Complementary fragmentation pattern analysis by gas chromatography-mass spectrometry and liquid chromatography tandem mass spectrometry confirmed the precious lignan content of Cirsium weeds.
In this paper, as novelties to the field, it is confirmed at first, that the fruits of Cirsium species, regarded as injurious weeds, do contain lignans, two, different butyrolactone-type glycoside/aglycone pairs: the well known arctiin/arctigenin and the particularly rare tracheloside/trachelogenin species. These experiences were supported by gas chromatography-mass spectrometry (GC-MS), by liquid chromatography tandem mass spectrometry (LC-MS/(MS)) and by nuclear magnetic resonance (NMR) spectroscopy. The study reflects the powerful impact of the complementary chromatographic mass fragmentation evidences resulting in the identification and quantification, the extremely rare, with on line technique not yet identified and described, tracheloside/trachelogenin pair lignans, without authentic standard compounds. Fragmentation pattern analysis of the trimethylsilyl (TMS) derivative of trachelogenin, based on GC-MS, via two different fragmentation pathways confirmed the detailed structure of the trachelogenin molecule. The complementary chromatographic evidences have been unambiguously confirmed, by (1)H and (13)C NMR analysis of trachelogenin, isolated by preparative chromatography. Identification and quantification of the fruit extracts of four Cirsium (C.) species (C. arvense, C. canum, C. oleraceum, and C. palustre), revealed that (i) all four species do accumulate the tracheloside/trachelogenin or the arctiin/arctigenin butyrolactone-type glycoside/aglycone pairs, (ii) the overwhelming part of lignans are present as glycosides (tracheloside 9.1-14.5 mg/g, arctiin 28.6-39.3 mg/g, expressed on dry fruit basis), (iii) their acidic and enzymatic hydrolyses to the corresponding aglycones, to trachelogenin and arctigenin are fast and quantitative and (iv) the many-sided beneficial trachelogenin and arctigenin can be prepared separately, without impurities, excellent for medicinal purposes.
Boldizsár
I
I
Institute of Biology, Department of Plant Anatomy, L. Eötvös University, Budapest 1117, Pázmány Péter sétány 1/C, Hungary.
Kraszni
M
M
Tóth
F
F
Noszál
B
B
Molnár-Perl
I
I
D015107:4-Butyrolactone / Q000031:analogs & derivatives; D002853:Chromatography, Liquid / Q000379:methods*; D031180:Cirsium / Q000737:chemistry*; D005638:Fruit / Q000737:chemistry; D008401:Gas Chromatography-Mass Spectrometry / Q000379:methods*; D005960:Glucosides; D017705:Lignans / Q000032:analysis* / Q000737:chemistry; D019906:Nuclear Magnetic Resonance, Biomolecular; D010091:Oximes; D010936:Plant Extracts / Q000737:chemistry; D021241:Spectrometry, Mass, Electrospray Ionization; D053719:Tandem Mass Spectrometry / Q000379:methods*; D014297:Trimethylsilyl Compounds
D005960:Glucosides; D017705:Lignans; D010091:Oximes; D010936:Plant Extracts; D014297:Trimethylsilyl Compounds; C079169:tracheloside; D015107:4-Butyrolactone