ABSTRACT
Nuclear Overhauser difference spectroscopy and variable temperature studies of the 9beta,19-cyclopropyl sterols 24,25-dehydropollinastanol (4,4-desmethyl-5alpha-cycloart-24-en-3beta-ol) and cyclolaudenol [(24S)-24-methyl-5alpha-cycloart-25(27)-en-3beta-ol] have shown the solution conformation of the B/C rings to be twist-chair/twist-boat rather than boat/chair as suggested in the literature. This is very similar to the known crystal structure conformation of 9beta,19-cyclopropyl sterols. The effect of these conformations on the molecular shape is highly significant: the first conformation orients into a pseudoplanar or flat shape analogous to lanosterol, whereas the latter conformation exhibits a bent shape. The results are interpreted to imply that, for conformational reasons, cyclopropyl sterols can be expected to maintain the pseudoplanar shape in membrane bilayers.
ABSTRACT
Natural-abundance solid-state 13C nuclear magnetic resonance spectra were obtained for bacterial spores for the first time by using the technique of cross-polarization magic-angle-spinning nuclear magnetic resonance spectroscopy. A resonance at about 150 ppm, detectable in spore samples having a Mn content of less than 0.05%, was consistent with an identification as the alpha-carbon signal of calcium dipicolinate; this signal was missing from a spore sample treated with acid to release dipicolinate and from a spore coat preparation. Carbohydrate peaks were particularly intense in spores and coat preparations of Bacillus macerans. Signals ascribable to beta-hydroxybutyrate were prominent in a B. cereus sample.
