Dynamics of Bacteriorhodopsin in the Dark-Adapted State from Solution Nuclear Magnetic Resonance Spectroscopy

To achieve efficient proton pumping in the light-driven proton pump bacteriorhodopsin (bR), the protein must be tightly coupled to the retinal to rapidly convert retinal isomerization into protein structural rearrangements. Methyl group dynamics of bR embedded in lipid nanodiscs were determined in the dark-adapted state, and were found to be mostly well ordered at the cytosolic side. Methyl groups in the M145A mutant of bR, which displays only 10 % residual proton pumping activity, are less well ordered, suggesting a link between side-chain dynamics on the cytosolic side of the bR cavity and proton pumping activity. In addition, slow conformational exchange, attributed to low frequency motions of aromatic rings, was indirectly observed for residues on the extracellular side of the bR cavity. This may be related to reorganization of the water network. These observations provide a detailed picture of previously undescribed equilibrium dynamics on different time scales for ground-state bR.     

Selective Catalytic Isomerization of β-Pinene Oxide to Perillyl Alcohol Enhanced by Protic Tetraimidazolium Nitrate

A series of tetraimidazolium salts with different anions was prepared and applied in the isomerization of β-pinene oxide. After examining the activity of different catalysts, a remarkable enhancement of the selectivity of perillyl alcohol (47 %) was obtained over [PEimi][HNO₃]₄ under mild reaction conditions and using DMSO as the solvent. Furthermore, noncovalent interactions between solvent molecules and the catalyst were found by FT-IR spectroscopy and confirmed by computational chemistry. The homogeneous catalyst showed excellent stability and was reused up to six times without significant loss.     

A Promising MoO_x-based Catalyst for n-Heptane Isomerization

The increasing demand for higher-octane gasoline and the regulations limiting the amount of aromatics in the fuel motivate the interest in catalytic isomerization of n-alkanes. In the last ten years, transition metal oxides or oxycarbides based on molybdenum or tungstate have attracted much attention due to their high activity and isomerization selectivity compared to the conventional bifunctional supported platinum catalyst and high resistance to sulphur and nitrogen catalyst poisons1-5. Ma…     

Quinone imine dye formation via photocycloaddition between isocyanates and chloranil

Photochemical [2+2]cycloaddition between electron-donating aryl isocyanates and chloranil was observed in acetonitrile or benzene, and the following elimination of carbon dioxide resulted in the formation of the corresponding quinone imine dyes. This new route for synthesis of quinone imine was investigated by product analyses, laser flash photolyses, and molecular orbital calculation.     

Chemiluminescence upon isomerization of dimethyldioxirane in the gas phase and on a sorbent surface

Chemiluminescence (CL) was found upon the isomerization of dimethyldioxirane in the gas phase under argon atmosphere. The intensity of CL increases as temperature increases and decreases with time at constant temperature. If Silipor is placed in a cell containing the dimethyldioxirane vapor in argon, the intensity of CL sharply increases (more than 10 times) and then decreases following the exponential law. In all cases tripletly excited methyl acetate is the emitter of chemiluminescence.[/ p]Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2582–2583, October 1996.     

Synthesis and cyclization of 1-arylalk-1-ene-3,5-diynylamines

An investigation of the reaction of 1-lithio-1,3-diynes, generated in situ, with nitriles has been carried out. In the case of aromatic nitriles 1-arylalk-1-ene-3,5-diynylamines are formed, which undergo dimerization and cyclization on isolation, giving 3-(alka-1,3-diynyl)-4-(alk-2-ynyl)-2,6-diarylpyridines. The effect of the nature of the substituent in the benzonitrile molecule on the selectivity of the reaction and the yield of the products has been determined. A scheme is proposed for the conversions and the structures of the intermediates have been established. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 701–710, May, 2006.     

Identification of new catalysts for the asymmetric reduction of imines into chiral amines with polymethylhydrosiloxane using high-throughput screening

The use of high-throughput techniques allowed the rapid identification of new catalysts for the enantioselective reduction of imines using polymethylhydrosiloxane (PMHS) as a reducing agent. By a simple modification of the chiral ligand structure that came out of the screening, the enantioselectivity of the reduction was increased from 40% ee to 60% ee.