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31.
Xiongchao Lin Keiko Ideta Jin Miyawaki Yusuke Nishiyama Isao Mochida Seong‐Ho Yoon 《Magnetic resonance in chemistry : MRC》2012,50(4):289-294
A general strategy of structural analysis of alumina silicate by combining various solid‐state NMR measurements such as single pulse, multi‐quantum magic angle spinning, double‐quantum homo‐nuclear correlation under magic angle spinning (DQ‐MAS), and cross‐polarization hetero‐nuclear correlation (CP‐HETCOR) was evaluated with the aid of high magnetic field NMR (800 MHz for 1H Larmor frequency) by using anorthite as a model material. The high magnetic field greatly enhanced resolution of 27Al in single pulse, DQ‐MAS, and even in triple‐quantum magic angle spinning NMR spectra. The spatial proximities through dipolar couplings were probed by the DQ‐MAS methods for homo‐nuclear correlations between both 27Al–27Al and 29Si–29Si and by CP‐HETCOR for hetero‐nuclear correlations between 27Al–29Si in the anorthite framework. By combining various NMR methodologies, we elucidated detailed spatial correlations among various aluminum and silicon species in anorthite that was hard to be determined using conventional analytical methods at low magnetic field. Moreover, the presented approach is applicable to analyze other alumina‐silicate minerals. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
32.
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
33.
Koyuki Sakai Hiroki Nishiyama Shinsuke Inagi Ikuyoshi Tomita Yusuke Hibi Motonori Komura Keiji Nose Tomokazu Iyoda 《Journal of polymer science. Part A, Polymer chemistry》2019,57(24):E1-E8
A block copolymer composed of a flexible polar poly(ethylene glycol) (PEG) and a less polar liquid crystalline poly(allene) segments is prepared by the living coordination polymerization of an allene derivative possessing trans‐azobenzene‐containing mesogenic substituent by the use of a π‐allylnickel macroinitiator bearing PEG segment. The thin film of the block copolymer is prepared by the spin coating of its solution onto mica or silicon wafer which proves to possess perpendicularly oriented nanocylindrical microphase separated structures as supported by the differential calorimetric, polarized optical microscopic, grazing‐incidence small‐angle X‐ray scattering, transmission electron microscope, and atomic force microscope measurements. 相似文献
34.
Shofu Matsuda Yuuki Okuda Yoshiki Obu Norio Nagayama Minoru Umeda 《Electroanalysis》2019,31(12):2466-2471
With the objective of understanding the kinetic redox properties of triphenylamine derivatives in association with chemical reactions, for their future application in functional organic semiconductor devices, the electrochemical characteristics of 4‐(2,2‐diphenylethenyl)‐N,N‐bis(4‐methylphenyl)‐benzenamine (TPA) were evaluated. Based on cyclic voltammograms of TPA on Pt disk electrodes with diameters of 300 μm and 10 μm at slow and fast scan rates in an acetonitrile solution, the TPA.+ is stable, while the TPA2+ is unstable. Importantly, the unstable TPA2+ appears to break down by a subsequent chemical reaction. A Cottrell plot analysis from chronoamperometry of a solution containing TPA reveals that both the first and second oxidations are one‐electron reactions. Concerning the stabilization mechanism of the first oxidation state of TPA, the results of molecular orbital calculations indicate that the electrons of the HOMO level are distributed in the triphenylamine group, which induces a resonance‐stabilized TPA.+. Based on these results, TPA/TPA.+ is suggested to have a sufficient stability for further application in organic semiconductor devices. 相似文献
35.
Fujiko Iwasaki Hideyuki Nishiyama Noriko Manabe Masanori Yasui Noboru Matsumura 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1):429-430
Abstract Novel metal-carbene complexes (4) with a metallapentalene framework have been obtained from hypervalent diazadiselenathiapentalenes (3) by treating with Pt(PPh3)4, Pd(PPh3)4 and RhCl(PPh3)3. X-Ray investigations revealed that the central hypervalent sulfur atom in 3 was substituted by a metal atom to form M-Se bonds in the resultant metallapentalene framework. 相似文献
36.
37.
Novel symmetric and non-symmetric chiral twin compounds possessing one or two thioether groups in a central spacer were prepared, and the effect of substituting oxygen for sulphur on the liquid crystalline properties investigated. Chiral twin compounds possessing an alkylsulphanyl spacer showed an antiferroelectric phase exclusively. However, replacing the alkyloxy chain of the analogous monomer by the alkylsulphanyl chain has no significant effect on the phase transition behaviour, i.e. both of the monomers showed the ferro- and ferri-electric phases as well as the antiferroelectric phase. Thus, different effects of introducing the thioether linkage were for the first time observed between twin and monomeric systems. The introduction of oxygen or sulphur atoms into the central alkyl spacer of the chiral twin was also investigated, and these modifications were found to stabilize the SmA phase. Furthermore, the twin compound possessing a thiaalkyl spacer showed two different molecular assemblies in the smectic A phase. 相似文献
38.
Junling Bai Toshifumi Nakatani Yuuki Sasaki Sadanobu Inoue Nobuo Takahashi 《International journal of environmental analytical chemistry》2013,93(9):856-865
Effectiveness of Pd/Mg chemical modifier for the accurate direct determination of zinc in marine/lacustrine sediments by graphite furnace atomic absorption spectrometry (GF-AAS) using slurry samples was evaluated. A calibration curve prepared by aqueous zinc standard solution with addition of Pd/Mg chemical modifier is used to determine the zinc concentration in the sediment. The accuracy of the proposed method was confirmed using Certified Reference Materials, NMIJ CRM 7303-a (lacustrine sediment) from National Metrology Institute of Japan, National Institute of Advanced Industrial Science and Technology, Japan, and MESS-3 (marine sediment) and PACS-2 (marine sediment) from National Research Council, Canada. The analytical results obtained by employing Pd/Mg modifier are in good agreement with the certified values of all the reference sediment materials. Although for NRC MESS-3 an accurate determination of zinc is achieved even without the chemical modifier, the use of Pd/Mg chemical modifier is recommended as it leads to establishment of a reliable and accurate direct analytical method. One quantitative analysis takes less than 15 minutes after we obtain dried sediment samples, which is several tens of times faster than conventional analytical methods using acid digested sample solutions. The detection limits are 0.13?µg?g?1 (213.9?nm) and 16?µg?g?1 (307.6?nm), respectively, in sediment samples, when 40?mg of dried powdered samples are suspended in 20?mL of 0.1?mol?L?1 nitric acid and a 10?µl portion of the slurry sample is measured. The precision of the proposed method is 8–15% (RSD). 相似文献
39.
Dr. Jun‐ichi Ito Kohei Fujii Prof. Dr. Hisao Nishiyama 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(2):601-605
NCN‐pincer Ru‐complexes containing bis(oxazolinyl)phenyl ligands serve as suitable catalysts in the direct conjugate additions of α,β‐unsaturated carbonyl compounds, including ketones, esters, and amides, as well as vinylphosphonates, giving various β‐alkynyl carbonyl and phosphonate compounds. A bis(oxazolinyl)phenyl (phebox)–Ru complex also catalyzes the asymmetric conjugate addition of an alkyne with a β‐substituted, α,β‐unsaturated ketone to produce a chiral β‐alkynyl ketone. 相似文献
40.
Kuniaki Marui Yuuki Higashiura Shintaro Kodama Suguru Hashidate Akihiro Nomoto Shigenobu Yano Michio Ueshima Akiya Ogawa 《Tetrahedron》2014
The oxidation of alcohols using catalytic amounts of metal complexes is highly attractive from the viewpoint of green chemistry principles. However, examples of metal complex-catalyzed oxidations of alcohols with O2 using water as the solvent are still rare, and precious metals, high-pressure O2 or air, and a stoichiometric amount of base are often required. In this study, it was found that an oxovanadium-4,4′-t-Bubpy (4,4′-di-tert-butyl-2,2′-bipyridyl) complex exhibited high catalytic activity in the oxidation of benzhydrols under an atmosphere of O2 in water as the sole solvent. Interestingly, this catalytic oxidation method could be applied to the gram-scale aerobic oxidation of alcohols in water under the atmosphere. 相似文献