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81.
Prof. Dr. Yoshinobu Isono Toshihiro Kamohara Atsushi Takano Toshio Kase 《Rheologica Acta》1997,36(3):245-251
Simultaneous measurements of stress relaxation and differential dynamic modulus were made at 268 K over a time scale of 10 to 1045 s for nearly monodisperse polybutadiene (M
w
=2.2x105, 1,2-structure 70%, M
e
=3600) and also one having coarse cross-linking (M
c
=29000). Static shear strain ranged from 0.1 to 2.0. In a long-time region (t>
k
), the relaxation modulus G (; t) could be expressed by the product G (0; t) h (y). The observed h() agreed well with the Doi-Edwards theory without use of IA approximation. Both the cured and uncured samples showed initial drop of the differential storage modulus G (), ; t) followed by gradual recovery, but did not attain the value before shearing G (, ; t) for the uncured sample showed smaller values than that for the cured one in the whole measured time scale at the higher strain, confirming the two origins of nonlinear viscoelasticity of well entangled polymer; induced chain anisotropy and induced decrement in entanglement density. G (, ; t) curves for the cured sample agreed well with the BKZ predictions. But the curves for the uncured sample agreed well with the BKZ prediction only at the time scale of t<
k
. BKZ prediction showed significant upward deviations at t>
k
. Such the differences are discussed in terms of the two origins.Dedicated to Prof. John D. Ferry on the occasion of his 85th birthday. 相似文献
82.
In the lead optimization process, medicinal chemists must consider various chemical properties of active compounds, including ADME/Tox properties, and find the best compromise among these. This study presents a novel data mining method for multiobjective optimization of chemical properties, which consists of the hierarchical classification and visualization of multidimensional data. A hierarchical classification tree model is generated by an extension of recursive partitioning that utilizes averaged information gains for multiple objective variables as a quality-of-split criterion. All the hierarchically structured data objects are represented using a large-scale data visualization technique. The technique is an extension of HeiankyoView, which displays data objects as colored icons and group nodes as rectangular borders. Each icon is divided into subregions with different colors, so that it can present multidimensional data according to brightness of the colors. The proposed method was applied to the structure-activity relationship analysis for cytochrome P450 (CYP) substrates. The substrate specificity of six CYP isoforms was successfully delineated: e.g., CYP2C9 substrates are anionic compounds, while CYP2D6 substrates are cationic; and CYP2E1 substrates are smaller compounds, while CYP3A4 substrates are larger compounds. 相似文献
83.
Margadonna S Takabayashi Y McDonald MT Kasperkiewicz K Mizuguchi Y Takano Y Fitch AN Suard E Prassides K 《Chemical communications (Cambridge, England)》2008,(43):5607-5609
The newly discovered superconductor FeSe(1-x) (x approximately 0.08, T(c)(onset) approximately 13.5 K at ambient pressure rising to 27 K at 1.48 GPa) exhibits a structural phase transition from tetragonal to orthorhombic below 70 K at ambient pressure-the crystal structure in the superconducting state shows remarkable similarities to that of the REFeAsO(1-x)F(x) (RE = rare earth) superconductors. 相似文献
84.
Stereoselective synthesis of benzyl-protected β-galactosides by propionitrile-mediated glycosylation
Akiharu Ueki Masafumi Hirota Keiko Komatsu Yutaka Takano Michio Iwaoka Hironobu Hojo Yoshiaki Nakahara 《Tetrahedron》2008,64(11):2611-2618
β-Selective galactosylation was studied using a series of 2-O-benzylated phenyl 1-thio-galactosides and glycosyl acceptors in propionitrile with BSP-TTBP-Tf2O. The glycosylation enabled us to synthesize useful precursors of N-acetyllactosamine and core 1 O-glycoserine derivatives in a highly convergent manner. 相似文献
85.
Dr. Yu Harabuchi Dr. Hiroki Hayashi Dr. Hideaki Takano Prof. Tsuyoshi Mita Prof. Satoshi Maeda 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2023,135(1):e202211936
Systematic reaction path exploration revealed the entire mechanism of Knowles's light-promoted catalytic intramolecular hydroamination. Bond formation/cleavage competes with single electron transfer (SET) between the catalyst and substrate. These processes are described by adiabatic processes through transition states in an electronic state and non-radiative transitions through the seam of crossings (SX) between different electronic states. This study determined the energetically favorable SET path by introducing a practical computational model representing SET as non-adiabatic transitions via SXs between substrate's potential energy surfaces for different charge states adjusted based on the catalyst's redox potential. Calculations showed that the reduction and proton shuttle process proceeded concertedly. Also, the relative importance of SET paths (giving the product and leading back to the reactant) varies depending on the catalyst's redox potential, affecting the yield. 相似文献
86.
Jianxia Jiao Qun Xu Limin Li Takano Tsubasa Takaomi Kobayashi 《Colloid and polymer science》2008,286(13):1485-1491
Titania–silica composite have been prepared using polyethylene glycol (PEG) with different molecular weights (M
w), PEG20000, PEG10000, and PEG2000, as template in supercritical carbon dioxide (SC CO2). The composite precursors were dissolved in SC CO2 and impregnated into PEG templates using SC CO2 as swelling agent and carrier. After removing the template by calcination at suitable temperature, the titania–silica composite
were obtained. The composite were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, and nitrogen
sorption–desorption experiment. Photocatalytic activity of the samples has been investigated by photodegradation of methyl
orange. Results indicate that there are many Si–O–Ti linkages in the TiO2/SiO2 composite; the PEG template has a significant influence on the structure of TiO2/SiO2. In addition, the TiO2/SiO2 prepared with PEG10000 exhibited high photocatalytic efficiency. So this work supplies a clue to control and obtain the TiO2/SiO2 composite with different photocatalytic reactivity with the aid of suitable PEG template in supercritical CO2. 相似文献
87.
A Programmable Signaling Molecular Recognition Nanocavity Prepared by Molecular Imprinting and Post‐Imprinting Modifications 下载免费PDF全文
Ryo Horikawa Dr. Hirobumi Sunayama Dr. Yukiya Kitayama Dr. Eri Takano Prof. Dr. Toshifumi Takeuchi 《Angewandte Chemie (International ed. in English)》2016,55(42):13023-13027
Inspired by biosystems, a process is proposed for preparing next‐generation artificial polymer receptors with molecular recognition abilities capable of programmable site‐directed modification following construction of nanocavities to provide multi‐functionality. The proposed strategy involves strictly regulated multi‐step chemical modifications: 1) fabrication of scaffolds by molecular imprinting for use as molecular recognition fields possessing reactive sites for further modifications at pre‐determined positions, and 2) conjugation of appropriate functional groups with the reactive sites by post‐imprinting modifications to develop programmed functionalizations designed prior to polymerization, allowing independent introduction of multiple functional groups. The proposed strategy holds promise as a reliable, affordable, and versatile approach, facilitating the emergence of polymer‐based artificial antibodies bearing desirable functions that are beyond those of natural antibodies. 相似文献
88.
Nagamitsu T Takano D Marumoto K Fukuda T Furuya K Otoguro K Takeda K Kuwajima I Harigaya Y Omura S 《The Journal of organic chemistry》2007,72(8):2744-2756
The total synthesis of borrelidin has been achieved. The best feature of our synthetic route is macrocyclization at C11-C12 for the construction of an 18-membered ring after esterification between two segments. A detailed examination of the macrocyclization led us to the samarium(II) iodide-mediated intramolecular Reformatsky-type reaction as the most efficient synthetic approach. The two key segments were synthesized through regioselective methylation, directed hydrogenation, stereoselective Reformatsky-type reaction, and MgBr2.Et2O-mediated chelation-controlled allylation. 相似文献
89.
90.
Takayoshi Fujii Tomoyoshi Takano Hiroyuki Morita Toshiaki Yoshimura 《Tetrahedron》2006,62(41):9622-9627
The fluorination of 10-oxo-10H-5λ4,10λ4-thianthren-5-ylideneamine (2) with Selectfluor™ affords 5-fluoro-10-oxo-5,10-dihydro-5λ6,10λ4-thianthren-5-nitrile (4). The amination of 4 with morpholine gives 5-morpholino-10-oxo-5,10-dihydro-5λ6,10λ4-thianthren-5-nitrile (5). The stereochemical course of both reactions has been studied, while the configurations of their products, cis-isomer 4 and trans-5-morpholino-10-oxo-5,10-dihydro-5λ6,10λ4-thianthren-5-nitrile (trans-5) are elucidated by the use of X-ray crystallographic analyses. 相似文献