Variations in distributions of C25 highly branched isoprenoid (HBI) alkenes in the diatom, Haslea ostrearia: influence of salinity

C₂₅ HBI alkenes of the diatom, Haslea ostrearia, have been examined in experiments in which the algae were cultured for up to 10 days at 14–15°C at nine different salinities (15 to 40 per mil). H. ostrearia proved to be an osmotolerant organism and growth was observed at all salinities. After 10 days growth at the lowest and highest salinities of 15 and 40 per mil, the concentrations of 2,10,14-trimethyl-6-methylene-7-(3-methylpent-1-enyl)pentadec-9-ene, which was the only HBI present in any of the samples, averaged 1.2±0.7 and 2.1±0.7 pg cell⁻¹, respectively. These were slightly lower than the HBI concentrations at 25 to 35 per mil (2.8±0.5 pg cell⁻¹). The data indicate that although salinity has an influence on HBI production in H. ostrearia, factors other than salinity are probably more important in controlling the large variations of HBI alkene concentrations and distributions found in sedimentary environments.     

Structural identification of the C25 highly branched isoprenoid pentaene in the marine diatom Rhizosolenia setigera

2,6,10,14-tetramethyl-7-(3-methylpent-4-enyl)-pentadeca-2,5E,9E,13-tetraene I possessing a C₂₅ highly branched isoprenoid skeleton has been isolated from the marine diatom Rhizosolenia setigera and identified by ¹H and ¹³C NMR spectroscopy.     

The nature and fate of natural resins in the geosphere--VIII. NMR and Py-GC-MS characterization of soluble labdanoid polymers, isolated from Holocene class I resins

Soluble polylabdanoids isolated by sequential solvent extraction have been characterized by liquid-state ¹³C- and ¹H NMR and ¹³C-¹H HMQC (heteronuclear correlation) NMR spectroscopy in addition to solid-state NMR and Py-GC-MS techniques. Two Holocene resins originating from Santander, Colombia and Mombasa, Kenya were analyzed. Soluble polymers were isolated by extraction with a 1:1 (v/v) methylene chloride-methanol mixture following sequential extractions with methylene chloride and methanol. The molecular weight of polymer extracts was shown by GPC analyses to exceed that of non-polymeric occluded terpenoids. Py-GC-MS, solid-state ¹³C CP/MAS and ¹³C cross-polarization/depolarization NMR spectroscopy results indicated that chemical compositions of soluble polymers isolated from immature resins are highly representative of the structure of corresponding insoluble polymers, i.e. polylabdatrienes. These data provide evidence for cross-linking or cyclization of side-chain olefinic carbons during or shortly after polymerization. Generally, the characterization of soluble resin polymers by liquid-state NMR spectroscopy has proven to be an excellent means for investigating the maturation mechanism of polylabdanoid resinites, and has potential for furthering the application of Class I resinites as geothermal indicators.