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71.
Salt‐Free Reduction of Nonprecious Transition‐Metal Compounds: Generation of Amorphous Ni Nanoparticles for Catalytic C–C Bond Formation 下载免费PDF全文
Dr. Taiga Yurino Yohei Ueda Dr. Yoshiki Shimizu Dr. Shinji Tanaka Haruka Nishiyama Prof. Dr. Hayato Tsurugi Prof. Dr. Kazuhiko Sato Prof. Dr. Kazushi Mashima 《Angewandte Chemie (International ed. in English)》2015,54(48):14437-14441
A salt‐free procedure for the generation of a wide variety of metal(0) particles, including Fe, Co, Ni, and Cu, was achieved using 2,3,5,6‐tetramethyl‐1,4‐bis(trimethylsilyl)‐1,4‐diaza‐2,5‐cyclohexadiene ( 1 ), which reduced the corresponding metal precursors under mild conditions. Notably, Ni particles formed in situ from the treatment of Ni(acac)2 (acac=acetylacetonate) with 1 in toluene exhibited significant catalytic activity for reductive C? C bond‐forming reactions of aryl halides in the presence of excess amounts of 1 . By examination of high‐magnification transmission electron microscopy images and electron diffraction patterns, we concluded that amorphous Ni nanoparticles (Ni aNPs) were essential for the high catalytic activity. 相似文献
72.
Kotaro Hayashi Hiroyuki Chaya Shigeto Fukushima Sumiyo Watanabe Hiroyasu Takemoto Kensuke Osada Nobuhiro Nishiyama Kanjiro Miyata Kazunori Kataoka 《Macromolecular rapid communications》2016,37(6):486-493
Polyion complexes (b‐PICs) are prepared by mixing single‐ or double‐stranded oligo RNA (aniomer) with poly(ethylene glycol)‐b‐poly(l ‐lysine) (PEG‐PLL) (block catiomer) to clarify the effect of aniomer chain rigidity on association behaviors at varying concentrations. Here, a 21‐mer single‐stranded RNA (ssRNA) (persistence length: 1.0 nm) and a 21‐mer double‐stranded RNA (small interfering RNA, siRNA) (persistence length: 62 nm) are compared. Both oligo RNAs form a minimal charge‐neutralized ionomer pair with a single PEG‐PLL chain, termed unit b‐PIC (uPIC), at low concentrations (<≈0.01 mg mL−1). Above the critical association concentration (≈0.01 mg mL−1), ssRNA b‐PICs form secondary associates, PIC micelles, with sizes up to 30–70 nm, while no such multimolecular assembly is observed for siRNA b‐PICs. The entropy gain associated with the formation of a segregated PIC phase in the multimolecular PIC micelles may not be large enough for rigid siRNA strands to compensate with appreciably high steric repulsion derived from PEG chains. Chain rigidity appears to be a critical parameter in polyion complex association.
73.
Michiko Shimizu Tsuguyuki Saito Yoshiharu Nishiyama Shinichiro Iwamoto Hiroyuki Yano Akira Isogai Takashi Endo 《Macromolecular rapid communications》2016,37(19):1581-1586
The dimensions of nanocelluloses are important factors in controlling their material properties. The present study reports a fast and robust method for estimating the widths of individual nanocellulose particles based on the turbidities of their water dispersions. Seven types of nanocellulose, including short and rigid cellulose nanocrystals and long and flexible cellulose nanofibers, are prepared via different processes. Their widths are calculated from the respective turbidity plots of their water dispersions, based on the theory of light scattering by thin and long particles. The turbidity‐derived widths of the seven nanocelluloses range from 2 to 10 nm, and show good correlations with the thicknesses of nanocellulose particles spread on flat mica surfaces determined using atomic force microscopy.
74.
Ilia?NegriEmail authorView authors OrcID profile Yoichi?Nishiyama 《Statistical Inference for Stochastic Processes》2017,20(3):387-397
The problem to establish the asymptotic distribution of statistical estimators as well as the moment convergence of such estimators has been recognized as an important issue in advanced theories of statistics. This problem has been deeply studied for M-estimators for a wide range of models by many authors. The purpose of this paper is to present an alternative and apparently simple theory to derive the moment convergence of Z-estimators. In the proposed approach the cases of parameters with different rate of convergence can be treated easily and smoothly and any large deviation type inequalities necessary for the same result for M-estimators do not appear in this approach. Applications to the model of i.i.d. observation, Cox’s regression model as well as some diffusion process are discussed. 相似文献
75.
The nondestructive testing technique is applied to evaluate the temper embrittlement of normalized and tempered
steel; it is based on the anodic polarization behavior in calcium nitrate solution. The steel specimen is aged at a stress of 210 MPa at 450°C for up to 8800 h in order to examine the effect of applied stress on the enhancement of intergranular segregation of phosphorus. The secondary peak observed in the polarization curve for the material aged under stress was compared with that for the non-stressed. It can be quantified with the degree of intergranular segregation of phosphorus. The data suggest that the enhancement of phosphorus segregation due to the applied stress is only recognized after 3000 h of aging. This effect diminishes with increasing aging time. 相似文献
76.
Rui UmedaTakashi Nishimura Kenta KaibaToshimasa Tanaka Yuuki TakahashiYutaka Nishiyama 《Tetrahedron》2011,67(38):7217-7221
It was found that rhenium complex was an efficient catalyst for the acylative cleavage of C-O bond of ethers with acyl chlorides. When acyclic ethers were allowed to react with acyl chlorides in the presence of a catalytic amount of ReBr(CO)5, acylative cleavage of C-O bond of acyclic ethers smoothly proceeded to give the corresponding esters in moderate to good yields. Similarly, cyclic ethers were acylative cleaved by acyl chlorides to give the corresponding chloro substituted esters in good yields by the use of Re2O7 catalyst. 相似文献
77.
The carbazoles 1 and dibenzofurans 2 having naphthalimide unit were synthesized by the cross coupling reaction of 4-bromonaphthalimide 3 with aniline and phenol derivatives followed by the intramolecular cyclization, respectively. The chromophores 1c and 2c substituted methoxy group exhibited the strong fluorescence solvatochromism. 相似文献
78.
Masahisa Wada Yoshiharu Nishiyama Giovanni Bellesia Trevor Forsyth S. Gnanakaran Paul Langan 《Cellulose (London, England)》2011,18(2):191-206
The hydrogen bond arrangement in a complex of cellulose with ammonia has been studied using neutron crystallography in combination
with molecular dynamics simulations. The O6 atom of the hydroxymethyl group is donor in a highly occupied hydrogen bond to
an ammonia molecule. This rotating ammonia molecule is donor in partially occupied and transient hydrogen bonds to the O2,
O3 and O6 atoms of the hydroxyl groups of other chains. The hydrogen atom bound to the O3 atom is disordered but it is almost
always involved in some type of hydrogen bonding. It is donated in a hydrogen bond most of the time to the O5 atom on the
same chain. However, it also rotates away from this O5 atom to be donated to an ammonia molecule part of the time. On the
other hand the hydrogen atom bound to the O2 atom is free from hydrogen bonding most of the time. It is donated in a hydrogen
bond to the O6 atom on a neighboring chain only with a relatively small probability. These results provide new insights into
how hydrogen bonds are rearranged during the conversion of cellulose I to cellulose IIII by ammonia treatment. 相似文献
79.
Matsuoka H Shen JR Kawamori A Nishiyama K Ohba Y Yamauchi S 《Journal of the American Chemical Society》2011,133(12):4655-4660
The oxidation of a redox-active tyrosine residue Y(Z) in photosystem II (PSII) is coupled with proton transfer to a hydrogen-bonded D1-His190 residue. Because of the apparent proximity of Y(Z) to the water-oxidizing complex and its redox activity, it is believed that Y(Z) plays a significant role in water oxidation in PSII. We investigated the g-anisotropy of the tyrosine radical Y(Z)(?) to provide insight into the mechanism of Y(Z)(?) proton-coupled electron transfer in Mn-depleted PSII. The anisotropy was highly resolved by electron paramagnetic resonance spectroscopy at the W-band (94.9 GHz) using PSII single crystals. The g(X)-component along the phenolic C-O bond of Y(Z)(?) was calculated by density functional theory (DFT). It was concluded from the highly resolved g-anisotropy that Y(Z) loses a phenol proton to D1-His190 upon tyrosine oxidation, and D1-His190 redonates the same proton back to Y(Z)(?) upon reduction. 相似文献
80.
Motoyama Y Sakakura T Takemoto T Shimozono K Aoki K Nishiyama H 《Molecules (Basel, Switzerland)》2011,16(7):5387-5401
Bis(oxazolinyl)phenylrhodium(III) aqua complexes, (Phebox)RhX?(H?O) [X = Cl, Br], were found to be efficient Lewis acid catalysts for the enantioselective addition of allyl- and methallyltributyltin reagents to amino aldehydes. The reactions proceed smoothly in the presence of 5-10 mol % of (Phebox)RhX?(H?O) complex at ambient temperature to give the corresponding amino alcohols with modest to good enantioselectivity (up to 94% ee). 相似文献