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…     

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.     

偶氮侧基聚合物光致异构动力学研究

本文对偶氮侧基聚合物相位共轭光时间特性进行了研究,得到了相位共扼光产生机制─光致异构过程的时间常数.在相位共轭光上升阶段,其时间常数在0.4～0.5s之间,在相让共轭光的衰减过程,衰减满足双指数关系,分段拟合得到较好的结果,且得到快过程的时间常数为0.27s,慢过程的时间常数为0.78s.     

羰基铁催化黄樟油素、丁香酚异构化反应的研究——Ⅰ.异黄樟油素、异丁香酚的合成

本文报道了异黄樟油素、异丁香酚的新合成途径,即在羰基铁光催化下或多核羰基铁加热催化下,使黄樟油素、丁香酚异构化。其转化率几乎是定量的。反应产物经GC,GC/MC分析及UV,IR,NMR,折光率的鉴定,证明合成过程中发生了异构化反应,而且产物以反式异构体为主。     

无机锡催化δ-酮腈异构化成吡啶酮反应的研究

本文分别对三种无机锡(SnCl~2,SnO和SnO~2)催化δ-酮腈异构化成吡啶酮的条件进行了考察。实验结果表明:SnCl~2和SnO具有很高的催化活性。