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

Abstract

Lignans in eighteen samples of Linum species (L. tauricum ssp. tauricum, serbicum, bulgaricum and linearifolium; L. elegans; L. flavum ssp. sparsiflorum, L. capitatum var. laxiflorum), all members of the section Syllinum occurring in Bulgaria, were analysed by HPLC-ESI/MS and HPLC-UV/DAD. The ESI/MS fragmentation pathways recently established for aryltetralin lignans are now extended to ester and glycoside derivatives. In total, 22 different lignans, mainly of the aryltetralin type, were identified. 6-Methoxypodophyllotoxin and its glucoside were present as major constituents in all samples. Differences between the investigated taxa were observed especially with respect to the accumulation of 6-deoxy-7-hydroxy-aryltetralins such as podophyllotoxin and of 6-hydroxy-7-deoxy-aryltetralin lignans of the peltatin type. The distribution of aryltetralin lignans with different oxygenation patterns in the various samples, and correlations between the chemical data and the molecular phylogeny based on an analysis of ITS sequences of the investigated species are discussed.

Key words

Aryltetralin lignan - HPLC-ESI/MS - HPLC-UV/DAD - Linum L. - Linaceae - chemical and molecular systematics

References

• 1 Ayres D C, Loike J D. Lignans: chemical, biological, and clinical properties. Cambridge, New York; Cambridge University Press 1990
• 2 Rogers C M. The systematics of Linum sect. Linopsis (Linaceae).  Plant Syst Evol. 1982;  140 225-334
• 3 Westcott N D, Muir A D. Chemical studies on the constituents of Linum spp. In: Westcott ND, Muir AD, editors Flax - the genus Linum. London; Routledge 2003: 55-73
• 4 Mohagheghzadeh A, Schmidt T J, Alfermann A W. Arylnaphthalene lignans from in-vitro cultures of Linum austriacum .  J Nat Prod. 2002;  65 69-71
• 5 Konuklugil B, Ionkova I, Vasilev N, Schmidt T J, Windhövel J, Fuss E. et al . Lignans from Linum species of sections Syllinum and Linum.  Nat Prod Res. 2007;  21 1-6
• 6 Schmidt T J, Vößing S, Klaes M, Grimme S. An aryldihydronaphthalene lignan with a novel type of ring system and further new lignans from Linum perenne L.  Planta Med. 2007;  73 1574-80
• 7 Schmidt T J, Hemmati S, Fuss E, Alfermann A W. A combined HPLC-UV and HPLC-MS method for the identification of lignans and its application to the lignans of Linum usitatissimum L. and L. bienne Mill.  Phytochem Anal. 2006;  17 299-311
• 8 Konuklugil B, Schmidt T J, Alfermann A W. Accumulation of aryltetraline lactone lignans in cell suspension cultures of Linum nodiflorum L.  Planta Med. 1999;  65 587-8
• 9 Konuklugil B, Schmidt T J, Alfermann A W. Accumulation of lignans in suspension cultures of Linum mucronatum L.  Z Naturforsch. 2001;  56c 1164-5
• 10 Mohagheghzadeh A, Schmidt T J, Bayindir Ü, Fuss E, Mehregan I, Alfermann A W. Diarylbutyrolactone lignans from Linum corymbulosum in vitro cultures.  Planta Med. 2006;  72 1165-7
• 11 Vasilev N P, Ionkova I. Cytotoxic activity of extracts from Linum cell cultures.  Fitoterapia. 2005;  76 50-3
• 12 Vasilev N P, Ionkova I. Lignan production by cell cultures of Linum setaceum and Linum campanulatum.  Pharm Biol. 2005;  43 501-11
• 13 Petrova A. Taxonomic study of the wild species of the genus Linum L. (Flax) in Bulgaria.  Izv Bot Inst (Sofia). 1973;  23 15-76
• 14 Broomhead A J, Dewick P M. Aryltetralin lignans from Linum flavum and L. capitatum.  Phytochemistry. 1990;  29 3839-44
• 15 Palumbi S. Nucleic acids II: the polymerase chain reaction. In: Hillis DM, Moritz C, Mable BK, editors Molecular systematics, 2nd edition. Sunderland (USA); Sinauer Associates 1996: 407-514
• 16 Muir G, Schlötterer C. Limitations to the phylogenetic use of ITS sequences in closely related species and populations - a case study in Quercus petraea (Matt.) Liebl. In: Gillet EM, editor Which DNA marker for which purpose? http://webdoc.sub.gwdg.de/ebook/y/1999/whichmarker/index.htm; 1999. 
• 17 Swofford D. PAUP* phylogenetic analysis using parsimony (*and other methods). Version 4. Sunderland; Sinauer Associates 2003
• 18 Posada D, Crandall K A. Modeltest: testing the model of DNA substitution.  Bioinformatics. 1998;  14 817-8
• 19 Wichers H J, Versluis-De Haan G G, Marsman J W, Harkes M P. Podophyllotoxin and related lignans in plants and cell cultures of Linum flavum.  Phytochemistry. 1991;  30 3601-4
• 20 Federolf K, Alfermann A W, Fuss E. Aryltetralin-lignan formation in two different cell suspension cultures of Linum album: Deoxypodophyllotoxin 6-hydroxylase, a key enzyme for the formation of 6-methoxypodophyllotoxin.  Phytochemistry. 2007;  68 1397-406