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401.
Kobayashi T Shiga M Murakami A Nakamura S 《Journal of the American Chemical Society》2007,129(20):6405-6424
Phenol blue (PB) is a primary skeletal structure part of indoaniline dyes and well-known as a solvatochromic dye. It has been recently observed by pump-probe (PP) transient absorption measurements that PB shows ultrafast ground state recovery within a few hundred femtoseconds after photoexcitation. In this work, the ultrafast photochemical reaction mechanism of PB has been investigated using direct ab initio (CASSCF) nonadiabatic molecular dynamics with the trajectory surface hopping (TSH) method. The swarm of trajectories starting from the S1 Franck-Condon (FC) point has mostly shown surface hops (nonadiabatic transitions) from the S1 state to the S0 state at 110-120 fs in the vicinity of an S1/S0 conical intersection and after decay to the S0 state bifurcated into two (Reverse and Forward) directions with almost the same branching ratio and reached the vicinity of the S0 minimum energy point at 200-300 fs, which is in good agreement with the fast time component of the ground state recovery in the PP measurements. After reaching the vicinity of the S0 minimum energy point, the trajectories showed a coherent vibration of bending motion between quinoneimine and aniline rings with a low frequency of 43 cm-1, which presumably corresponds to a coherently photoexcitation-induced vibrational mode with a low frequency recently observed by the PP measurements. 相似文献
402.
Kimura S Iizuka T Miyazaki H Irizawa A Muro Y Takabatake T 《Physical review letters》2011,106(5):056404
We report the anisotropic changes in the electronic structure of a Kondo semiconductor CeOs(2)Al(10) across an anomalous antiferromagnetic ordering temperature (T(0)) of 29 K, using optical conductivity spectra. The spectra along the a and c axes indicate that an energy gap due to the hybridization between conduction bands and nearly local 4f states, namely the c-f hybridization gap, emerges from a higher temperature continuously across T(0). Along the b axis, on the other hand, another energy gap with a peak at 20 meV becomes visible at 39 K (>T(0)) and fully opens at T(0) because of a charge instability. This result implies that the appearance of the energy gap, as well as the change in the electronic structure along the b axis, induces the antiferromagnetic ordering below T(0). 相似文献
403.
Nagai D Suzuki A Maki Y Takeno H 《Chemical communications (Cambridge, England)》2011,47(31):8856-8858
Reversible chain association/dissociation phenomenon via CO(2) responsive crosslinking/decrosslinking was detected in aqueous solutions of polyallylamine (PAA). The chain association/dissociation behavior was reversible and useful in the synthesis of porous crosslinked polystyrene, which suggested potential utility in the area of CO(2)-responsive separable adhesives, switches and sensors. 相似文献
404.
Glucose/xylose mixtures (90 g/L total sugar) were evaluated for their effect on ethanol fermentation by a recombinant flocculent Saccharomyces cerevisiae, MA-R4. Glucose was utilized faster than xylose at any ratio of glucose/xylose, although MA-R4 can simultaneously co-ferment both sugars. A high percentage of glucose can increase cell biomass production and therefore increase the rate of glucose utilization (1.224 g glucose/g biomass/h maximum) and ethanol formation (0.493 g ethanol/g biomass/h maximum). However, the best ratio of glucose/xylose for the highest xylose consumption rate (0.209 g xylose/g biomass/h) was 2:3. Ethanol concentration and yield increased and by-product (xylitol, glycerol, and acetic acid) concentration decreased as the proportion of glucose increased. The maximum ethanol concentration was 41.6 and 21.9 g/L after 72 h of fermentation with 90 g/L glucose and 90 g/L xylose, respectively, while the ethanol yield was 0.454 and 0.335 g/g in 90 g/L glucose and 90 g/L xylose media, respectively. High ethanol yield when a high percentage of glucose is available is likely due to decreased production of by-products, such as glycerol and acetic acid. These results suggest that ethanol selectivity is increased when a higher proportion of glucose is available and reduced when a higher proportion of xylose is available. 相似文献
405.
Shimoyama A Saeki A Tanimura N Tsutsui H Miyake K Suda Y Fujimoto Y Fukase K 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(51):14464-14474
Helicobacter pylori is a common cause of gastroduodenal inflammatory diseases such as chronic gastritis and peptic ulcers and also an important factor in gastric carcinogenesis. Recent reports have demonstrated that bacterial inflammatory processes, such as stimulation with H. pylori lipopolysaccharide (LPS), initiate atherosclerosis. To establish the structures responsible for the inflammatory response of H. pylori LPS, we synthesized various kinds of lipid A structures (i.e., triacylated lipid A and Kdo‐lipid A compounds), with or without the ethanolamine group at the 1‐phosphate moiety, by a new divergent synthetic route. Stereoselective α‐glycosylation of Kdo N‐phenyltrifluoroacetimidate was achieved by use of microfluidic methods. None of the lipid A and Kdo‐lipid A compounds were a strong inducer of IL‐1β, IL‐6, or IL‐8, suggesting that H. pylori LPS is unable to induce acute inflammation. In fact, the lipid A and Kdo‐lipid A compounds showed antagonistic activity against cytokine induction by E. coli LPS, except for the lipid A compound with the ethanolamine group, which showed very weak agonistic activity. On the other hand, these H. pylori LPS partial structures showed potent IL‐18‐ and IL‐12‐inducing activities. IL‐18 has been shown to correlate with chronic inflammation, so H. pylori LPS might be implicated in the chronic inflammatory responses induced by H. pylori. These results also indicated that H. pylori LPS can modulate the immune response: NF‐κB activation through hTLR4/MD‐2 was suppressed, whereas production of IL‐18 and IL‐12 was promoted. 相似文献
406.
Hirotaka Ogawa Akinori Kan Makoto Ohsashi 《Physica C: Superconductivity and its Applications》2008,468(6):447-452
The superconductivity of ZnO-doped (Bi, Pb)-2223 thick film on the Ni and NiO substrates, which was prepared by the spray deposition technique with cold forging, was investigated by characterizing the critical current density (Jc), the critical temperature (Tc), the orientation factor (f), and the microstructure of the film. The thickness of the thick film prepared by the spray deposition method was approximately 10 μm. The maximum Jc value of (Bi, Pb)-2223 film on NiO substrate was approximately 2200 A/cm2 (Ic = 110 mA) when the film was sintered at 865 °C for 1 h with a cooling rate of 0.5 °C/min from 865 °C to 650 °C; in the case of Ni substrate, a maximum Jc value of approximately 2000 A/cm2 (Ic = 100 mA) was obtained for the (Bi, Pb)-2223 thick film when a cooling rate was 3 °C/min. Such a difference in the Jc values of (Bi, Pb)-2223 thick film on Ni and NiO substrates is attributed to the presence of reaction layer at the (Bi, Pb)-2223 and substrate interface. In addition, the variations in the orientation factor of (Bi, Pb)-2223 thick film on NiO substrate related to those of Jc values. The Jc values of (Bi, Pb)-2223 film on NiO substrate with ZnO doping extremely depended on the amount of ZnO doping and the 0.5 wt% ZnO-doped (Bi, Pb)-2223 thick film deposited on NiO substrate, which was sintered at 835 °C for 1 h in air with a cooling rate of 1 °C/min, showed a Jc value of approximately 1200 A/cm2 (Ic = 60 mA). Thus, it is considered that a small amount of ZnO doping was effective in lowering the sintering temperature of (Bi, Pb)-2223 thick film, resulting the improvement in the intragranular weak bonding or Josephson junction. 相似文献
407.
Binary blends of poly(vinyl chloride) (PVC) and chitin-graft-poly(2-methyl-2-oxazoline) showed miscibility in the blend fraction range of the latter lower than ca. 10 wt.-%. The glass transition temperature of PVC, which was determined by differential scanning calorimetry, changed to lower temperatures with increasing modified chitin contents up to 10 wt.-%. Segmental interaction between PVC and the graft copolymer was confirmed by the carbonyl stretching band shift in the FT-IR analysis. 相似文献
408.
Akinori Takasu Terumi Niwa Hisashi Itou Yoshihito Inai Tadamichi Hirabayashi 《Macromolecular rapid communications》2000,21(11):764-769
A new procedure for chemical modification of poly(vinyl alcohol) (PVA) was established by a glycosidation reaction of hydroxyl groups in PVA with triacetylated sugar oxazoline 1 . 1H and 13C NMR analyses indicated that triacetylated N‐acetyl‐D‐glucosamine (GlcNAc) was introduced onto a PVA backbone selectively via a β‐O‐glycoside linkage. Deacetylation of triacetylated GlcNAc‐substituted PVA 2 resulted in GlcNAc‐substituted PVA 3 in good yield. These modified PVAs 2 and 3 exhibited solubilities and thermal properties different from the original PVA. 相似文献
409.
As a new class of biopolymer-based hybrid materials, the present paper describes the binary blends of a modified chitin and poly(vinyl alcohol) (PVA) which are miscible in the whole range of compositions. The blend films were prepared by the solvent cast method from a homogeneous aqueous solution of PVA and a chitin derivative having poly(2-methyl-2-oxazoline) side chains. Miscibility between PVA and poly(2-methyl-2-oxazoline) homopolymer was also revealed. Differential scanning calorimetry and FT-IR analyses were used to investigate the blends. 相似文献
410.
Fengniu Lu Akira Shinohara Izuru Kawamura Akinori Saeki Tomohisa Takaya Koichi Iwata Takashi Nakanishi 《Helvetica chimica acta》2023,106(8):e202300050
Achieving the lowest phase transition temperature with minimal chemical modification in highly crystalline π-conjugated molecules is a universal problem in related research fields. This paper reports room-temperature liquefication of diphenylpyrene isomers by introducing bulky yet flexible branched alkyl chains through molecular desymmetrization. Six isomers with different symmetries depending on the positions of the phenyl groups and alkyl groups were synthesized, and three of the isomers were found to be liquids at 25 °C, a state in which they have remained for more than five years. Although it is generally believed that the lower the symmetry of a molecule, the less likely it is to crystallize, one molecule with a relatively high molecular symmetry unexpectedly did not crystallize, which was evidenced by the kinetic inhomogeneity of this amorphous material (practically stable liquid) assessed by rheological analysis. 相似文献