• Combination of gas chromatography-mass spectrometry and mass spectral deconvolution for structural elucidation of an unusual C29-steroid detected in a complex sedimentary matrix
    Y. Finck, N. Aydin, C. Pellaton, G. Gorin and F.O. Gülaçar
    Journal of Chromatography A, 1049 (1-2) (2004), p227-231
    DOI:10.1016/j.chroma.2004.08.004 | unige:3613 | Abstract | Article HTML | Article PDF

A complex sedimentary sample from the Monterey Formation (CA, USA) has been submitted to GC–MS analysis followed by mass spectral deconvolution using Automated Mass Spectral Deconvolution and Identification System (AMDIS). Adjusting the parameters of the software allowed for the extraction of the spectrum of an unusual steroidal hydrocarbon coeluting with the major compound of the chromatogram. Following a careful interpretation of the “extracted” mass spectrum, the structure of the unknown has been postulated to be the 4,14-dimethylcholestane (DMC). Possible origins of this rare steroid are briefly discussed. Thus, application of AMDIS appears to be particularly suitable for the GC–MS analysis of natural complex mixtures characterized by a high number of analytes present in low amounts.
The 132,173-cyclopheophorbide a enol (CPP) is shown to convert mainly to a ~1:1 mixture of (132R/S) chlorophyllones a (Chlone), when chromatographed over silica gel or alumina supports. 151-hydroxychlorophyllonelactone a and some other chlorophyll a related compounds are also tentatively identified as minor transformation products of CPP. This raises the possibility that the chlorophyllones reported in recent sediments may be analytical artifacts from CPP. However, data for the surface sediments from Lake Motte as well as literature data for other contemporary sediments show that, (i) they are not artifacts, (ii) considering that CPP is the intermediate compound in the formation of chlorophyllones from chlorophyll a, the hydroxylation of CPP in the sedimentary environment involves an enzymatic process leading preferentially to 132S chlorophyllone a.

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