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61.
Yoshino Katsurayama Prof. Yasuhiro Ikabata Prof. Hajime Maeda Prof. Masahito Segi Prof. Hiromi Nakai Prof. Taniyuki Furuyama 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(2):e202103223
The high penetration of near-infrared (NIR) light makes it effective for use in selective reactions under light-shielded conditions, such as in sealed reactors and deep tissues. Herein, we report the development of phthalocyanine catalysts directly activated by NIR light to transform small organic molecules. The desired photocatalytic properties were achieved in the phthalocyanines by introducing the appropriate peripheral substituents and central metal. These phthalocyanine photocatalysts promote cross-dehydrogenative-coupling (CDC) under irradiation with 810 nm NIR light. The choice of solvent is important, and a mixture of a reaction-accelerating (pyridine) and -decelerating (methanol) solvents was particularly effective. Moreover, we demonstrate photoreactions under visible-light-shielded conditions through the transmission of NIR light. A combined experimental and computational mechanistic analysis revealed that this NIR reaction does not involve a photoredox-type mechanism with electron transfer, but instead a singlet-oxygen-mediated mechanism with energy transfer. 相似文献
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Takashi Kitayama Maki Nakahira Kae Yamasaki Hiromi Inoue Chika Imada Yuji Yonekura Masataka Awata Hikaru Takaya Yasushi Kawai Kohta Ohnishi Akira Murakami 《Tetrahedron》2013
Zerumbone 1, having powerful latent reactivity and containing two conjugated double bonds and a double conjugated carbonyl group is the major component of the essential oil of wild ginger, Zingiber zerumbet Smith. The conjugation system plays an important role in the expression of biological activity. N-Bromosuccinimide (NBS) reaction of 1 gave high reactive intermediate 2 with an exo-methylene group, which was obtained from 1 quantitatively. Treatment of 2 with nucleophiles gave various zerumbone-pendant derivatives, including C–H, C–O, C–N, and C–C bond formation, maintaining the conjugation system through SN2′-type reaction. Almost all zerumbone-pendant derivatives showed a good value of IC50 against the suppressive effect of NO generation. Among them, amine derivative 5, binding with 2 mol of zerumbone, showed the strongest activity (IC50: 0.24 μM). 相似文献
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Acceleration of self‐consistent field convergence in ab initio molecular dynamics simulation with multiconfigurational wave function 下载免费PDF全文
The Lagrange interpolation of molecular orbital (LIMO) method, which reduces the number of self‐consistent field iterations in ab initio molecular dynamics simulations with the Hartree–Fock method and the Kohn–Sham density functional theories, is extended to the theory of multiconfigurational wave functions. We examine two types of treatments for the active orbitals that are partially occupied. The first treatment, as denoted by LIMO(C), is a simple application of the conventional LIMO method to the union of the inactive core and the active orbitals. The second, as denoted by LIMO(S), separately treats the inactive core and the active orbitals. Numerical tests to compare the two treatments clarify that LIMO(S) is superior to LIMO(C). Further applications of LIMO(S) to various systems demonstrate its effectiveness and robustness. © 2014 Wiley Periodicals, Inc. 相似文献
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Hiromi NAKANISHI Atsushi MORI Kouki TAKEDA Houdo TANAKA Natsuko KOBAYASHI Keitaro TANOI Takashi YAMAKAWA Satoshi MORI 《Proceedings of the Japan Academy. Series B, Physical and biological sciences》2015,91(4):160-174
Six months after the explosion of TEPCO’s Fukushima Dai-ichi nuclear power plant, radioactive
silver (110mAg), was detected in concentrations of 3754 Bq/kg in Nephila
clavata (the orb-web spider; Joro-gumo in Japanese) collected at
Nimaibashi, Iitate village in Fukushima Prefecture, whereas 110mAg in the soil was
43.1 Bq/kg. A survey of 35 faunal species in the terrestrial environment during the 3.5 years
after the accident showed that most of Anthropoda had two orders higher 110mAg in
their tissues than soils, although silver is not an essential element for their life. However,
tracing of the activity of 110mAg detected in spider Atypus karschi
collected regularly at a fixed location showed that it declined much faster than the physical
half-life. These results suggest that 110mAg was at once biologically concentrated
by faunal species, especially Arthropoda, through food chain. The factors affecting the
subsequent rapid decline of 110mAg concentration in faunal species are
discussed. 相似文献
68.
Ryota Kudo Masahiro Sonobe Yoshiaki Chino Yu Kitazawa Mutsumi Kimura 《Molecules (Basel, Switzerland)》2020,25(23)
The synthesis and characterization of two phthalocyanine (Pc) structural isomers, 1 and 2, in which four 2,6-di(hexyloxy)phenyl units were attached directly to the 1,8,15,22- or 1,4,15,18-positions of the Pc rings, are described. Both Pcs 1 and 2 exhibited low melting points, i.e., 120 and 130 °C respectively, due to the reduction in intermolecular π-π interaction among the Pc rings caused by the steric hindrance of 2,6-dihexyloxybenzene units. The thermal behaviors were investigated with temperature-controlled polarizing optical microscopy, differential scanning calorimetry, powder X-ray diffraction, and absorption spectral analyses. Pc 1, having C4h molecular symmetry, organized into a lamellar structure containing lateral assemblies of Pc rings. In contrast, the other Pc 2 revealed the formation of metastable crystalline phases, including disordered stacks of Pcs due to rapid cooling from a melted liquid. 相似文献
69.
Shusuke Sato Fumitaka Kudo Michel Rohmer Tadashi Eguchi 《Angewandte Chemie (International ed. in English)》2020,59(1):237-241
Adenosylhopane is a crucial intermediate in the biosynthesis of bacteriohopanepolyols, which are widespread prokaryotic membrane lipids. Herein, it is demonstrated that reconstituted HpnH, a putative radical S‐adenosyl‐l ‐methionine (SAM) enzyme, commonly encoded in the hopanoid biosynthetic gene cluster, converts diploptene into adenosylhopane in the presence of SAM, flavodoxin, flavodoxin reductase, and NADPH. NMR spectra of the enzymatic reaction product were identical to those of synthetic (22R)‐adenosylhopane, indicating that HpnH catalyzes stereoselective C?C formation between C29 of diploptene and C5′ of 5′‐deoxyadenosine. Further, the HpnH reaction in D2O‐containing buffer revealed that a D atom was incorporated at the C22 position of adenosylhopane. Based on these results, we propose a radical addition reaction mechanism catalyzed by HpnH for the formation of the C35 bacteriohopane skeleton. 相似文献
70.