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81.
Hiroko X. Kondo Ayumi Kusaka Colin K. Kitakawa Jinta Onari Shusuke Yamanaka Haruki Nakamura Yu Takano 《Journal of computational chemistry》2019,40(23):2043-2052
Hydrogen-bond (H-bond) interaction energies in α-helices of short alanine peptides were systematically examined by precise density functional theory calculations, followed by a molecular tailoring approach. The contribution of each H-bond interaction in α-helices was estimated in detail from the entire conformation energies, and the results were compared with those in the minimal H-bond models, in which only H-bond donors and acceptors exist with the capping methyl groups. The former interaction energies were always significantly weaker than the latter energies, when the same geometries of the H-bond donors and acceptors were applied. The chemical origin of this phenomenon was investigated by analyzing the differences among the electronic structures of the local peptide backbones of the α-helices and those of the minimal H-bond models. Consequently, we found that the reduced H-bond energy originated from the depolarizations of both the H-bond donor and acceptor groups, due to the repulsive interactions with the neighboring polar peptide groups in the α-helix backbone. The classical force fields provide similar H-bond energies to those in the minimal H-bond models, which ignore the current depolarization effect, and thus they overestimate the actual H-bond energies in α-helices. © 2019 The Authors. Journal of Computational Chemistry published by Wiley Periodicals, Inc. 相似文献
82.
Takashi Fujikawa Hiroko Arai Rie Suzuki Hiroshi Shinotsuka Lszl Kvr Nobuo Ueno 《Journal of Electron Spectroscopy and Related Phenomena》2008,162(3):146-157
Recoil effects of photoelectrons excited by high-energy X-rays are studied beyond the simplest approximation where elastic scatterings of photoelectrons are completely neglected (single-site approximation). At first we have shown that the simple free atom energy shift is accurately obtained within the harmonic and the single-site approximations. Beyond the single-site approximation, this simple formula does not work, but still simple classically acceptable formula can be used to explain the recoil energy shift. Illustrative numerical calculations show that the energy shifts caused by the photoelectron diffraction amounts to 5–8 meV for graphite-like carbon and about 100 meV for LiI6 cluster at ?k=5–7 keV, and show oscillations as functions of the photoelectron energy. Furthermore we discuss the recoil effects in photoemission from extended levels by use of the tight-binding approach. Our approach naturally provides not only Debye–Waller factors but also the recoil factors. In addition to the phonon excitation, we also study the recoil effects associated with plasmon losses where intrinsic and extrinsic processes can interfere each other. Only the latter can contribute to the recoil energy shift. 相似文献
83.
Demizu Y Kubo Y Miyoshi H Maki T Matsumura Y Moriyama N Onomura O 《Organic letters》2008,10(21):5075-5077
The first catalytic process for protection of hydroxyl groups in sugars has been developed. Highly regioselective protection was accomplished along with high chemical yield. The regioselectivity of the benzoylation was realized as an intrinsic character of sugars based on a stereorelationship among their hydroxyl groups. Furthermore, complete protection of alpha-methyl glucoside and beta-methyl xyloside was accomplished. 相似文献
84.
Arai N Suzuki K Sugizaki S Sorimachi H Ohkuma T 《Angewandte Chemie (International ed. in English)》2008,47(9):1770-1773
85.
Takamizawa A Maeda H Kambara S Furuya H Hiraoka K 《Rapid communications in mass spectrometry : RCM》2008,22(16):2453-2456
A gold (Au) capillary has higher thermal conductivity than a stainless steel capillary and can withstand capillary over-heating induced by high CO(2) laser irradiation (over 2.5 W) better than a stainless steel capillary. For this study, a laser spray using an Au capillary was applied for the detection of sugars. The signal of cationized compounds [M+Na](+) can be detected with higher sensitivity than with conventional laser sprays using high laser power (over 2.7 W). Using 3.5 W of laser power, the signal intensity is 15 times higher than the maximum value with stainless steel (2.3 W) in a 10(-5) M maltose aqueous solution. It is considered that almost all the water molecules evaporate by laser irradiation, which is impossible to achieve using a stainless steel capillary. 相似文献
86.
Tomohiro Nuida Toshiya Hozumi Hiroko Tokoro Kazuhito Hashimoto Shin-ichi Ohkoshi 《Journal of Solid State Electrochemistry》2007,11(6):763-772
This article describes novel optical functionalities such as photomagnetic effects and magnetization-induced second harmonic
generation (MSHG) in several cyano-bridged metal assemblies. Single crystal- and film-types of a cyano-bridged Cu–Mo bimetallic
assembly, , were electrochemically prepared. When this compound was irradiated with light, spontaneous magnetization with a Curie temperature
(T
C) of 23 K was observed. Electrochemically prepared FeII[CrIII(CN)6]2/3·5H2O thin film, which was a ferromagnet with T
C=21 K, showed photoreduced magnetization. This photomagnetism is due to the change of ferromagnetic coupling between FeII and CrIII. MSHG was observed in CsICoII[CrIII(CN)6]·0.5H2O. This -type Prussian blue analog-based magnet is proven to be a piezoelectric ferromagnet, i.e., condensed matter with both piezoelectric
and ferromagnetism. This MSHG is due to the coupling between a piezoelectric structure of and ferromagnetism with a T
C of 46 K.
相似文献
Shin-ichi OhkoshiEmail: |
87.
Kasai HF Tsubuki M Matsuo S Honda T 《Rapid communications in mass spectrometry : RCM》2007,21(7):1100-1114
Three cholestane glycosides including OSW-1 with antitumor activity and two new analogues with modified steroidal side chains, thienyl OSW-1 and silylated thienyl OSW-1, were synthesized. Analyses were performed using optimized, reversed-phase liquid chromatography (LC) with electrospray ionization and atmospheric pressure chemical ionization quadrupole mass spectrometry (MS). The ionization mode and polarity, cone voltage, and chromatographic conditions were evaluated. The optimum LC/MS conditions to obtain valuable ions, indispensable for identifying the structures, are described. The key fragmentation pathways, which will be useful for confirming the detailed structures of steroidal glycosides, are also proposed. 相似文献
88.
Wang M Xiao X Fujiwara H Sugimoto T Noguchi S Ishida T Mori T Katori HA 《Inorganic chemistry》2007,46(8):3049-3056
By the reaction of new donor molecules, bis(ethylenedithio)tetrathiafulvalenoquinone(-thioquinone)-1,3-dithiolemethides [BEDT-TTFVO (1) and BEDT-TTFVS (2)] with FeX3 (X = Cl, Br) in CS2/CH3CN, 1:1 salts of 1 or 2 with an FeX4- ion (1.FeX4 and 2.FeX4) were obtained as black needle crystals. Their crystal structures are very similar to each other, in which the donor molecules are strongly dimerized and the dimers construct a one-dimensional uniform chain along the a axis, while the FeX4- ions are located at an open space surrounded by the neighboring donor molecules and also construct a one-dimensional uniform chain along the a axis. There are close contacts between the donor molecules and the FeX4- ions and significant differences in the contact distances among the four salts. All of the salts are semiconductors with room-temperature electrical conductivities of 10-4-10-2 S cm-1. The Fe(III) d spins of the FeX4- ions are subject to dominant ferromagnetic interaction through the participation of one of the singlet pi spins to form a short-range ferromagnetic d-spin chain. Such neighboring chains interact antiferromagnetically with each other through the singlet pi spins and are ordered at 1.0, 2.4, and 0.8 K for 1.FeCl4, 1.FeBr4, and 2.FeCl4, respectively. On the other hand, the antiferromagnetic ordering occurred with some canted angle at 1.9 K to leave a small magnetization for 2.FeBr4. 相似文献
89.
Some bis(indolizin-1-yl) disulfides, readily obtainable from the treatment of 1-(benzoylthio)indolizines with piperidine, were prepared and their conformations were investigated. In comparison with those of 1-(benzoylthio)indolizines, the (1)H-NMR spectra of these disulfides showed considerable high field shifts (delta 0.13-0.82 ppm) on each pyridine ring proton and the UV spectra exhibited significant bathochromic and hyperchromic shifts. These results supported strongly the participation of an intramolecular pi-pi interaction between the two indolizine rings in these molecules and, hence, of a particular gauche (cis) conformation. However, the conformational considerations and molecular calculations (Mopac PM3) for some bis(indolizin-1-yl) disulfides showed the presence of four more stable gauche forms in which two are enantiomeric, resulting in three types of gauche structures. These three types of gauche structures were confirmed by X-ray analyses. 相似文献
90.
Synthesis of (23E)-cycloart-23-ene-3beta,25-diol (1) and its 23Z-isomer 2 was achieved by using cycloartenol as a starting material, thus revising the proposed structure of natural 2 to 1 unequivocally. These synthetic studies revealed that the structural revision (Z-form --> E-form) should also be applied to terpenoids such as (23Z)-3beta-acetoxyeupha-7,23-diene-25-ol, (23Z)-tirucalla-7,23-diene-3beta,25-diol, quadrangularol A, quadrangularic acid K, and daurichromene C. 相似文献