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61.
Kei Fujise Eiji Tsurumaki Gaku Fukuhara Nobuyuki Hara Yoshitane Imai Shinji Toyota 《化学:亚洲杂志》2020,15(16):2456-2461
Polycyclic aromatic hydrocarbons consisting of three fused anthracene units were designed as new π‐conjugated compounds having helical structures. These expanded helicenes were synthesized by Pt‐catalyzed cycloisomerization of the corresponding ethynyl‐substituted precursors. The nonplanar and helical structure was confirmed by X‐ray analysis and DFT calculations, and the barrier to helical inversion was estimated to be 34 kJ mol?1. The enantiomers of the diphenyl derivative were successfully resolved by chiral HPLC. Enantiopure samples showed good chiroptical performance in the CD (|Δ?| 1380 L mol?1 cm?1) and CPL (|glum| 0.013) spectra, and these values were considerably large for simple organic molecules. The unique chiroptical properties are discussed on the basis of the molecular structure and the electronic state with the aid of time‐dependent DFT calculations. 相似文献
62.
Dr. Takaaki Mitsuhashi Dr. Lena Barra Zachary Powers Volga Kojasoy Andrea Cheng Feng Yang Dr. Yoshimasa Taniguchi Dr. Takashi Kikuchi Prof. Dr. Makoto Fujita Prof. Dr. Dean J. Tantillo Prof. Dr. John A. Porco Jr Prof. Dr. Ikuro Abe 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(52):23980-23989
Fungal meroterpenoids are a diverse group of hybrid natural products with impressive structural complexity and high potential as drug candidates. In this work, we evaluate the promiscuity of the early structure diversity-generating step in fungal meroterpenoid biosynthetic pathways: the multibond-forming polyene cyclizations catalyzed by the yet poorly understood family of fungal meroterpenoid cyclases. In total, 12 unnatural meroterpenoids were accessed chemoenzymatically using synthetic substrates. Their complex structures were determined by 2D NMR studies as well as crystalline-sponge-based X-ray diffraction analyses. The results obtained revealed a high degree of enzyme promiscuity and experimental results which together with quantum chemical calculations provided a deeper insight into the catalytic activity of this new family of non-canonical, terpene cyclases. The knowledge obtained paves the way to design and engineer artificial pathways towards second generation meroterpenoids with valuable bioactivities based on combinatorial biosynthetic strategies. 相似文献
63.
Akio Urushima Dr. Daisuke Taura Makoto Tanaka Naomichi Horimoto Dr. Junki Tanabe Dr. Naoki Ousaka Prof. Tadashi Mori Prof. Eiji Yashima 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(19):7548-7556
A novel 2,6-anthrylene-linked bis(m-terphenylcarboxylic acid) strand ( 1 ) self-associates into a racemic double-helix. In the presence of chiral mono- and diamines, either a right- or left-handed double-helix was predominantly induced by chiral amines sandwiched between the carboxylic acid strands with accompanying stacking of the two prochiral anthracene linker units in an enantiotopic face-selective way, as revealed by circular dichroism and NMR spectral analyses. The photoirradiation of the optically active double helices complexed with chiral amines proceeded in a diastereo- (anti or syn) and enantiodifferentiating way to afford the chiral anti-photodimer with up to 98 % enantiomeric excess when (R)-phenylethylamine was used as a chiral double-helix inducer. The resulting optically active anti-photodimer can recognize the chirality of amines and diastereoselectively complex with chiral amines. 相似文献
64.
Noriaki Suetake Hideaki Kawano Go Tanaka Hidenobu Hashikami Eiji Uchino 《Optical Review》2011,18(6):423-429
In this paper, a new image enlargement method applying the backprojection for lost pixel (BPLP) to the predefined codebook-based
method is proposed. BPLP is a method for image restoration. In BPLP, the eigenspace reflecting the characteristics of an input
image is generated from the remained pixels and is used to restore the missing pixels. In the proposed method, the eigenspace
is replaced by one generated from the predefined codebook (PDC). PDC represents edge-blurring properties in a small image
patch and consists of pairs of low- and high-frequency image patches on various edge patterns. By replacing the PDC-based
estimation of lost high-frequency components with BPLP, a fast image enlargement method retaining its performance can be developed.
Through some experiments, the effectiveness of the proposed method was demonstrated. Especially, it was confirmed that the
processing time of the proposed method was shortened to about 1/50 that of the PDC-based method. 相似文献
65.
This paper reports the summary of experiments performed to successive generate small-scale underwater shock waves by means
of shock-induced collapse of microbubbles confined in a narrow gap. The project is motivated to develop a method for efficient
inactivation of marine bacteria contained in ship ballast water by high impulsive pressure loading. The shock wave–air bubbles
interaction was visualized by shadowgraph; the images were recorded by ImaCon200, and simultaneous pressure measurements were
performed by using an optical fiber pressure transducer with higher temporal resolution. Attaching small air bubbles on a
single nylon fiber and placing it in a confined space, we demonstrated sequential generation of impulsive high pressures at
the successive collapses of small bubbles at incident and reflected shock loadings. The values of the very short impulsive
pressures that occurred repeatedly for a relatively long term are found high enough to inactivate marine bacteria. 相似文献
66.
Takahiro Gunji Kengo Hirama Satoru Tsukada Yoshimoto Abe 《Journal of Sol-Gel Science and Technology》2014,72(1):80-84
An organic–inorganic hybrid was prepared by simply mixing a fullerene derivative with polymethoxysiloxane. First, C60 was subjected to a radical addition reaction with 4,4′-azobis(4-cyanovaleric acid) to provide a C60 derivative. Polymethoxysiloxane was prepared by a controlled hydrolytic condensation of tetramethoxysilane. These two compounds were mixed and heated to provide hybrid bulk body. The hybrid bulk body showed high mechanical strength and elastic modulus compared with polymethoxysiloxane or the C60/polymethoxysiloxane hybrid. The formation of a dense siloxane network was established by a homogeneous mixing of the C60 derivative with polymethoxysiloxane. 相似文献
67.
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
68.
Machiko Shigemi Takahiro Takekiyo Hiroshi Abe Nozomu Hamaya Yukihiro Yoshimura 《Journal of solution chemistry》2014,43(9-10):1614-1624
We have used Raman spectroscopy to investigate the high-pressure phase behavior of 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]), a representative ionic liquid, at pressures up to ~7.5 GPa. We have also studied how increasing pressure leads to conformational changes in the [bmim]+ cation. We have found that liquid [bmim][BF4] undergoes pressure-induced solidification (freezing) into a superpressed (metastable) state at 2.5 GPa; another structural change probably occurs at ~6 GPa. Remarkably, conformational changes in the [bmim]+ cation between trans and gauche conformers are concordant with the metastable structural changes of [bmim][BF4]. As the pressure is increased from ambient, the fraction of gauche conformers increases, but the gauche fraction decreases above the solidification pressure (2.5 GPa), and slope of the gauche/trans ratio changes again above 6 GPa. We interpret these results in terms of the fragility of the ionic liquid. 相似文献
69.
In this study, we achieved the first total synthesis of natural prunustatin A (1), a novel inhibitor of glucose-regulated protein 78 (GRP78) expression. A key feature included a 15-membered ring macrocyclization, which was successfully accomplished by employing Shiina macrolactonization using 2-methyl-6-nitrobenzoic anhydride (MNBA) and 4-dimethylaminopyridine (DMAP). 相似文献
70.
A one-pot approach to indolo[2,1-b]quinazolines from indole-3-carbaldehydes through the Dakin oxidation was developed. It was shown that the reaction proceeded through the condensation of indole-3-carbaldehydes with isatoic anhydrides, derived in situ from indole-3-carbaldehydes by the Dakin oxidation, and further oxidation/cyclization steps. 相似文献