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1.
Highly Segregated Lamello‐Columnar Mesophase Organizations and Fast Charge Carrier Mobility in New Discotic Donor–Acceptor Triads 下载免费PDF全文
Prof. Dr. Ke‐Qing Zhao Ling‐Ling An Xiao‐Bo Zhang Wen‐Hao Yu Prof. Ping Hu Prof. Bi‐Qin Wang Jing Xu Dr. Qing‐Dao Zeng Dr. Hirosato Monobe Dr. Yo Shimizu Dr. Benoît Heinrich Dr. Bertrand Donnio 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(29):10379-10390
Four new donor–acceptor triads (D–A–D) based on discotic and arylene mesogens have been synthesized by using Sonogashira coupling and cyclization reactions. This family of triads consists of two side‐on pending triphenylene mesogens, acting as the electron‐donating groups (D), laterally connected through short lipophilic spacers to a central perylenediimide (PI), benzo[ghi]perylenediimide (BI), or coronenediimide (CI) molecular unit, respectively, playing the role of the electron acceptor (A). All D–A–D triads self‐organize to form a lamello‐columnar oblique mesophase, with a highly segregated donor–acceptor (D–A) heterojunction organization, consequent to efficient molecular self‐sorting. The structure consists in the regular alternation of two disrupted rows of triphenylene columns and a continuous row of diimine species. High‐resolution STM images demonstrate that PI‐TP2 forms stable 2D self‐assembly nanostructures with some various degrees of regularity, whereas the other triads do not self‐organize into ordered architectures. The electron‐transport mobility of CI‐TP2, measured by time‐of‐flight at 200 °C in the mesophase, is one order of magnitude higher than the hole mobility. By means of this specific molecular designing idea, we realized and demonstrated for the first time the so‐called p–n heterojunction at the molecular level in which the electron‐rich triphenylene columns act as the hole transient pathways, and the coronenediimide stacks form the electron‐transport channels. 相似文献
2.
Hirosato Monobe Shoji Mima Takushi Sugino Yo Shimizu Masakatsu Ukon 《Liquid crystals》2013,40(8):1253-1258
The orientational behaviour of the nematic discotic phase of 2,3,6,7,10,11-hexa(4-n-octyloxybenzoyloxy)triphenylene (C8OBT) on substrates coated with a polyimide or cetyltrimethylammonium bromide (CTAB) was investigated by polarizing optical microscopy. The averaged order parameters and directions of the triphenylene core and the carbonyl groups of C8OBT were evaluated by an infrared dichroic method. The discotic nematic (ND) phase of C8OBT exhibits a homeotropic alignment on a polyimide film, a typical nematic schlieren texture on a glass substrate, and a tilted or planar homogeneous alignment on a CTAB-coated substrate. The order parameter of the triphenylene core is higher on a polyimide film (S = 0.6) than on a CTAB-coated substrate (S = 0.2), whereas that of the carbonyl groups remains roughly constant at 0.2 to 0.3 independent of the substrate for the ND phase. 相似文献
3.
Hiroshi Takikawa Arata Nishii Hiromu Takiguchi Hirotoshi Yagishita Masato Tanaka Keiichi Hirano Masanobu Uchiyama Ken Ohmori Keisuke Suzuki 《Angewandte Chemie (International ed. in English)》2020,59(30):12440-12444
An intramolecular benzyne–phenolate [4+2] cycloaddition is reported. Benzyne precursors, having vicinal halogen‐sulfonate functionalities, linked with a phenol(ate) by various tether groups undergo efficient intramolecular [4+2] cycloaddition by treatment with either Ph3MgLi or nBuLi for halogen–metal exchange to form various benzobarrelenes. 相似文献
4.
Saiko KitaharaTakuya Tashiro Yukihiro SugimotoMitsuru Sasaki Hirosato Takikawa 《Tetrahedron letters》2011,52(6):724-726
Sorgomol, isolated from Sorghum bicolor, is the germination stimulant for seeds of root parasitic weeds. The first synthesis of (±)-sorgomol has been achieved by starting from ethyl 2-oxocyclohexanecarboxylate. 相似文献
5.
Hironori Okamura Takanobu Fujioka Naoki Mori Tohru Taniguchi Kenji Monde Hidenori Watanabe Hirosato Takikawa 《Tetrahedron letters》2019,60(32):150917
Salinipostins are cyclic enol-phosphotriesters isolated from a marine-derived Salinispora sp. as antimalarial compounds. Herein, the first enantioselective synthesis of salinipostin A was achieved. Organocatalyst-mediated asymmetric cyclopropanation and regioselective cyclopropane ring opening were the key steps. 相似文献
6.
Shigeyuki Namiki Kenji Takikawa Mako Kamiya Prof. Tetsuo Nagano Prof. Yasuteru Urano Prof. Kenzo Hirose 《Angewandte Chemie (International ed. in English)》2014,53(24):6085-6089
Live imaging of exocytosis dynamics is crucial for a precise spatiotemporal understanding of secretion phenomena, but current approaches have serious limitations. We designed and synthesized small‐molecular fluorescent probes that were chemically optimized for sensing acidic intravesicular pH values, and established that they can be used to sensitively and reliably visualize vesicular dynamics following stimulation. This straightforward technique for the visualization of exocytosis as well as endocytosis/reacidification processes with high spatiotemporal precision is expected to be a powerful tool for investigating dynamic cellular phenomena involving changes in the pH value. 相似文献
7.
A series of novel 6H‐1,3,5‐oxathiazine S,S‐dioxides were synthesized by the m‐CPBA oxidation (2.2 equiv) of 6H‐1,3,5‐oxathizines. The synthetic utilities of the newly synthesized cyclic sulfones were investigated. In a thermal condition, compounds 6H‐1,3,5‐oxathiazine S,S‐dioxides were found relatively stable, but Lewis acid‐induced thermal reaction afforded the corresponding amides. The plausible pathway to amides from 6H‐1,3,5‐oxathiazine S,S‐dioxides was also discussed in this account. 相似文献
8.
The motion of a moored floating body under the action of wave forces, which is influenced by fluid forces, shape of the floating body and mooring forces, should be analysed as a complex coupled motion system. Especially under severe storm conditions or resonant motion of the floating body it is necessary to consider finite amplitude motions of the waves, the floating body and the mooring lines as well as non-linear interactions of these finite amplitude motions. The problem of a floating body has been studied on the basis of linear wave theory by many researchers. However, the finite amplitude motion under a correlated motion system has rarely been taken into account. This paper presents a numerical method for calculating the finite amplitude motion when a floating body is moored by non-linear mooring lines such as chains and cables under severe storm conditions. 相似文献
9.
Ryuji Hirase Koji Honda Mari Ishihara Hideki Yoshioka Hirosato Monobe 《Tetrahedron letters》2018,59(5):469-472
We have investigated synthesis as well as purification of 5,5?-bis(tridecafluorohexyl)-2,2′:5′,2″:5″,2?-quaterthiophene (BFH-4?T, n-type organic semiconducting material) using supercritical carbon dioxide (scCO2) as a green solvent. BFH-4T was obtained in good selectivity and high yield by TDAE/PdCl2-catalyzed reductive coupling reaction of 5-bromo-5′-(tridecafluorohexyl)-2,2′-bithiophene in scCO2. We have also successfully established purification of the reaction mixture by passing scCO2 in the reaction vessel. The product was yellow powder of BFH-4T with purity of more than 99% and Pd catalyst was not contained. 相似文献
10.
Fumoto M Hinou H Ohta T Ito T Yamada K Takimoto A Kondo H Shimizu H Inazu T Nakahara Y Nishimura S 《Journal of the American Chemical Society》2005,127(33):11804-11818
The chemoselective polymer blotting method allows for rapid and efficient synthesis of glycopeptides based on a "catch and release" strategy between solid-phase and water-soluble polymer supports. We have developed a heterobifunctional linker sensitive to glutamic acid specific protease (BLase). The general procedure consists of five steps, namely (i) the solid-phase synthesis of glycopeptide containing BLase sensitive linker, (ii) subsequent deprotections and the release of the glycopeptide from the resin, (iii) chemoselective blotting of the glycopeptide intermediates in the presence of water-soluble polymers with oxylamino functional groups, (iv) sugar elongations using glycosyltransferases, and (v) the release of target glycopeptides from the polymer platform by selective BLase promoted hydrolysis. The combined use of the solid-phase chemical syntheses of peptides and the enzymatic syntheses of carbohydrates on water-soluble polymers would greatly contribute to the production of complicated glycopeptide libraries, thereby enhancing applicative research. We report here a high-throughput synthetic system for the various types of MUC1 glycopeptides exhibiting a variety of sugar moieties. It is our belief that this concept will become part of the entrenched repertoire for the synthesis of biologically important glycopeptides on the basis of glycosyltransferase reactions in automated and combinatorial syntheses. 相似文献