.92 17.04 11.01 50 19.99 8.74 4.98 45.96 19.99 NL: 7.65E8 Base Peak F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas243 45.91 NL: 7.65E8 m/z= 426.5-427.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas243 27.61 17.04 12.98 100 45.91 31.58 24.97 1f 1a 1b 11.01 19.99 27.61 35.28 1e 1c 50 31.58 24.97 1d 35.28 NL: 5.46E7 7.81 100 2f 2a m/z= 412.5-413.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas243 14.37 50 *8.93 6.86 * 15.56 11.98 * Isomers of 2f and 2a 2b 21.18 38.20 NL: 5.22E7 9.87 4f 100 50 3a 4a 13.69 15.66 4.45 m/z= 396.5-397.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas243 19.50 25.68 27.22 43.95 45.62 37.31 NL: 2.54E7 5.74 100 m/z= 382.5-383.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas243 12.98 5a and derivatives not unambiguously detectable 6.51 50 4.17 7.62 8.01 16.79 8.65 100 20.09 24.26 25.07 26.24 32.35 33.95 35.28 40.67 45.91 NL: 1.44E8 m/z= 414.5-415.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas243 6a 6f 17.04 50 4.17 0 100 6.86 14.56 NL: 1.45E8 m/z= 400.5-401.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas243 4.98 7f 49.50 * 6.17 7a 11.64 50 *12.98 * Isomers of 7a and 7f 13.98 5 10 15 20 25 Time (min) 30 35 40 © Georg Thieme Verlag KG · DOI 10.1055/s-2008-1034298 · Planta Med 2008; 74: e68–e90 · Vasilev N et al. 45 50 7 Fig. 2S-3 L. tauricum ssp. tauricum (roots, accession 2) RT: 3.00 - 50.00 SM: 5B NL: 3.84E5 Channel E UV Thomas244 11.09 100 5.09 50 8.73 19.95 6.28 17.29 12.41 24.07 30.09 29.29 31.46 43.91 45.17 45.87 37.37 NL: 1.70E9 Base Peak F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas244 19.95 100 11.09 50 5.46 27.19 7.79 9.84 24.00 17.14 14.45 1f 100 32.72 1a 11.09 50 29.36 19.95 1b * 9.84 27.19 * 1c 17.82 * Isomers of 1f and 1a NL: 3.44E8 7.79 2f 100 2a 50 14.45 15.50 * Isomers of 2f and 2a 2b * *8.98 4.70 NL: 1.11E8 3f m/z= 396.5-397.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas244 4f 50 8.33 100 4a 3a 15.68 19.34 4b 25.20 13.47 NL: 1.30E8 5.46 * m/z= 382.5-383.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas244 50 7.52 7.87 * Isomer of 5f 20.05 13.03 8.70 NL: 1.35E8 m/z= 414.5-415.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas244 17.14 6f 100 6a 50 3.63 100 6.80 14.55 15.77 NL: 1.13E8 m/z= 400.5-401.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas244 5.03 6.25 7f * 7a 50 * 11.79 13.03 5 m/z= 412.5-413.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas244 20.89 10.23 100 NL: 1.70E9 m/z= 426.5-427.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas244 10 15 * Isomers of 7f and 7a 20 25 Time (min) 30 35 40 © Georg Thieme Verlag KG · DOI 10.1055/s-2008-1034298 · Planta Med 2008; 74: e68–e90 · Vasilev N et al. 45 50 8 Fig. 2S-4 L. tauricum ssp. tauricum (callus culture) RT: 3.00 - 50.00 SM: 5B 100 50 NL: 5.15E4 Channel E UV Thomas261 10.88 3.46 19.97 4.34 5.05 8.54 14.38 16.33 23.16 27.24 31.31 35.19 36.33 43.20 44.51 46.91 37.76 NL: 1.10E9 Base Peak F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas261 19.97 100 10.81 50 7.54 27.16 14.32 NL: 1.10E9 m/z= 426.5-427.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas261 19.97 100 1a 10.81 1f 1b 50 27.16 7.54 100 NL: 1.65E8 14.32 2f 2a 50 2b 15.32 20.97 NL: 2.26E7 9.64 100 4f 3f 3a 15.62 7.36 7.89 m/z= 396.5-397.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas261 4a 50 10.54 19.57 20.17 4b 25.43 27.06 NL: 6.77E6 12.11 13.21 100 50 100 m/z= 412.5-413.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas261 6.14 10.04 11.15 19.57 13.92 16.41 6.66 27.26 22.87 31.46 35.15 36.30 46.81 49.55 39.55 42.20 44.43 6a 6f 3.53 19.87 20.17 20.57 5a and derivatives not unambiguously detectable NL: 8.07E6 m/z= 414.5-415.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas261 17.17 8.46 12.31 14.32 50 19.77 20.07 22.87 10.63 100 27.86 30.32 33.06 35.87 38.32 39.55 45.47 48.20 4.03 5.19 11.62 6.24 12.01 17.00 50 5 10 15 7a and derivatives not detectable 17.92 20.47 20 25.64 m/z= 382.5-383.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas261 30.95 25 Time (min) 30 32.96 33.80 34.12 35 36.61 41.26 40 © Georg Thieme Verlag KG · DOI 10.1055/s-2008-1034298 · Planta Med 2008; 74: e68–e90 · Vasilev N et al. 46.60 47.22 45 NL: 2.25E6 m/z= 400.5-401.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas261 50 9 Fig. 2S-5 L. tauricum ssp. tauricum (cell suspension culture) RT: 3.00 - 50.00 SM: 5B 5.10 100 NL: 1.42E4 Channel E UV Thomas262 11.64 50 8.59 10.91 17.72 20.02 15.69 23.67 25.62 28.88 35.00 36.09 31.23 42.76 44.80 46.44 NL: 1.16E8 Base Peak F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas262 10.96 100 20.02 50 8.57 10.96 100 44.11 45.12 31.11 32.52 17.73 5.40 47.39 NL: 1.16E8 m/z= 426.5-427.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas262 1a 1f 20.02 50 1b 5.40 NL: 3.80E6 7.65 100 2f 2a 50 8.57 10.44 5.40 14.48 15.54 42.89 48.20 NL: 3.53E6 4f 3f 50 7.33 3.59 4a 3a 15.74 19.92 11.06 18.43 26.23 27.93 29.52 7.01 7.33 11.16 5a and derivatives not detectable49.10 NL: 1.34E6 24.76 16.48 29.00 38.23 39.13 41.17 32.52 m/z= 382.5-383.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas262 46.22 47.69 43.20 23.32 16.17 m/z= 396.5-397.5 F: + c ESI sid=35.00 Full ms [ 48.50 48.90 100.00-1000.00] MS Thomas262 46.12 41.57 33.77 35.18 36.88 20.12 100 8.57 100 6f 6a 50 17.27 3.70 100 35.29 37.50 40.11 27.28 28.34 30.70 19.72 20.02 9.80 100 50 m/z= 412.5-413.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS 49.31 Thomas262 6.91 10.44 15.64 33.98 19.19 21.59 25.29 26.65 29.42 33.13 38.03 41.67 47.59 48.70 4.88 7f 50 6.15 5 11.46 8.39 10 15.84 15 18.65 19.19 23.53 20 26.23 30.28 31.01 25 Time (min) 30 34.31 35 38.54 40.54 40 © Georg Thieme Verlag KG · DOI 10.1055/s-2008-1034298 · Planta Med 2008; 74: e68–e90 · Vasilev N et al. 47.19 46.59 45 NL: 5.40E6 m/z= 414.5-415.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas262 NL: 1.79E6 m/z= 400.5-401.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas262 50 10 Fig. 2S-6 L. tauricum ssp. serbicum (aerial parts) RT: 3.00 - 50.00 SM: 5B 7.55 100 NL: 2.70E5 Channel E UV Thomas248 50 8.23 12.30 3.79 6.69 13.70 15.26 17.93 20.75 28.07 29.76 21.47 45.58 20.75 100 47.21 11.77 50 7.56 28.11 35.71 13.73 6.68 47.28 10.54 25.63 17.86 31.99 20.75 100 1a 1f 47.21 1b 11.77 1e 28.11 1d 50 1c 25.63 35.71 2f NL: 5.14E7 * * 8.40 9.40 m/z= 412.5-413.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas248 2a 50 15.18 12.64 4.72 7.31 17.86 23.28 * Isomers of 2a and 2f 38.76 NL: 7.09E7 10.54 4f 3f 100 50 4a 3a 16.48 20.20 m/z= 396.5-397.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas248 26.22 27.63 4.15 100 NL: 1.02E9 m/z= 426.5-427.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas248 31.99 16.48 100 NL: 1.02E9 Base Peak F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas248 45.12 46.84 5.725f NL: 2.26E7 * m/z= 382.5-383.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas248 6.88 * Isomer of 5f 50 12.73 8.15 4.72 15.37 18.04 20.66 21.05 25.63 28.50 32.76 35.62 41.32 37.44 46.05 47.59 NL: 3.08E7 m/z= 414.5-415.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas248 17.86 100 6a 15.37 6f 9.31 50 3.89 7.22 11.49 20.95 23.69 28.40 29.49 46.93 NL: 2.60E8 m/z= 400.5-401.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas248 13.73 * 100 * 6.68 50 * Isomers of 7a and 7f 0 5 10 15 20 25 Time (min) 30 35 40 © Georg Thieme Verlag KG · DOI 10.1055/s-2008-1034298 · Planta Med 2008; 74: e68–e90 · Vasilev N et al. 45 50 11 Fig. 2S-7 L. tauricum ssp. serbicum (roots) RT: 3.00 - 50.00 SM: 5B NL: 1.52E5 Channel E UV Thomas249 11.73 100 7.56 50 5.72 10.84 8.32 20.34 13.76 20.92 21.77 27.67 28.74 47.86 NL: 1.23E9 Base Peak F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas249 11.78 100 20.92 50 5.73 7.53 10.87 28.82 13.80 11.78 100 1f 20.92 1a * Isomer of 1f 50 1b * 10.42 8.30 2f 100 47.69 1e 28.82 NL: 1.23E9 m/z= 426.5-427.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas249 47.69 NL: 1.62E8 * m/z= 412.5-413.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas249 9.37 50 2a * 15.22 16.54 5.05 7.53 * Isomers of 2a and 2f NL: 4.22E8 10.87 3f 100 m/z= 396.5-397.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas249 3a 50 20.33 9.92 100 5.73 NL: 2.70E8 * m/z= 382.5-383.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas249 50 * Isomer of 5f 8.30 6f 6a 3.79 50 NL: 3.27E7 m/z= 414.5-415.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas249 9.20 100 18.09 16.64 20.33 7.11 8.30 13.37 NL: 1.34E8 m/z= 400.5-401.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas249 6.66 100 * * 13.80 50 * Isomers of 7a and 7f 5.35 5 10 15 20 25 Time (min) 30 35 40 © Georg Thieme Verlag KG · DOI 10.1055/s-2008-1034298 · Planta Med 2008; 74: e68–e90 · Vasilev N et al. 45 50 12 Fig. 2S-8 L. tauricum ssp. bulgaricum (aerial parts) RT: 3.00 - 50.00 SM: 5B 6.58 100 50 NL: 3.87E5 Channel E UV Thomas245 10.22 11.41 3.56 16.12 5.16 100 46.12 20.23 14.89 44.15 29.17 20.23 11.49 47.79 46.16 NL: 1.21E9 Base Peak F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas245 46.16 NL: 1.21E9 m/z= 426.5-427.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas245 8.14 50 6.66 27.55 25.64 14.87 16.16 1f 100 34.96 20.23 11.49 1e 1a * Isomer of 1f 1b 50 1d 27.55 * 34.96 10.30 NL: 5.79E8 8.14 100 2f m/z= 412.5-413.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas245 2a 14.87 50 2b NL: 5.75E8 10.21 100 4f m/z= 396.5-397.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas245 4a 16.16 50 25.64 43.52 NL: 3.19E8 6.66 100 5f * 50 11.03 5.30 m/z= 382.5-383.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas245 5b 5a * Isomer of 5a 19.50 12.66 NL: 8.10E7 m/z= 414.5-415.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas245 16.16 <4a> 100 50 8.05 10.21 3.70 14.87 5.52 6a and derivatives not detectable 19.59 NL: 1.75E7 m/z= 400.5-401.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas245 6.91 100 50 4b 3a 9.14 11.03 7a and derivatives not detectable 13.42 26.19 5.30 9.53 16.80 19.31 22.37 28.72 31.02 34.56 36.09 42.14 42.74 47.11 47.65 0 5 10 15 20 25 Time (min) 30 35 40 © Georg Thieme Verlag KG · DOI 10.1055/s-2008-1034298 · Planta Med 2008; 74: e68–e90 · Vasilev N et al. 45 50 13 Fig. 2S-9 L. tauricum ssp. bulgaricum (roots) RT: 3.00 - 50.00 SM: 5B NL: 1.59E6 Channel E UV Thomas246 11.20 100 50 8.00 3.64 20.25 11.40 50 27.49 8.04 14.77 6.67 100 NL: 2.35E9 Base Peak F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas246 20.25 100 17.46 24.79 NL: 2.35E9 m/z= 426.5-427.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas246 20.25 * Isomer 1f 1a 1f 1b 11.40 50 27.49 * 10.08 14.38 8.04 NL: 6.44E8 2a 2f 100 1e 1c 17.46 m/z= 412.5-413.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas246 14.77 50 2b 4.87 21.31 10.46 100 NL: 2.94E8 4a 4f 3f m/z= 396.5-397.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas246 16.04 3a 4b 19.65 25.60 50 8.82 13.59 5f 100 50 NL: 1.50E8 6.58 m/z= 382.5-383.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas246 5b 5.49 7.51 8.21 19.56 20.45 12.89 NL: 5.15E7 m/z= 414.5-415.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas246 16.04 <4a> 100 3.72 8.04 50 7.12 0 100 8.92 14.77 10.08 13.19 17.46 19.65 6a and derivatives not detectable NL: 1.31E7 m/z= 400.5-401.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas246 6.49 7a and derivatives not detectable 5.28 50 9.20 5 10 13.19 15.57 15 20.55 20.95 25.10 27.09 28.58 19.03 20 25 Time (min) 30 37.26 35 40.60 40 © Georg Thieme Verlag KG · DOI 10.1055/s-2008-1034298 · Planta Med 2008; 74: e68–e90 · Vasilev N et al. 45.15 45 49.27 50 14 Fig. 2S-10 L. tauricum ssp. linearifolium (aerial parts) RT: 3.00 - 50.00 SM: 5B NL: 1.05E6 Channel E UV Thomas250 10.07 100 6.59 50 16.05 12.39 7.73 3.66 20.27 15.53 25.73 20.27 100 10.01 50 8 ( 11.24 16.03 12.38 6.58 7.60 46.50 25.67 27.66 NL: 1.41E9 Base Peak F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas250 17.46 20.27 100 1a 1f 1e 11.24 1b 50 46.50 1d 27.37 NL: 1.54E8 8.02 100 2f 2a m/z= 412.5-413.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas250 14.72 ** 50 15.73 9.00 4.87 10.01 16.94 * 22.09 2b * Isomers of 2a and 2b NL: 6.40E8 4b 16.03 4f 100 4a m/z= 396.5-397.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas250 25.67 3a 50 9.00 5f 100 19.70 13.60 NL: 4.16E8 12.38 * 5a 6.58 7.60 m/z= 382.5-383.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas250 5b 50 10.97 5.44 19.51 * Isomer of 5f NL: 1.73E8 m/z= 414.5-415.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas250 16.03 100 <4a> 6f 50 8.82 3.73 6a 10.01 8.10 17.46 13.80 12.30 <5a> 100 50 5.35 6.83 5 NL: 1.41E9 m/z= 426.5-427.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas250 7a and derivatives not detectable 10.97 10 15 20 25 Time (min) 30 35 40 © Georg Thieme Verlag KG · DOI 10.1055/s-2008-1034298 · Planta Med 2008; 74: e68–e90 · Vasilev N et al. 45 NL: 4.56E7 m/z= 400.5-401.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas250 50 15 Fig. 2S-11 L. tauricum ssp. linearifolium (roots) RT: 3.00 - 50.00 SM: 5B 50 NL: 2.59E5 Channel E UV Thomas251 11.16 100 10.01 8.83 7.96 3.62 15.83 12.19 20.03 24.21 27.41 29.11 31.09 46.78 NL: 1.20E9 Base Peak F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas251 11.27 100 8 (compare Fig. 3S) 20.03 50 7.90 10.37 27.36 15.87 16.80 6.52 1f 50 29.15 32.47 44.78 NL: 1.20E9 m/z= 426.5-427.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas251 1a 11.27 100 24.25 * Isomers of 1f and 1a 20.03 1b * 10.02 27.16 * 12.68 17.23 1e 1c 44.78 NL: 3.82E8 7.90 2f 100 * 16.80 2a 50 7.13 14.57 * 15.53 m/z= 412.5-413.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas251 2b * Isomers of 2a NL: 4.83E8 10.37 4f 100 3f m/z= 396.5-397.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas251 4a 15.87 50 3a 19.54 100 NL: 1.82E8 * 6.525f * 7.57 5.49 50 m/z= 382.5-383.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas251 5a 12.23 5b * Isomers of 5f 20.03 10.83 NL: 1.58E8 m/z= 414.5-415.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas251 8.90 6f 100 6a <4a> 15.87 17.23 50 3.68 100 4b 25.38 7.74 5.12 7f 10.02 6.35 NL: 1.67E7 m/z= 400.5-401.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas251 12.23 <5a> 50 10.73 13.17 16.36 20.03 27.06 36.30 40.06 49.12 0 5 10 15 20 25 Time (min) 30 35 40 © Georg Thieme Verlag KG · DOI 10.1055/s-2008-1034298 · Planta Med 2008; 74: e68–e90 · Vasilev N et al. 45 50 16 Fig. 2S-12 L. elegans (aerial parts) RT: 3.00 - 50.00 SM: 5B 5.98 100 50 NL: 2.24E5 Channel E UV Thomas252 11.48 5.26 8.19 20.16 12.06 13.49 17.44 46.18 48.02 NL: 1.80E9 Base Peak F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas252 20.16 100 11.49 50 6.07 10.49 17.48 13.52 27.90 NL: 1.80E9 m/z= 426.5-427.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas252 20.16 100 1a 1f 11.49 1b 50 1e 27.90 NL: 1.52E8 8.26 2f 100 *9.29 50 m/z= 412.5-413.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas252 * 2a 16.02 14.88 * Isomers of 2f and 2a NL: 6.48E7 10.40 4f 100 3f 3a 4a 16.11 50 4b 26.00 8.00 8.73 0 100 45.43 46.93 NL: 1.96E7 5a * 20.16 20.96 6.75 5.47 36.26 30.33 31.47 34.12 12.54 7.91 50 m/z= 396.5-397.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas252 19.66 11.58 13.44 14.98 m/z= 382.5-383.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas252 * Isomer of 5f 25.17 36.46 30.33 32.66 35.66 38.67 41.44 45.64 46.53 49.81 NL: 1.61E8 m/z= 414.5-415.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas252 17.48 6a 100 6f 9.19 50 7.19 16.11 100 * 7f 50 NL: 1.53E8 m/z= 400.5-401.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas252 13.52 5.30 * 7a 8.17 * Isomers of 7a and 7f 12.19 0 5 10 15 20 25 Time (min) 30 35 40 © Georg Thieme Verlag KG · DOI 10.1055/s-2008-1034298 · Planta Med 2008; 74: e68–e90 · Vasilev N et al. 45 50 17 Fig. 2S-13 L. elegans (roots) RT: 3.00 - 50.00 SM: 5B 50 NL: 1.87E5 Channel E UV Thomas254 12.11 100 5.41 8.77 21.22 18.76 13.54 12.14 100 50 8.78 6.38 36.59 37.89 NL: 1.33E9 Base Peak F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas254 28.42 9.77 15.53 NL: 1.33E9 m/z= 426.5-427.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas254 21.22 12.14 100 30.43 32.57 24.28 21.22 1a 1f * Isomer of 1f 1b 50 28.42 * 10.91 NL: 4.03E8 8.78 2f 100 *9.95 50 2a m/z= 412.5-413.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas254 * 15.53 16.81 * Isomers of 2a and 2f NL: 1.23E8 11.28 3f 100 m/z= 396.5-397.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas254 3a 20.72 50 4a 9.31 NL: 7.05E7 6.02 100 * m/z= 382.5-383.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas254 50 21.32 8.78 NL: 5.64E7 m/z= 414.5-415.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas254 6f 6a 4.05 8.78 18.34 7.55 100 * Isomer of 5f 9.67 100 50 18.61 13.54 16.91 NL: 4.02E7 m/z= 400.5-401.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas254 5.74 7f 50 7.09 8.61 21.42 12.76 14.13 5 10 15 20 25 Time (min) 30 35 40 © Georg Thieme Verlag KG · DOI 10.1055/s-2008-1034298 · Planta Med 2008; 74: e68–e90 · Vasilev N et al. 45 50 18 Fig. 2S-14 L. flavum ssp. sparsiflorum (aerial parts) RT: 3.00 - 50.00 SM: 5B 50 NL: 2.25E5 Channel E UV Thomas255 12.03 100 6.87 3.88 20.93 14.21 8.57 9.49 18.17 48.93 28.47 23.33 NL: 2.23E9 Base Peak F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas255 20.93 100 12.03 50 3.89 6.18 28.46 14.20 16.65 18.14 10.84 49.40 NL: 2.23E9 m/z= 426.5-427.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas255 20.93 1a 100 1f * Isomer of 1f 12.03 50 1b 1e 28.46 * 10.75 49.40 NL: 3.46E8 16.65 100 * 2f 50 * 2a 9.72 m/z= 412.5-413.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas255 15.40 8.57 * Isomers of 2f and 2a 11.41 NL: 2.27E8 10.84 4f 100 3f 4a 16.65 50 m/z= 396.5-397.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas255 3a 20.33 4b 26.43 8.23 100 NL: 8.18E7 13.07 x 5a x constituent not related to 5a 50 5.83 11.50 15.85 m/z= 382.5-383.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas255 20.93 21.81 NL: 1.79E8 m/z= 414.5-415.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas255 18.14 6a 100 6f 9.45 50 15.67 7.46 3.89 10.75 * * 50 NL: 2.97E8 m/z= 400.5-401.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas255 14.20 100 7f 6.90 5.49 5 * Isomers of 7f and 7a 12.81 10 15 20 25 Time (min) 30 35 40 © Georg Thieme Verlag KG · DOI 10.1055/s-2008-1034298 · Planta Med 2008; 74: e68–e90 · Vasilev N et al. 45 50 19 Fig. 2S-15 L. flavum ssp. sparsiflorum (roots) RT: 3.00 - 50.00 SM: 5B NL: 4.78E5 Channel E UV Thomas256 12.67 100 50 5.59 21.89 11.41 6.64 0 100 NL: 2.01E9 Base Peak F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas256 21.89 12.70 50 11.30 9.16 1a 12.70 * Isomer of 1f 1b 50 * 11.30 Relative Abundance NL: 2.01E9 m/z= 426.5-427.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas256 21.89 1f 100 29.35 18.80 19.61 29.35 18.80 19.61 NL: 1.98E8 9.16 2f 100 2a * 50 10.35 16.05 5.53 8.24 m/z= 412.5-413.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas256 * 17.31 * Isomers of 2f and 2a NL: 1.35E8 11.77 3f 100 50 3a 4a 9.70 m/z= 396.5-397.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas256 21.29 17.31 NL: 9.03E7 6.28 100 * m/z= 382.5-383.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas256 50 8.80 100 4.10 19.14 11.30 * Isomer of 5f NL: 7.56E7 m/z= 414.5-415.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas256 6f 10.07 50 6a 18.97 7.79 5.03 0 100 21.89 22.48 6.01 7f 14.12 17.41 NL: 2.82E7 m/z= 400.5-401.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas256 7.35 * 50 3.53 8.89 13.42 14.59 17.13 22.77 * Isomer of 7f 0 5 10 15 20 25 Time (min) 30 35 40 © Georg Thieme Verlag KG · DOI 10.1055/s-2008-1034298 · Planta Med 2008; 74: e68–e90 · Vasilev N et al. 45 50 20 Fig. 2S-16 L. capitatum var. laxiflorum (aerial parts) RT: 3.00 - 50.00 SM: 5B NL: 3.89E5 Channel E UV Thomas257 12.17 100 21.37 9.67 5.75 50 6.37 18.49 4.97 15.65 NL: 2.80E9 Base Peak F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas257 21.37 100 12.12 50 5.74 6.42 8.77 18.51 15.68 28.96 NL: 2.80E9 m/z= 426.5-427.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas257 21.37 1a 100 1f 12.12 50 1b 28.96 8.77 NL: 3.59E8 2a 2f 100 m/z= 412.5-413.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas257 15.68 * 50 16.80 * Isomer of 2a 11.20 4f 100 NL: 1.75E8 3a 3f 4a 50 m/z= 396.5-397.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas257 20.77 16.98 NL: 1.41E7 8.51 100 7.27 50 16.28 13.23 3.25 m/z= 382.5-383.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas257 5a and derivatives not detectable 21.57 20.96 11.67 23.06 26.85 28.86 32.85 34.98 36.78 39.45 41.93 46.24 47.80 NL: 3.44E8 m/z= 414.5-415.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas257 18.43 100 6a 6f 9.68 50 7.53 4.01 100 16.98 NL: 1.37E8 m/z= 400.5-401.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas257 5.74 7f 7a 50 * 5 12.89 14.19 * 8.60 10 15 * Isomers of 7f and 7a 20 25 Time (min) 30 35 40 © Georg Thieme Verlag KG · DOI 10.1055/s-2008-1034298 · Planta Med 2008; 74: e68–e90 · Vasilev N et al. 45 50 21 Fig. 2S-17 L. capitatum var. laxiflorum (roots) RT: 3.00 - 50.00 SM: 5B 100 NL: 3.59E5 Channel E UV Thomas258 8.05 10.31 4.59 50 11.19 16.49 19.14 NL: 1.37E9 Base Peak F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas258 10.35 100 19.14 50 7.17 5.32 10.35 * Isomer of 1f 50 19.14 1b * 26.69 9.19 NL: 3.27E8 7.17 2f 100 2a 50 8.36 * Isomer of 2a 13.83 15.08 NL: 1.81E8 m/z= 396.5-397.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas258 3f 4f 50 50 * m/z= 412.5-413.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas258 9.54 100 100 NL: 1.37E9 m/z= 426.5-427.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas258 1a 1f 100 26.69 16.52 15.63 6.83 5.94 4a 3a 15.08 18.78 NL: 8.46E6 7.34 19.14 4.02 10.09 16.77 12.75 8.07 26.49 26.79 31.29 31.60 34.23 39.24 45.48 48.26 48.55 NL: 2.11E8 m/z= 414.5-415.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas258 6a 6f 100 21.02 m/z= 382.5-383.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas258 5a and derivatives not detectable 16.52 50 3.39 100 7.09 NL: 1.48E8 m/z= 400.5-401.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas258 4.64 7f 7a * 50 5.77 11.28 * Isomer of 7f 7.26 0 5 10 15 20 25 Time (min) 30 35 40 © Georg Thieme Verlag KG · DOI 10.1055/s-2008-1034298 · Planta Med 2008; 74: e68–e90 · Vasilev N et al. 45 50 22 Fig. 2S-18 L. capitatum var. laxiflorum (flowers) RT: 3.00 - 50.00 SM: 5B 10.94 100 50 19.90 NL: 4.60E5 Channel E UV Thomas260 19.90 NL: 2.93E9 Base Peak F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas260 8.62 11.74 5.50 6.13 17.18 14.46 0 100 10.86 50 14.39 7.69 5.40 26.98 17.11 1a 1f 50 NL: 2.95E9 m/z= 426.5-427.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas260 19.90 100 * Isomer of 1f 1b 10.86 26.98 * 9.78 12.88 NL: 4.26E8 14.39 7.69 100 2a 2f m/z= 412.5-413.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas260 * 50 15.47 2b * Isomer of 2a NL: 2.01E8 9.87 100 4f 3f 4a 15.73 50 m/z= 396.5-397.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas260 3a 19.31 0 NL: 1.13E7 7.44 100 m/z= 382.5-383.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas260 19.80 20.10 6.24 50 10.78 12.11 5a and derivatives not detectable 14.95 17.95 3.71 27.08 29.05 33.84 34.46 38.94 42.35 46.16 47.68 49.85 NL: 3.41E8 m/z= 414.5-415.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas260 17.11 6f 100 21.66 6a 8.59 50 6.83 3.53 100 15.73 NL: 7.09E7 m/z= 400.5-401.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] MS Thomas260 4.89 7f 50 7a * 6.07 * * Isomers of 7a and 7f 11.62 13.06 7.69 0 5 10 15 20 25 Time (min) 30 35 40 45 50 Fig 2S HPLC-ESI/MS and –UV/DAD analysis of 18 Linum samples. Chromatogram traces from top to bottom: UV-chromatogram detected at 280 nm; ESI/MS (positive mode) total ion chromatogram; single ion chromatograms detected at m/z ratios characteristic of the various aryltetralin lignans: 427: 1a and derivatives; 413: 2a and derivatives; 397: 3a, 4a and derivatives; 383: 5a and derivatives; 415: 6a and derivatives; 401: 7a and derivatives. © Georg Thieme Verlag KG · DOI 10.1055/s-2008-1034298 · Planta Med 2008; 74: e68–e90 · Vasilev N et al. 23 RT: 3.00 - 50.00 NL: 1.65E9 20.17 100 m/z= 426.5-427.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] M S Thomas250 A Relative Abundance 80 60 11.24 40 46.40 27.37 20 3.25 4.87 0 4 6.83 6 8.19 8 9.84 13.15 13.70 10 12 14 21.23 22.85 17.38 18.08 16 18 20 22 25.07 24 29.79 31.23 31.97 26 28 Time (min) 30 32 34.18 34 35.40 35.77 37.99 36 38 40.09 42.12 40 42 47.84 44.76 44 46 48 50 RT: 3.00 - 50.00 NL: 5.08E8 m/z= 364.5-365.5 F: + c ESI sid=35.00 Full ms [ 100.00-1000.00] M S Thomas250 27.66 100 B Relative Abundance 80 60 40 20 5.25 6.33 6.50 7.68 7.93 0 4 6 8 10.88 10 12.46 12.80 12 14 16.42 16.77 19.15 19.79 16 18 20 22.09 23.91 22 28.92 26.13 24 26 28 Time (min) 30.74 31.33 33.07 30 32 34 35.30 36.52 38.17 36 40.68 41.70 43.59 44.96 38 40 42 44 46.69 46 48.84 48 50 Tho mas250 # 1166 RT: 27.27 A V: 1 NL: 2.39E8 F: +c ESI sid=35.00 Full ms [ 100.00-1000.00] Relative Abundance 100 427.1 C 80 60 40 428.1 20 0 100 215.2 133.1 145.0 167.0 206.9 150 200 259.1 250 343.2 312.3 342.2 300 350 989.4 503.9 395.2 455.0 400 450 488.2 500 504.9 532.1 579.6 603.3 550 m/z 600 642.3 650 675.3 709.2 700 741.0 790.8 820.3 750 800 853.0 862.4 850 912.5 900 960.2 950 1000 Tho mas250 # 1182 RT: 27.66 A V: 1 NL: 5.08E8 F: +c ESI sid=35.00 Full ms [ 100.00-1000.00] Relative Abundance 100 365.1 D 80 60 40 366.2 20 119.0 137.0 168.3 207.2 215.1 0 100 150 200 335.2 259.1 303.2 321.3 250 300 350 427.1 367.2 397.1 400 428.2 450 476.1 503.8 521.8 556.2 589.8 624.5 646.1 500 550 m/z 600 650 745.8 751.0 709.2 728.3 700 750 801.7 800 852.5 867.6 873.8 922.5 850 900 963.8 992.1 950 1000 Fig. 3S Identification of justicidin B (8) in L. tauricum ssp. linearifolium (aerial parts); compare also Fig. 2S10; A: ion chromatogram at m/z = 427 (characteristic of 6-methoxypodophyllotoxin 1a and derivatives, see Table S1); B: Ion chromatogram at m/z = 365, characteristic of justicidin B 8 [7]; C: mass spectrum taken at t = 27.27 min, corresponding to 6-methoxypodophyllotoxin acetate (1b); D: mass spectrum taken at t = 27.66 min, corresponding to justicidin B (8); some overlap with the previous compound is observed (e.g. ions at m/z = 504, 427); MS, UV and retention time were identical with an authentic reference sample [7]. © Georg Thieme Verlag KG · DOI 10.1055/s-2008-1034298 · Planta Med 2008; 74: e68–e90 · Vasilev N et al.