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1.
Dongshuang Wu Kohei Kusada Tomokazu Yamamoto Takaaki Toriyama Syo Matsumura Ibrahima Gueye Okkyun Seo Jaemyung Kim Satoshi Hiroi Osami Sakata Shogo Kawaguchi Yoshiki Kubota Hiroshi Kitagawa 《Chemical science》2020,11(47):12731
We report the synthesis of high-entropy-alloy (HEA) nanoparticles (NPs) consisting of five platinum group metals (Ru, Rh, Pd, Ir and Pt) through a facile one-pot polyol process. We investigated the electronic structure of HEA NPs using hard X-ray photoelectron spectroscopy, which is the first direct observation of the electronic structure of HEA NPs. Significantly, the HEA NPs possessed a broad valence band spectrum without any obvious peaks. This implies that the HEA NPs have random atomic configurations leading to a variety of local electronic structures. We examined the hydrogen evolution reaction (HER) and observed a remarkably high HER activity on HEA NPs. At an overpotential of 25 mV, the turnover frequencies of HEA NPs were 9.5 and 7.8 times higher than those of a commercial Pt catalyst in 0.05 M H2SO4 and 1.0 M KOH electrolytes, respectively. Moreover, the HEA NPs showed almost no loss during a cycling test and were much more stable than the commercial Pt catalyst. Our findings on HEA NPs may provide a new paradigm for the design of catalysts.RuRhPdIrPt high-entropy-alloy nanoparticles with a broad and featureless valence band spectrum show high hydrogen evolution reaction activity. 相似文献
2.
Direct Introduction of a Dimesitylboryl Group Using Base‐Mediated Substitution of Aryl Halides with Silyldimesitylborane 下载免费PDF全文
Dr. Eiji Yamamoto Kiyotaka Izumi Ryosuke Shishido Prof. Dr. Tomohiro Seki Noriaki Tokodai Prof. Dr. Hajime Ito 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(49):17547-17551
The first dimesitylboryl substitution of aryl halides with a silylborane bearing a dimesitylboryl group in the presence of alkali‐metal alkoxides is described. The reactions of aryl bromides or iodides with Ph2MeSi?BMes2 and Na(OtBu) afforded the desired aryl dimesitylboranes in good to high yields and with high borylation/silylation ratios. Selective reaction of the sterically less‐hindered C?Br bond of dibromoarenes provided monoborylated products. This reaction was used to rapidly construct a D‐π‐A aryl dimesityl borane with a non‐symmetrical biphenyl spacer. 相似文献
3.
4.
Synthesis of a Pentacene‐Type Silaborin via Double Dehydrogenative Cyclization of 1,4‐Diboryl‐2,5‐disilylbenzene 下载免费PDF全文
Tatsuya Hirofuji Dr. Toshiaki Ikeda Prof. Dr. Takeharu Haino Prof. Dr. Yohsuke Yamamoto Prof. Dr. Atsushi Kawachi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(28):9734-9739
A new pentacene‐type silaborin, in which three benzene rings are bridged by silicon and boron atoms, has been synthesized and characterized by using NMR spectroscopy and X‐ray crystallographic analysis. The precursor, 1,4‐bis(dimesitylboryl)‐2,5‐bis(phenylsilyl)benzene ( 4 ), was prepared by stepwise introduction of a silyl group and a boryl group to a benzene ring starting from 1,4‐dibromobenzene. Double cyclization of 4 proceeds by a H‐Mes exchange and a B‐H/C‐H dehydrogenative condensation to afford pentacene‐type silaborin 5 . X‐ray crystal structure analysis reveals that 5 adopts a bent structure rather than a planar one. UV/Vis spectra and DFT calculations for 5 reveal a lowering of the LUMO energy level compared with corresponding anthracene‐type 3 . 相似文献
5.
Dr. Takeshi Matsumoto Risa Yamamoto Dr. Masanori Wakizaka Dr. Akinobu Nakada Prof. Dr. Ho-Chol Chang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(43):9609-9619
The global demand for energy and the concerns over climate issues renders the development of alternative renewable energy sources such as hydrogen (H2) important. A high-spin (hs) FeII complex with o-phenylenediamine (opda) ligands, [FeII(opda)3]2+ (hs- [6R] 2+), was reported showing photochemical H2 evolution. In addition, a low-spin (ls) [FeII(bqdi)3]2+ (bqdi: o-benzoquinodiimine) (ls- [0R] 2+) formation by O2 oxidation of hs- [6R] 2+, accompanied by ligand-based six-proton and six-electron transfer, revealed the potential of the complex with redox-active ligands as a novel multiple-proton and -electron storage material, albeit that the mechanism has not yet been understood. This paper reports that the oxidized ls- [0R] [PF6]2 can be reduced by hydrazine giving ls-[FeII(opda)(bqdi)2][PF6]2 (ls- [2R] [PF6]2) and ls-[FeII(opda)2(bqdi)][PF6]2 (ls- [4R] [PF6]2) with localized ligand-based proton-coupled mixed-valence (LPMV) states. The first isolation and characterization of the key intermediates with LPMV states offer unprecedented molecular insights into the design of photoresponsive molecule-based hydrogen-storage materials. 相似文献
6.
Yuta Yamamoto Shogo Nakano Fumio Seki Yasuteru Shigeta Sohei Ito Hiroaki Tokiwa Makoto Takeda 《Molecules (Basel, Switzerland)》2021,26(5)
Infection of hosts by morbilliviruses is facilitated by the interaction between viral hemagglutinin (H-protein) and the signaling lymphocytic activation molecule (SLAM). Recently, the functional importance of the n-terminal region of human SLAM as a measles virus receptor was demonstrated. However, the functional roles of this region in the infection process by other morbilliviruses and host range determination remain unknown, partly because this region is highly flexible, which has hampered accurate structure determination of this region by X-ray crystallography. In this study, we analyzed the interaction between the H-protein from canine distemper virus (CDV-H) and SLAMs by a computational chemistry approach. Molecular dynamics simulations and fragment molecular orbital analysis demonstrated that the unique His28 in the N-terminal region of SLAM from Macaca is a key determinant that enables the formation of a stable interaction with CDV-H, providing a basis for CDV infection in Macaca. The computational chemistry approach presented should enable the determination of molecular interactions involving regions of proteins that are difficult to predict from crystal structures because of their high flexibility. 相似文献
7.
Optical Review - This paper proposes a novel steganography method to show an aerial image that is formed with aerial imaging by retro-reflection by use of dual transparent balls made of acrylic... 相似文献
8.
Prof. Dr. Erika Nakashima Prof. PhD Hisashi Yamamoto 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(35):e202103989
Since the global peptide drug market demand has been predicted to increase, highly efficient and inexpensive mass scale peptides are required. However, the production process raises questions about the cost of energy input, scale-up production, raw materials, and solvents treatment. This paper introduces 2 methods for the 2–4 mer oligopeptides bond formation for batch reaction utilizing 50–100 mol% of a mild Brønsted acid under the mild condition. One of the methods has been capably adapted to flow synthesis at room temperature using organic solvents with boiling points below 100 °C. The method applies the tert-butoxycarbonyl amino methoxy group, forming the desired dipeptide without solvent at mild temperatures. Furthermore, the conversion of the carboxylic acid leaving the group to phenyl ester promotes peptide bond formation, and the reaction were applied to di, tri, and tetrapeptide bond formation in excellent yield without notable racemization at ambient temperature (up to >99 % yield and 99 : 1 dr). Finally, this study proposes this new production method to overcome the limited scale-up production by reaction device scale: liquid phase biomimetic catalytic peptide flow synthesis utilizing a mild Brønsted acid. 相似文献
9.
Feng Cheng Shuqi Wu Wenwei Zheng Shengqun Su Takumi Nakanishi Wenhuang Xu Pritam Sadhukhan Hibiki Sejima Shimon Ikenaga Kaoru Yamamoto Kaige Gao Shinji Kanegawa Prof. Osamu Sato 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(59):e202202161
The crystallization of a complex having electron transfer properties in a polar space group can induce the polarization switching of a crystal in a specific direction, which is attractive for the development of sensors, memory devices, and capacitors. Unfortunately, the probability of crystallization in a polar space group is usually low. Noticing that enantiopure compounds crystallize in Sohncke space groups, this paper reports a strategy for the molecular design of non-ferroelectric polarization switching crystals based on the use of intramolecular electron transfer and chirality. In addition, this paper describes the synthesis of a mononuclear valence tautomeric (VT) cobalt complex bearing an enantiopure ligand. The introduction of enantiomer enables the crystallization of the complex in the polar space group (P21). The polarization of the crystals along the b-axis direction is not canceled out and the VT transition is accompanied by a change in the macroscopic polarization of the polar crystal. Polarization switching via electron transfer is realized at around room temperature. 相似文献
10.
Application of DEM modified with enlarged particle model to simulation of bead motion in a bead mill
We applied the discrete element method (DEM) of simulation modified by an enlarged particle model to simulate bead motion in a large bead mill. The stainless-steel bead mill has inner diameter of 102 mm and mill length of 198 mm. The bead diameter and filling ratio were fixed respectively at 0.5 mm and 85%. The agitator rotational speed was changed from 1863 to 3261 rpm. The bead motion was monitored experimentally using a high-speed video camera through a transparent mill body. For the simulation, enlarged particle sizes were set as 3-6 mm in diameter. With the DEM modified by the enlarged particle model, the motion of enlarged particles in a mill was simulated.The velocity data of the simulated enlarged particles were compared with those obtained in the experiment. The simulated velocity of the enlarged particles depends on the virtual frictional coefficient in the DEM model. The optimized value of the virtual frictional coefficient can be determined by considering the accumulated mean value. Results show that the velocity of the enlarged particles simulated increases with an increase in the optimum virtual frictional coefficient, but the simulated velocity agrees well with that determined experimentally by optimizing the virtual frictional coefficient in the simulation. The computing time in the simulation decreases with increased particle size. 相似文献