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71.
Dr. Masayuki Gon Junko Wakabayashi Masashi Nakamura Prof. Dr. Kazuo Tanaka Prof. Dr. Yoshiki Chujo 《化学:亚洲杂志》2021,16(6):696-703
We demonstrate that multi-fluorinated boron-fused azobenzene (BAz) complexes can work as a strong electron acceptor in electron donor-acceptor (D-A) type π-conjugated polymers. Position-dependent substitution effects were revealed, and the energy level of the lowest unoccupied molecular orbital (LUMO) was critically decreased by fluorination. As a result, the obtained polymers showed near-infrared (NIR) emission (λPL=758–847 nm) with high absolute photoluminescence quantum yield (ΦPL=7–23%) originating from low-lying LUMO energy levels of the BAz moieties (−3.94 to −4.25 eV). Owing to inherent solid-state emissive properties of the BAz units, deeper NIR emission (λPL=852980 nm) was detected in film state. Clear solvent effects prove that the NIR emission is from a charge transfer state originating from a strong D-A interaction. The effects of fluorination on the frontier orbitals are well understandable and predictable by theoretical calculation with density functional theory. This study demonstrates the effectiveness of fluorination to the BAz units for producing a strong electron-accepting unit through fine-tuning of energy gaps, which can be the promising strategy for designing NIR absorptive and emissive materials. 相似文献
72.
We present the single-mode single-polarization regime of a circular-hole holey fiber consisting of a core with large elliptical holes. The elliptical holes in the core, which produce large anisotropies, split the fundamental mode into two orthogonally polarized fundamental modes, often referred to as slow and fast modes. This fiber can guide only one polarization state of the fundamental mode when a fundamental space-filling mode index of the cladding region is designed to lie between these indices of the slow and fast modes of the core region. We demonstrate one design example of this fiber and show that the single-polarization regime can be achieved over a wide wavelength range. 相似文献
73.
74.
Dual Catalysis with Copper and Rhenium for Trifluoromethylation of Propargylic Alcohols: Efficient Synthesis of α‐Trifluoromethylated Enones 下载免费PDF全文
Dr. Hiromichi Egami Takafumi Ide Masashi Fujita Toshifumi Tojo Prof.Dr. Yoshitaka Hamashima Prof.Dr. Mikiko Sodeoka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(38):12061-12065
Trifluoromethylation of propargylic alcohols to provide (Z)‐α‐trifluoromethylated enones and β‐unsubstituted α‐trifluoromethylated enones proceeded with high yield and selectivity in the presence of CuI/Re2O7. The Z isomer was formed under kinetic control, though it is less stable than the E isomer in terms of steric repulsion. 相似文献
75.
Assembly of Na3V2(PO4)3 Nanoparticles Confined in a One‐Dimensional Carbon Sheath for Enhanced Sodium‐Ion Cathode Properties 下载免费PDF全文
Dr. Satoshi Kajiyama Dr. Jun Kikkawa Junichi Hoshino Dr. Masashi Okubo Dr. Eiji Hosono 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(39):12636-12640
Structural and morphological control is an effective approach for improvement of electrochemical properties in rechargeable batteries. One‐dimensionally assembled structure composed of NASICON‐type Na3V2(PO4)3 nanoparticles were fabricated through an electrospinning method to meet the requirements for the development of efficient electrode materials in Na‐ion batteries. High‐temperature treatment of electrospun precursor fibers under an argon flow provides a nonwoven fabric of nanowires comprising crystallographically oriented nanoparticles of NASICON‐type Na3V2(PO4)3 within a carbon sheath. The mesostructure comprising NASICON‐type Na3V2(PO4)3 and carbon give a short sodium‐ion transport pass and an efficient electron conduction pass. Electrochemical properties of NASICON‐type Na3V2(PO4)3 are improved on the basis of one‐dimensional nanostructures designed in the present study. 相似文献
76.
Direct Asymmetric Mannich‐Type Reaction of α‐Isocyanoacetates with Ketimines using Cinchona Alkaloid/Copper(II) Catalysts 下载免费PDF全文
Masashi Hayashi Masaru Iwanaga Noriyuki Shiomi Dr. Daisuke Nakane Prof. Dr. Hideki Masuda Prof. Dr. Shuichi Nakamura 《Angewandte Chemie (International ed. in English)》2014,53(32):8411-8415
The enantioselective direct Mannich‐type reaction of ketimines with α‐isocyanoacetates has been developed. Excellent yields and enantioselectivity were observed for the reaction of various ketimines and α‐isocyanoacetates using cinchona alkaloid/Cu(OTf)2 and a base. Both enantiomers of the products could be obtained by using pseudoenantiomeric chiral catalysts. This process offers an efficient route for the synthesis of α,β‐diamino acids. 相似文献
77.
Dr. Hiromu Kashida Hidenori Azuma Ryoko Maruyama Dr. Yasuyuki Araki Prof. Dr. Takehiko Wada Prof. Dr. Hiroyuki Asanuma 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(28):11456-11459
Herein we report the construction of efficient light-harvesting antennae by hybridization of DNA oligonucleotides containing high densities of fluorophores into DNA junctions through d -threoninol. Six pyrene donors could be incorporated into each arm without self-quenching. A perylene acceptor was located at the center of the junction. Antenna effects of a duplex and three- to eight-way junctions were systematically compared. Six- and eight-way junctions had the highest antenna effects, and their effective absorption coefficients were 8.5 times higher than that of perylene. Interestingly, even-numbered junctions had higher efficiencies than odd-numbered junctions. Nondenaturing gel analyses and fluorescence lifetime measurements demonstrated that the strong odd–even effects were derived from differences in the stability of junctions. The results presented will guide the design of efficient artificial photosynthetic systems. 相似文献
78.
Yulu Jiang Taro Ozaki Mei Harada Tadachika Miyasaka Hajime Sato Kazunori Miyamoto Junichiro Kanazawa Chengwei Liu Jun‐ichi Maruyama Masaatsu Adachi Atsuo Nakazaki Toshio Nishikawa Masanobu Uchiyama Atsushi Minami Hideaki Oikawa 《Angewandte Chemie (International ed. in English)》2020,59(41):17996-18002
Lolitrems are tremorgenic indole diterpenes that exhibit a unique 5/6 bicyclic system of the indole moiety. Although genetic analysis has indicated that the prenyltransferase LtmE and the cytochrome P450 LtmJ are involved in the construction of this unique structure, the detailed mechanism remains to be elucidated. Herein, we report the reconstitution of the biosynthetic pathway for lolitrems employing a recently established genome‐editing technique for the expression host Aspergillus oryzae. Heterologous expression and bioconversion of the various intermediates revealed that LtmJ catalyzes multistep oxidation to furnish the lolitrem core. We also isolated the key reaction intermediate with an epoxyalcohol moiety. This observation allowed us to establish the mechanism of radical‐induced cyclization, which was firmly supported by density functional theory calculations and a model experiment with a synthetic analogue. 相似文献
79.
Vinyl-substituted silylenes, 2,5-bis(methylene)-1-silacyclopentane-1,1-diyl ( 1 ) and 2-methylene-1-silacyclopentane-1,1-diyl ( 2 ), generated photochemically from the corresponding trisilanes in 3-methylpentane (3-MP) at 77 K, showed broad bands at 505 and 475 nm, respectively, which were assigned to the n(Si)-3p(Si) transition. The origin of the red shift in the n(Si)-3p(Si) transition is ascribed to the significant lowering of the 3p(Si) orbital level caused by the vinyl substitution on the silylene; the relatively high-lying 3p(Si) orbital can interact more effectively with the antibonding π* orbital than with the bonding π orbital of the vinyl group. The absorption spectra for 1 and 2 in the presence of several bases in 3-MP glass matrix shifted significantly to blue due to the formation of the corresponding base complexes. Analysis of the spectral change of the silylenes upon complexation with bases was very constructive for the understanding of the structural characteristics of substituted silylenes. 相似文献
80.
Yukiko Yasuoka Yuichiro Izumi Takashi Fukuyama Haruki Omiya Truyen D. Pham Hideki Inoue Tomomi Oshima Taiga Yamazaki Takayuki Uematsu Noritada Kobayashi Yoshitaka Shimada Yasushi Nagaba Tetsuro Yamashita Masashi Mukoyama Yuichi Sato Susan M. Wall Jeff M. Sands Noriko Takahashi Katsumasa Kawahara Hiroshi Nonoguchi 《Molecules (Basel, Switzerland)》2022,27(3)
Anemia is a major complication of chronic renal failure. To treat this anemia, prolylhydroxylase domain enzyme (PHD) inhibitors as well as erythropoiesis-stimulating agents (ESAs) have been used. Although PHD inhibitors rapidly stimulate erythropoietin (Epo) production, the precise sites of Epo production following the administration of these drugs have not been identified. We developed a novel method for the detection of the Epo protein that employs deglycosylation-coupled Western blotting. With protein deglycosylation, tissue Epo contents can be quantified over an extremely wide range. Using this method, we examined the effects of the PHD inhibitor, Roxadustat (ROX), and severe hypoxia on Epo production in various tissues in rats. We observed that ROX increased Epo mRNA expression in both the kidneys and liver. However, Epo protein was detected in the kidneys but not in the liver. Epo protein was also detected in the salivary glands, spleen, epididymis and ovaries. However, both PHD inhibitors (ROX) and severe hypoxia increased the Epo protein abundance only in the kidneys. These data show that, while Epo is produced in many tissues, PHD inhibitors as well as severe hypoxia regulate Epo production only in the kidneys. 相似文献