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51.
We applied a time-resolved small-angle neutron scattering technique to the vesicle system of dimyristoylphosphatidylcholine for the first time to determine lipid kinetics. The observed kinetics could be explicitly represented by a simple model that includes two independent kinetic parameters, i.e., the rates of transbilayer and interbilayer exchange. This technique is perfectly suited for the determination of lipid exchange kinetics in equilibrium and applicable to evaluation of the activity of the factors relevant to lipid migration, such as translocase and lipid transfer proteins. 相似文献
52.
53.
The mechanism and dynamics of the formation of a hydrogen molecule by incorporating two hydrogen atoms in a stepwise manner into the cavity of some POSS (polyhedral oligomeric silsesquioxanes) compounds has been investigated by ab initio molecular orbital and ab initio molecular dynamics (AIMD) methods. The host molecules in the present reactions are two types of POSS, T(8) ([HSiO(1.5)](8)) and T(12)(D(2d)) ([HSiO(1.5)](12)). AIMD simulations were performed at the CASSCF level of theory, in which two electrons and two orbitals of the colliding hydrogen atoms are included in the active space. The trajectories were started by inserting the second hydrogen atom into the hydrogen atom-encapsulated-POSS (H + H@T(n) → H(2)@T(n); n = 8 and 12). In many cases, the gradual formation of a hydrogen molecule has been observed after frequent collisions of two hydrogen atoms within the cages. The effect of the introduction of an argon atom in T(12) is discussed as well. 相似文献
54.
Morohashi N Noji S Nakayama H Kudo Y Tanaka S Kabuto C Hattori T 《Organic letters》2011,13(13):3292-3295
Powdery crystals of p-tert-butylthiacalix[4]arene (2) selectively include EtOH from 1:1 mixtures of MeOH-EtOH and EtOH-PrOH, and EtCO(2)H from HCO(2)H-EtCO(2)H. On the other hand, no acid is included from HCO(2)H-MeCO(2)H, even though MeCO(2)H is included from the neat acid. The origins of these phenomena are discussed based on X-ray analysis of inclusion crystals prepared separately by crystallization. 相似文献
55.
A Rh-doped SrTiO(3) (SrTiO(3):Rh) photocatalyst electrode that was readily prepared by pasting SrTiO(3):Rh powder onto a transparent indium tin oxide electrode gave a cathodic photocurrent under visible-light irradiation (λ > 420 nm), indicating that the SrTiO(3):Rh photocatalyst electrode possessed p-type semiconductor character. The cathodic photocurrent increased with an increase in the amount of doped Rh up to 7 atom %. The incident-photon-to-current efficiency at 420 nm was 0.18% under an applied potential of -0.7 V vs Ag/AgCl for the SrTiO(3):Rh(7 atom %) photocatalyst electrode. The photocurrent was confirmed to be due to water splitting by analyzing the evolved H(2) and O(2). The water splitting proceeded with the application of an external bias smaller than 1.23 V versus a Pt counter electrode under visible-light irradiation and also using a solar simulator, suggesting that solar energy conversion should be possible with the present photoelectrochemical water splitting. 相似文献
56.
M Shibasaki A Takahashi T Aoki H Sato S Yamada M Kudo K Kogi S Narita 《Chemical & pharmaceutical bulletin》1992,40(1):279-281
A synthesis of a novel and chemically stable homoisocarbacyclin analog, TY-11223 (3), has been accomplished. The analog (3), given intravenously or orally, showed potent and long-lasting activities in inhibiting platelet aggregation and, in addition, a good selectivity in biological activities. 相似文献
57.
The dechannelling cross section of a circular Frank dislocation loop of radius 19 Å, and of Burgers vector (a/3)(111) in gold crystal is calculated for (001) channeling of 2 MeV He+. The calculated value σc = 210 ± 10 Å2 is satisfactory compared with the experimental value σe = 235 Å2 by Merkel et al. 相似文献
58.
The reliability of the single comparator method in neutron activation analysis has been studied by comparing the calculated and experimental k values and by determining the concentration of trace elements in iron. The method has been applied to the analysis of tea leaves for thirteen elements; their concentrations varied over five orders of magnitude. 相似文献
59.
Reaction profiles and energetics for the reactions of substituted benzaldehydes with a series of different simple metal hydrides (BH(3), BMeH(2), BMe(2)H, AlH(3), and AlMe(2)H) are examined computationally. B3LYP/6-31G optimizations and MP2/6-311G single point energy calculations revealed that the Al reagents are more reactive than B reagents. Replacement of H with Me on BH(3) or AlH(3) makes the reduction transition state (TS) less stable. Accordingly the overall reactivity is in the order AlH(3) > AlMe(2)H > BH(3) > BMe(2)H. The Hammett rho value for substituted benzaldehydes (BAs) is negative for the initial complex formation and positive for the hydride-transfer step. The size and the sign of the apparent rho value depend on the relative stabilities of the separated reactants and the complex. The TS structures vary according to the Hammond postulate for substituted BAs and the variation is reflected in carbonyl-carbon and aldehyde-deuterium isotope effects. Comparison of the reaction profiles of the monomer and dimer reagents reveals that the real reacting species is the monomer in the gas phase for BH(3) but the dimer for BMe(2)H. 相似文献
60.
Yokoyama K Kudo F Kuwahara M Inomata K Tamegai H Eguchi T Kakinuma K 《Journal of the American Chemical Society》2005,127(16):5869-5874
The doubly functional aminotransferase BtrS in the 2-deoxystreptamine (DOS) biosynthesis, in which two transaminations are involved, was characterized by a genetic as well as a chemical approach with the heterologously expressed enzyme. The gene disruption study clearly showed that BtrS is involved, in addition to the previously confirmed first transamination, in the second transamination as well. This dual function of BtrS for the DOS biosynthesis was further confirmed by the structural determination of the reverse reaction product from DOS. Enantiospecific formation of the reverse reaction product from DOS clearly showed that BtrS distinguishes the enantiotopic amino groups of DOS, but in contrast, both enantiomers of 2-deoxy-scyllo-inosose (DOI) were efficiently accepted by BtrS to give a racemic product. This unique stereochemical recognition of DOI chirality and DOS prochirality by BtrS is mechanistically explained by a specific hydrogen-bond donating force in the enzyme active site as a particular feature of this doubly functional enzyme. 相似文献