In addition to the production of phytol (from chlorophylls) and sterols, a limited number of diatom
species are capable of synthesising unusual C25 and C30 highly branched isoprenoid (HBl) alkenes. At
the outset of the current investigation, the structures of most C25 and C30 HBIs had been identified.
Some environmental factors had been shown to control their production, although a detailed
understanding of these remained unclear. In addition, the biological functions of the chemicals
remained unknown, and the reasons for their production by some species and not by others, was not
understood.
Investigations on the distributions of C25 and C30 HBl alkenes biosynthesised by Rhizosolenia
setigera demonstrated a dependence on the physiological status of the cells, as measured by the
position of this diatom in its life cycle. Thus, while C30 HBIs were observed at every stage of the life
cycle, C25 HBIs were not always present in the cells. Since the synthesis of C25 HBIs appears to be
stimulated by the onset of auxosporulation (sexual reproduction), an explanation is provided as to
why they have rarely been observed in previous studies.
Two novel monocyclic C30 alkenes (previously reported in other strains of Rhizosolenia setigerd), and
a novel monocyclic C25 alkene were also observed during life cycle experiments. The two C30
hydrocarbons structures were subsequently characterised and the potential geochemical relevance of
these compounds was highlighted by comparison of their mass spectral and chromatographic
properties with those of alkenes reported in sediments and suspended water column particles.
An investigation of terpenoid (including HBl) biosynthesis in the diatoms Haslea ostrearia,
Rhizosolenia setigera and Pleurosigma intermeclium has been performed. Evidence for species and
organelle dependent biosynthetic pathways has been observed. Phytol is synlhesised by each species
investigated according to the recently discovered methyl-erythritol phosphate (MEP) pathway. This
pathway is also involved in the synthesis of C25 HBIs in the two species Haslea ostrearia and
Pleio-osigma intermedium. In contrast, C25 and C30 HBIs, and (at least) one monocyclic C30 alkene,
appear to be made predominantly via the mevalonate (MVA) route in the diatom R. setigera.
Evidence for the contribution of the MVA pathway to the biosynthesis of sterols was found for the
diatoms Rhizosolenia setigera, and Pleurosigma intermedium. In contrast, only contributions from
the MEP pathway were found for the biosynthesis of sterols in Haslea ostrearia. Preliminary
evidence for dynamic interchange between the two pathways has also been observed.
Fractionation of Rhizosolenia setigera cells revealed that phytol was present in the chloroplasts, while
sterols and HBIs were present in the cytoplasm.
Date of Award | 2003 |
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Original language | English |
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Awarding Institution | |
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HIGHLY BRANCHED ISOPRENOID ALKENES FROM DIATOMS: A BlOSYNTHETIC AND LIFE CYCLE INVESTIGATION
Masse, G. G. (Author). 2003
Student thesis: PhD