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144.
Machiko Shigemi Takahiro Takekiyo Hiroshi Abe Nozomu Hamaya Yukihiro Yoshimura 《Journal of solution chemistry》2014,43(9-10):1614-1624
We have used Raman spectroscopy to investigate the high-pressure phase behavior of 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]), a representative ionic liquid, at pressures up to ~7.5 GPa. We have also studied how increasing pressure leads to conformational changes in the [bmim]+ cation. We have found that liquid [bmim][BF4] undergoes pressure-induced solidification (freezing) into a superpressed (metastable) state at 2.5 GPa; another structural change probably occurs at ~6 GPa. Remarkably, conformational changes in the [bmim]+ cation between trans and gauche conformers are concordant with the metastable structural changes of [bmim][BF4]. As the pressure is increased from ambient, the fraction of gauche conformers increases, but the gauche fraction decreases above the solidification pressure (2.5 GPa), and slope of the gauche/trans ratio changes again above 6 GPa. We interpret these results in terms of the fragility of the ionic liquid. 相似文献
145.
Yoshinari Sawama Takahiro Imanishi Ryosuke NakataniYuta Fujiwara Yasunari MonguchiHironao Sajiki 《Tetrahedron》2014
While gem-dichloromethyl groups can be directly synthesized by the mono-dechlorination of the corresponding trichloromethyl groups, the suppression control of the over-reduction to form chloromethyl or methyl functionalities is quite difficult. We have established the efficient and widely applicable mono-dechlorination method of the trichloromethyl groups to form the corresponding gem-dichloromethyl groups using platinum on carbon in dimethylacetamide as a specific solvent at 25 °C under a hydrogen atmosphere. The mono-dechlorination of the α,α,α-trichloromethylcarbonyl groups smoothly proceeded by the use of platinum on carbon as a catalyst in a highly chemoselective manner, while the efficient mono-dechlorination of the alkyl- and aryl-trichloromethyl groups required the combined use of Bu3SnH. 相似文献
146.
The catalytic activities of the cationic synthetic flavin adduct 1 with various dendritic and non-dendritic 2,6-bis(acylamino)pyridines 2 were examined for the oxidation of organic sulfides with H2O2. The adduct of 5-ethyllumiflavinium perchlorate 1a with 2b–d bearing poly(benzyl ether) dendron units acts as an efficient organocatalyst for the oxidative transformation of sulfides to the corresponding sulfoxides under mild conditions. 相似文献
147.
[4+1] Cycloaddition reaction between isocyanides and N-acylimine derivatives generated from N-acyl N,O-acetals acting as isocyanophiles has been developed. These reactions proceeded smoothly and cleanly to afford the corresponding 5-aminooxazoles in high yields. This reaction was extended to the syntheses of 5-aminothiazoles by using N-thioacyl N,O-acetals. A wide range of N-acyl N,O-acetals, N-thioacyl N,O-acetals, and isocyanides were found to be applicable to this reaction. 相似文献
148.
Tubiferal A, a triterpenoid isolated from myxomycete Tubifera dimorphotheca, exhibits a reversal effect of vincristine (VCR) resistance against VCR-resistant KB cell lines. The compound possesses a complex structure involving the 6-7-6-5 polycyclic carbon framework with various functional groups. The stereoselective synthesis of the right-hand segment of tubiferal A was achieved on the basis of the cyclopentene annulation method and the semi-pinacol rearrangement reaction of an epoxy alcohol for constructing the trans-fused 6-5 bicyclic skeleton possessing two quaternary carbon atoms at the angular positions. 相似文献
149.
We previously reported that the peptide containing a Cys-Pro ester (CPE) moiety is spontaneously transformed into a peptide thioester via an N to S acyl shift followed by diketopiperazine formation. In an attempt to identify more reactive structures for the formation of a peptide thioester, we modified the CPE structure, in which the Pro residue in the CPE moiety was replaced with N-substituted glycine derivatives. These peptides were transformed into a peptide thioester more rapidly. Alternatively, the addition of an amino acid residue at the C-terminus of the CPE moiety also accelerated thioester formation. 相似文献
150.
On the induced‐fit mechanism of substrate‐enzyme binding structures of nylon‐oligomer hydrolase
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Takeshi Baba Ryuhei Harada Masayoshi Nakano Yasuteru Shigeta 《Journal of computational chemistry》2014,35(16):1240-1247
We present a detailed computational investigation of the induced‐fit motion in a nylon‐oligomer hydrolase (NylB) upon substrate binding. To this aim, we resort on the recently introduced parallel cascade selection molecular dynamics approach, allowing for an accelerated access to the set of conformational changes from an open‐ to a closed‐state structure to form the enzyme‐substrate complex in a specific induce‐fit mechanism. The structural investigation is quantitatively complemented by free energy analyses within the umbrella sampling algorithm accompanied by weighted histogram analysis. We find that the stabilization free energy is about 1.4 kcal/mol, whereas the highest free energy barrier to be overcome is about 2.3 kcal/mol. Conversely, the energetic contribution for the substrate binding is about 20 kcal/mol, as estimated from Generalized Born/Surface Area. This means that the open‐close induced‐fit motion could occur frequently once the substrate binds to the open state of NylB. © 2014 Wiley Periodicals, Inc. 相似文献