Clinical analysis on steroids. XII. Occurrence of D-homoannulation during the hot acid hydrolysis of 5β-pregnane-3α,20α-diol disulfate

Two D-homosteroids were isolated from the hydrolyzate of 5β-pregnane -3α,20α-diol disulfate (II) when it was refluxed in 3N hydrochloric acid. The structures of these steroids have been elucidated as 17α-methyl-D-homo-5β-androstane-3α, 17aβ-diol (VI) and 17α-methyl-17aγb-chloro-D-homo-5β-androstan-3α-ol (VIII) by instrumental analyses. The former was identical with a synthetic specimen derived from 5β-pregnane-3α,20β-diol di-sulfate (IV) by uranediol rearrangement. The main hydrolyzates obtained were 17α-ethyl-17β-methyl-18-nor-5β-androst-13-en-3α-ol (V) and 5β-pregnane-3α, 20α-diol (III).     

Conformational transitions of the hydrophobic polyacids

The conformational transitions of the alternating maleic acid copolymers with styrene (MA-St)n, and alpha-methyl styrene (MA-MSt)(n) in aqueous solutions were studied by means of various methods. The following results were obtained: 1) The conformational transitions of (MA-St)n from the compact to extended coil form are observed in various salt solutions, as in aqueous NaCl, and the compact form is stabilized by Rb+ and Cs+, but destabilized by Li+. The coions, Br-, I-, ClO4- and SCN- affect scarcely the stability of the compact form. 2) The temperature coefficient of viscosity d In [eta]/dT of (MA-St)n in 0.09 M NaCl was positive for the compact form, but negative for the coil form, and it reflects the transition. 3) The difference between specific heats for the compact and coil forms of (MA-St)n in 0.03 M NaCl is determined to be about 15% of the corresponding heat of transfer of benzene to aqueous medium. 4) A remarkable dilution of the bound monomeric acridine orange to the compact form (MA-St)n is observed and the dimerization free energy of the dye in the compact form is about -2.1 kcal mole at 25 degrees C. 5) Potentiometric, dilatometric and viscometric titrations of (MA-MSt)n in aqueous NaCl at 25 degrees C show a similar conformational transition to that of (MA-St)n. Also, the difference in the molar extinction coefficient at 261 nm indicates the transition. The compact form of (MA-MSt)n is more unstable than that of (MA-St)n. From the results, the compact conformations and the transition mechanism of both the polyacids were discussed in comparison with the results for the maleic acid copolymers with n-alkyl vinyl ethers.     

The Pro to glycine mutation of staphylococcal nuclease simplifies the unfolding—folding kinetics

Kinetics of unfolding and refolding of a staphylococcal nuclease mutant, in which Pro¹¹⁷ is replaced by glycine, have been investigated by stopped-flow circular dichroism, and the results are compared with those for the wild-type protein. In contrast to the biphasic unfolding of the wild-type nuclease, the unfolding of the mutant is represented by a single-phase reaction, indicating that the biphasic unfolding for the wild-type protein is caused by cis-trans isomerization about the prolyl peptide bond in the native state. The proline mutation also simplifies the kinetic refolding. Importance of the results in elucidating the folding mechanism is discussed.     

The influence of light and nutrient addition upon the sediment chemistry of iron in an arctic lake

The geochemical response of sediments to increased nutrient input to an Alaskan, arctic lake was examined using direct measurements of sediment-water chemical fluxes. An unexpected increase in Fe flux occurred when sediments were exposed to high incident radiation and nutrient concentrations. Correlation between light and acid-soluble Fe concentrations suggests that photoreduction of Fe(III) oxides may occur, but nutrient addition enhanced the effect indicating that primary productivity was also important. The processes controlling the flux of Fe from sediments in this lake were complex and included the redox potential (dissolved oxygen concentration) of the water, quality of organic matter present in the sediment, light, and nutrients supplied from the sediments and/or water column. These four factors together with the possibility of direct uptake of Fe by phytoplankton and the possible release of algal reductants may contribute to Fe cycling in this lake.     

Possible influence of lysophospholipase on the production of 1-acyl-2-acetylglycerophosphocholine in macrophages.

The rate of production of 1-O-alkyl-2-acetyl-sn-glycero-3-phosphocholine (PAF) and 1-acyl-2-acetyl-sn-glycero-3-phosphocholine (acylPAF) was measured in macrophages following the incorporation of [3H]acetate. Upon activation by A23187, guinea pig alveolar macrophages incorporated [3H]acetate into PAF, but a little radioactivity was found in acylPAF. However, labeling of acylPAF and PAF with [3H]acetate was greatly enhanced in A23187-stimulated alveolar macrophages that had been pretreated with phenylmethanesulphonyl fluoride (PMSF). [3H]PAF was predominantly converted to 1-[3H]alkyl-2-acyl glycerophosphocholine, but [14C]acylPAF rapidly hydrolyzed to 14C-labeled free fatty acid by the incubation with lysates prepared from macrophages. The deacetylation of [14C]acylPAF and [3H]PAF by acetylhydrolase and also the hydrolysis of [14C]lysoPC by lysophospholipase were strongly inhibited in macrophages that had been pretreated with PMSF, while PMSF failed to inhibit the activities of acetyltransferase and acyltransferase. The relative proportions of PAF and acylPAF were quite different in different types of cells. In contrast to alveolar macrophages, peritoneal macrophages, neutrophils and spleen cells from guinea pigs incorporated 2-4 times more [3H]acetate into acylPAF than into PAF. The presence of high levels of acylPAF in peritoneal macrophages was confirmed by GLC-MS analysis. The activities of lysophospholipase, acetylhydrolase and acetyltransferase were measured in alveolar and peritoneal macrophages to determine whether the preferential formation of acylPAF as compared to PAF in peritoneal macrophages was due to differences in these activities between alveolar and peritoneal macrophages. The activity of acetylhydrolase of peritoneal macrophages was almost the same as that in alveolar macrophages. The activity of acetyltransferase in peritoneal macrophages was about half of that in alveolar macrophages. However, the activity of lysophospholipase in peritoneal macrophages was one-sixth of that in alveolar macrophages. These results suggest that lysophospholipase is one of the primary factors involved in the control of the production of acylPAF in activated cells, and that it acts by modulating the availability of lysoPC for the synthesis of acylPAF. Furthermore, high levels of activity of lysophospholipase allow the preferential formation of PAF, via the rapid hydrolysis of lysoPC which would act as a competitive inhibitor of the incorporation of acetate into lysoPAF.     

Synthesis of D-manno-3-heptulose,D-ido-3-heptulose,and some aldoheptoses via isopropylidene derivatives of heptitols

D-manno-3-Heptulose (5) was synthesized by dimethyl sulfoxide-phosphorus pentaoxide oxidation of 1,2:3,4:6,7-tri-O-isopropylidene-D-glycero-D-manno-heptitol (3, prepared from volemitol), followed by hydrolysis. D-ido-3-Heptulose (8) was synthesized similarly by oxidation of 1,2:4,5:6,7-tri-O-isopropylidene-D-glycero-l-galacto-heptitol (7, prepared from D-glycero-l-galacto-heptitol, 6). Another tri-O-isopropylidene derivative (11), having a free primary hydroxyl group, was produced in larger amount than 7, and 11 yielded D-glycero-l-galacto-heptose (14). Compound 8 was also synthesized by way of 1,2:4,5.6,7-tri-O-isopropylidene-D-glycero-l-gulo-heptitol (15). The production of 15 from D-glycero-l-gulo-heptitol (13) was accompanied by a larger amount of 2,3:4,5:6,7-tri-O-isopropylidene-D-glycero-D-ido-heptitol (17) which, upon oxidation followed by hydrolysis, yielded D-glycero-D-ido-heptose (18). One of the two tri-O-isopropylidene derivatives obtained by acetonation of perseitol, 2,3:4,5:6,7-tri-O-isopropylidene-D-glycero-D-galacto-heptitol (19), yielded D-glycero-D-galacto-heptose (20).     

Protein-Calcium-Phytic Acid Relationships in Soybean

This paper constitutes the first report in a research series undertaken in order to clarify the interactive relationships among soybean meal protein, calcium and phytic acid in solution and in precipitate.

Data presented are mainly concerned with solubility characteristics of soybean meal proteins as a function of pH. The results support the suggestion as follows; phosphorus and calcium give the remarkable effects on solubility characteristics of protein, the complex containing protein, calcium and phosphorus is formed above isoelectric point of protein and the combinations are labile above at pH 8, especially by heating.     

Genetic diversity,structure, and demography of Pandanus boninensis (Pandanaceae) with sea drifted seeds,endemic to the Ogasawara Islands of Japan: Comparison between young and old islands

Pandanus boninensis, endemic to the Ogasawara Islands, Japan, is distributed on both the older Bonin and younger Volcano Islands. In this study, we conducted population genetic analyses of P. boninensis on these islands to examine the population diversity and structure across old and young islands, to assess potential differences in population demography with island age, and to collect any evidence of migration between old and young islands. We found that the genetic diversity of expressed sequence tag (EST)–based microsatellite (SSR) markers, the nucleotide diversity of nuclear DNA sequences, and the haplotype diversity of chloroplast DNA on young islands were lower than those on old islands. Clustering analyses of EST‐SSR indicated that populations on old islands were strongly diverged from those on young islands. Approximate Bayesian computation analysis of EST‐SSR suggested that population expansion occurred on old islands while population reduction occurred on young islands. We also found evidence of migration among old islands (mostly from south to north), while it appears that there have been very few migration events between old and young islands. These differences could be due to the fact that young islands tend to be geographically isolated and support smaller populations that began a shorter time ago from limited founders. The P. boninensis populations on the Volcano Islands are interesting from an evolutionary perspective as they constitute a classic example of the early stages of progressive colonization on oceanic islands with small effective population sizes and low genetic diversity.