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1.
Proton Order–Disorder Phenomena in a Hydrogen‐Bonded Rhodium–η5‐Semiquinone Complex: A Possible Dielectric Response Mechanism 下载免费PDF全文
Dr. Minoru Mitsumi Kazunari Ezaki Yuuki Komatsu Prof. Dr. Koshiro Toriumi Dr. Tatsuya Miyatou Prof. Dr. Motohiro Mizuno Nobuaki Azuma Prof. Dr. Yuji Miyazaki Prof. Dr. Motohiro Nakano Prof. Dr. Yasutaka Kitagawa Dr. Takayasu Hanashima Dr. Ryoji Kiyanagi Dr. Takashi Ohhara Prof. Dr. Kazuhiro Nakasuji 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(27):9682-9696
A newly synthesized one‐dimensional (1D) hydrogen‐bonded (H‐bonded) rhodium(II)–η5‐semiquinone complex, [Cp*Rh(η5‐p‐HSQ‐Me4)]PF6 ([ 1 ]PF6; Cp*=1,2,3,4,5‐pentamethylcyclopentadienyl; HSQ=semiquinone) exhibits a paraelectric–antiferroelectric second‐order phase transition at 237.1 K. Neutron and X‐ray crystal structure analyses reveal that the H‐bonded proton is disordered over two sites in the room‐temperature (RT) phase. The phase transition would arise from this proton disorder together with rotation or libration of the Cp* ring and PF6? ion. The relative permittivity εb′ along the H‐bonded chains reaches relatively high values (ca., 130) in the RT phase. The temperature dependence of 13C CP/MAS NMR spectra demonstrates that the proton is dynamically disordered in the RT phase and that the proton exchange has already occurred in the low‐temperature (LT) phase. Rate constants for the proton exchange are estimated to be 10?4–10?6 s in the temperature range of 240–270 K. DFT calculations predict that the protonation/deprotonation of [ 1 ]+ leads to interesting hapticity changes of the semiquinone ligand accompanied by reduction/oxidation by the π‐bonded rhodium fragment, producing the stable η6‐hydroquinone complex, [Cp*Rh3+(η6‐p‐H2Q‐Me4)]2+ ([ 2 ]2+), and η4‐benzoquinone complex, [Cp*Rh+(η4‐p‐BQ‐Me4)] ([ 3 ]), respectively. Possible mechanisms leading to the dielectric response are discussed on the basis of the migration of the protonic solitons comprising of [ 2 ]2+ and [ 3 ], which would be generated in the H‐bonded chain. 相似文献
2.
Kazuki Komatsu Stefan Klotz Satoshi Nakano Shinichi Machida Takanori Hattori Asami Sano-Furukawa 《高压研究》2020,40(1):184-193
ABSTRACTA new high pressure cell for neutron diffraction experiments using nano-polycrystalline anvils is presented. The cell design, off-line pressure generation tests and a gas-loading procedure for this cell are described. The performance is illustrated by powder neutron diffraction patterns of ice VII to ~82?GPa. We also demonstrate the feasibility of single crystal neutron diffraction experiments of Fe3O4 at ambient conditions using this cell and discuss the current limitation and future developments. 相似文献
3.
Dr. Yoji Horii Prof. Dr. Keiichi Katoh Prof. Dr. Yuji Miyazaki Dr. Marko Damjanović Tetsu Sato Prof. Dr. Liviu Ungur Prof. Dr. Liviu F. Chibotaru Prof. Dr. Brian K. Breedlove Prof. Dr. Motohiro Nakano Prof. Dr. Wolfgang Wernsdorfer Prof. Dr. Masahiro Yamashita 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(36):8076-8082
Gd3+ complexes have been shown to undergo unusual slow magnetic relaxation processes similar to those of single-molecule magnets (SMMs), even though Gd3+ does not exhibit strong magnetic anisotropy. To reveal the origin of the slow magnetic relaxation of Gd3+ complexes, we have investigated the magnetic properties and heat capacities of two Gd3+-phthalocyaninato triple-decker complexes, one of which has intramolecular Gd3+–Gd3+ interactions and the other does not. It was found that the Gd3+–Gd3+ interactions accelerate the magnetic relaxation processes. In addition, magnetically diluted samples, prepared by doping a small amount of the Gd3+ complexes into a large amount of diamagnetic Y3+ complexes, underwent dual magnetic relaxation processes. A detailed dynamic magnetic analysis revealed that the coexistence of spin–lattice relaxation and phonon-bottleneck processes is the origin of the dual magnetic relaxation processes. 相似文献
4.
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
5.
Dr. Pengfei Wu Prof. Dr. Adriana Pietropaolo Dr. Mariagrazia Fortino Dr. Masayoshi Bando Prof. Dr. Katsuhiro Maeda Dr. Tatsuya Nishimura Shuhei Shimoda Dr. Hiroyasu Sato Prof. Dr. Naofumi Naga Prof. Dr. Tamaki Nakano 《Angewandte Chemie (International ed. in English)》2023,62(29):e202305747
Optically active, hyperbranched, poly(fluorene-2,4,7-triylethene-1,2-diyl) [poly(fluorenevinylene)] derivatives bearing a neomenthyl group and a pentyl group at the 9-position of the fluorene backbone at various ratios acted as a chirality donor (host polymers) efficiently included naphthalene, anthracene, pyrene, 9-phenylanthracene, and 9,10-diphenyanthracene as a chirality acceptor (guest molecules) in their interior space in film as well as in solution, with the guest molecules exhibiting intense circular dichroism through chirality transfer with chirality amplification. The efficiency of the chirality transfer was much higher with higher-molar-mass polymers than lower-molar-mass ones as well as with hyperbranched polymers compared to the analogous linear ones. The hyperbranched polymers include the small molecules in their complex structure without any specific interactions at various stoichiometries. The included molecules may have ordered intermolecular arrangement that may be somewhat similar to those of liquid crystals. Naphthalene, anthracene, and pyrene included in the polymer exhibited efficient circularly polarized luminescence, where the chirality was remarkably amplified in excited states, and anthracene exhibited especially high anisotropies in the emission on the order of 10−2. 相似文献
6.
Frontispiece: Entropy‐Driven 1,2‐Type Friedel–Crafts Reaction of Phenols with N‐tert‐Butoxycarbonyl Aldimines 下载免费PDF全文
7.
Effect of Acid Treatment of Montmorillonite on “Support‐Activator” Performance to Support Metallocene for Propylene Polymerization Catalyst 下载免费PDF全文
Takao Tayano Hideshi Uchino Takehiro Sagae Katsuyuki Yokomizo Koji Nakayama Shigeki Ohta Hiroshi Nakano Masahide Murata 《大分子反应工程》2017,11(2)
This work is focused on montmorillonite (MMT)‐based “support‐activators” (S‐As) for the metallocene‐catalyzed propylene polymerization. This catalyst was previously industrialized; however, for further technological advances, the activation mechanism is investigated. The chemical and morphological requirements of the S‐A are surveyed using both commercially available raw clay minerals (non‐acid‐treated) and acid‐treated clay minerals. The S‐A possessing strong‐acid sites (pK a < ?8.2) gives a highly active catalyst. Acid treatment of MMT induces morphological changes as well as the formation of strong acid sites. Based on pore size distribution analysis and atomic force microscopy observations, it is concluded that the strong acid sites are located in the small pores around the edge of the clay mineral (not in the interlayer), where the structure is disordered by the acid treatment.
8.
Dr. Neil J. Stewart Hitomi Nakano Shuto Sugai Mitsushi Tomohiro Yuki Kase Yoshiki Uchio Dr. Toru Yamaguchi Yujirou Matsuo Dr. Tatsuya Naganuma Dr. Norihiko Takeda Dr. Ikuya Nishimura Dr. Hiroshi Hirata Dr. Takuya Hashimoto Dr. Shingo Matsumoto 《Chemphyschem》2021,22(10):915-923
Hyperpolarized [1-13C]fumarate is a promising magnetic resonance imaging (MRI) biomarker for cellular necrosis, which plays an important role in various disease and cancerous pathological processes. To demonstrate the feasibility of MRI of [1-13C]fumarate metabolism using parahydrogen-induced polarization (PHIP), a low-cost alternative to dissolution dynamic nuclear polarization (dDNP), a cost-effective and high-yield synthetic pathway of hydrogenation precursor [1-13C]acetylenedicarboxylate (ADC) was developed. The trans-selectivity of the hydrogenation reaction of ADC using a ruthenium-based catalyst was elucidated employing density functional theory (DFT) simulations. A simple PHIP set-up was used to generate hyperpolarized [1-13C]fumarate at sufficient 13C polarization for ex vivo detection of hyperpolarized 13C malate metabolized from fumarate in murine liver tissue homogenates, and in vivo 13C MR spectroscopy and imaging in a murine model of acetaminophen-induced hepatitis. 相似文献
9.
Katsumi Katoh Nobuyuki Saeki Eiko Higashi Yuki Hirose Masahiko Sugimoto Katsuyuki Nakano 《Journal of Thermal Analysis and Calorimetry》2013,113(3):1275-1279
As a fundamental study on the development of dismantlable adhesives containing chemically reactive materials, the thermal behavior and dismantlability of an epoxy adhesive containing one of the twenty-seven inorganic salts (chlorides, perchlorates, and nitrates) were observed. In the thermal behavior measured by the differential scanning calorimetry, epoxy adhesives with inorganic salts containing iron, copper, zinc, and aluminum cations released heats of reaction at lower temperatures than the adhesive alone or the adhesives with other inorganic salts. Since such inorganic salts were considered to be effective candidates as fillers in dismantlable adhesives, the adhesion strengths of their mixtures with the adhesive were observed after heat aging at 270 °C for 30 min. The results showed that both chloride and perchlorate salts specifically decreased the adhesion strength after heating. On the other hand, the effect of nitrate salts on the decrease in adhesion strength was low in comparison with the chloride and perchlorate salts. 相似文献
10.
Katsumi Katoh Seiichiro Nagayama Eiko Higashi Katsuyuki Nakano 《Journal of Thermal Analysis and Calorimetry》2013,113(3):1239-1244
In the hydrosilylation of 1,6-divinyl(perfluorohexane) (FDV) with trichlorosilane (TCS) in the presence of catalytic chloroplatinic acid (Pt-Cat) under an air atmosphere (0.99 MPa), a runaway reaction accompanied by a severe pressure release occurred when Fe2O3 was present as an impurity in the system. In this study, we investigated the mechanism of action of Fe2O3 on this hydrosilylation by monitoring the thermal behavior of TCS/FDV/Pt-Cat/Fe2O3 mixtures with various compositions, using an accelerating rate calorimeter (ARC). In the case of TSC/FDV/Pt-Cat, a typical hydrosilylation composition in the industrial process, heat release, possibly due to hydrosilylation, began at 90 °C. On the other hand, for TCS/FDV/Pt-Cat/Fe2O, the heat release due to hydrosilylation was hardly observed, but abrupt heat and pressure releases occurred at higher temperatures (>170 °C). Like TCS/FDV/Pt-Cat/Fe2O3, TCS/FDV, which contain neither Pt-Cat nor Fe2O3, released heat and pressure at high temperatures (>210 °C), while the heat and pressure release rates were comparatively low. From these results, the runaway reaction may occur when hydrosilylation is prevented, and Fe2O3 behaves as a negative catalyst for hydrosilylation. In the FT-IR spectrum of TCS/FDV/Pt-Cat/Fe2O3 after heating, an absorption peak at approximately 1,710 cm?1, which may be attributed to a carbonyl group, was observed. Thus, it is considered that the runaway reaction observed during the hydrosilylation results from the action of Fe2O3 as a negative catalyst for hydrosilylation as well as as an oxidation catalyst for the by-product generated from the reaction between TCS and FDV. 相似文献