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Molecular-organization and biosynthesis of pigment-protein complexes of Rhodopseudomonas capsulata.

The photosynthetic apparatus of the facultative phototrophic bacterium Rhodopseudomonas capsulata contains three bacteriochlorophyll-carotenoid-protein complexes: the reaction center and the light-harvesting (LH) antenna complexes LHI (B870) and LHII (B800--850). In contrast to green anoxygenic phototrophic bacteria and the oxygenic cyanobacteria, the light-harvesting complexes of Rhodospirillaceae and Chromatiaceae are integral membrane particles. Variations in light fluxes induce membrane differentiation mainly expressed as variations in the size of the photosynthetic unit and in the area of intracytoplasmic membrane per cell. The B800--850 complex is the variable part of the photosynthetic apparatus. Synthesis of bacteriochlorophyll and of the polypeptides of the pigment complexes was found to be strongly coordinated. The synthesis of these polypeptides was followed immediately by the assembly of the complexes in the membrane. Bacteriochlorophyll or a signal substance triggered by bacteriochlorophyll synthesis regulated the synthesis of these polypeptides at the level of translation. The pigment-binding subunits of the B800--850 complex form oligomeric structures which interact with subunit H of the reaction center. A model of the topographical relationships of the pigment complexes is discussed.

Bacterial Proteins↗

Hydrophobically directed selective reduction of ketones.

Three hydrophobic borohydrides carrying phenyl, pentafluorophenyl, and beta-naphthyl groups were used to reduce ketones in water and in methanol. With ketones carrying phenyl, naphthyl, or biphenyl substituents, there was preferential reduction in methanol of competing acetyl groups, either intermolecular or intramolecular, but preferential reduction of the aryl ketones in water. In the most extreme case, there was a 40-fold selectivity reversal. Lithium borohydride showed no such change in selectivity and favored acetyl reduction in both solvents. Salt and cosolvent effects indicate that hydrophobic packing is involved in the reaction of hydrophobic reagents with the aryl ketones. Some special interaction of the pentafluorophenyl group with aryl rings was also detected.

Benzoates↗

Microbial reduction of alpha-chloroketone to alpha-chlorohydrin.

Microbial reduction of alpha-chloroketone to alpha-chlorohydrin was studied as one of the approaches for construction of the chiral center of the corresponding epoxide. About 100 microorganisms covering many species of Candida, Pichia, Hansenula, Geotrichum, Rhodococcus and Aureobasidium were screened to reduce the alpha-chloroketone stereospecifically. Many strains provided the R-alpha-chlorohydrin with 100% enantiomeric excess (ee), e.g., Candida sonorensis SC 16117, Geotrichum candidum SC 5469, Rhodotorula glutinis SC 16293, Sphingomonas paucimobilis SC 16113, Pichia silvicola SC 16159 and Rhodococcus equi SC 15835. Few microorganisms showed preferential formation of S-alpha-chlorohydrin after reduction. Among them, Pichia pinus SC 13864 and two Pichia methanolica strains SC 16116 and SC 13860 were the best, providing the S-alpha-chlorohydrin with ee of 88%, 79% and 78%, respectively. The enantiospecificity of the reduction by these Pichia species can be modified by changing the pH or prior heat treatment of the cells and S-alpha-chlorohydrin with > or =95% ee was obtained by appropriate modification of reaction conditions.

Bacteria↗