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131.
132.
Reduction‐Induced Highly Selective Uptake of Cesium Ions by an Ionic Crystal Based on Silicododecamolybdate 下载免费PDF全文
Saori Seino Ryosuke Kawahara Dr. Yoshiyuki Ogasawara Prof. Noritaka Mizuno Dr. Sayaka Uchida 《Angewandte Chemie (International ed. in English)》2016,55(12):3987-3991
Cation adsorption and exchange has been an important topic in both basic and applied chemistry relevant to materials synthesis and chemical conversion, as well as purification and separation. Selective Cs+ uptake from aqueous solutions is especially important because Cs+ is expensive and is contained in radioactive wastes. However, the reported adsorbents incorporate Rb+ as well as Cs+, and an adsorbent with high selectivity toward Cs+ has not yet been reported. Highly selective uptake of Cs+ by an ionic crystal (etpyH)2[Cr3O(OOCH)6(etpy)3]2[α‐SiMo12O40]?3 H2O (etpy =4‐ethylpyridine) is described. The compound incorporated up to 3.8 mol(Cs+) mol(s)?1 (where s=solid) by cation‐exchange with etpyH+ and reduction of silicododecamolybdate with ascorbic acid. The amount of Cs+ uptake was comparable to that of Prussian blue, which is widely recognized as a good Cs+ adsorbent. Moreover, other alkali‐metal and alkaline‐earth‐metal cations were almost completely excluded (<0.2 mol mol(s)?1). 相似文献
133.
Kikukawa Y Yamaguchi S Nakagawa Y Uehara K Uchida S Yamaguchi K Mizuno N 《Journal of the American Chemical Society》2008,130(47):15872-15878
A novel dialuminum-substituted silicotungstate TBA(3)H[gamma-SiW(10)O(36){Al(OH(2))}(2)(mu-OH)(2)] x 4 H(2)O (1, TBA = tetra-n-butylammonium) was synthesized by the reaction of the potassium salt of [gamma-SiW(10)O(36)](8-) (SiW10) with 2 equiv of Al(NO(3))(3) in an acidic aqueous medium. It was confirmed by the X-ray crystallographic analysis that compound 1 was a monomer of the gamma-Keggin dialuminum-substituted silicotungstate with the {Al(2)(mu-OH)(2)} diamond core. The cluster framework of 1 maintained the gamma-Keggin structure in the solution states. The reaction of 1 with pyridine yielded TBA(3)[(C(5)H(5)N)H][gamma-SiW(10)O(36){Al(C(5)H(5)N)}(2)(mu-OH)(2)] x 2 H(2)O (2), and the molecular structure was successfully determined by the X-ray crystallographic analysis. In compound 2, two of three pyridine molecules coordinated to the axial positions of aluminum centers and one of them existed as a pyridinium cation, showing that compound 1 has two Lewis acid sites and one Br?nsted acid site. Compound 1 showed high catalytic activity for the intramolecular cyclization of citronellal derivatives such as (+)-citronellal (3) and 3-methylcitronellal (4) without formation of byproduct resulting from etherification and dehydration. For the 1-catalyzed cyclization of 3, the diastereoselectivity toward (-)-isopulegol (3a) reached ca. 90% and the value was the highest level among those with reported systems so far. The reaction rate for the 1-catalyzed cyclization of 3 decreased by the addition of pyridine, and the cyclization hardly proceeded in the presence of 2 equiv of pyridine with respect to 1. On the other hand, the reaction rate and diastereoselectivity to 3a in the presence of 2,6-lutidine were almost the same as those in the absence. Therefore, the present cyclization is mainly promoted by the Lewis acid sites (aluminum centers) in 1. DFT calculations showed that the formation of the transition state to produce 3a is sterically and electronically more favorable than the other three transition states for the present 1-catalyzed cyclization of 3. 相似文献
134.
Hiroyuki Kai Sayaka Ohara Atsutaka Kunai Young-Woo Kwak 《Journal of organometallic chemistry》2008,693(23):3490-3494
Optical, electrochemical, and electron-transporting properties of disilane- and siloxane-bridged biphenyl and bithiophene derivatives were investigated, in comparison with those of the monosilane-bridged analogues (siloles). The UV spectra and cyclic voltammograms indicated that elongation of the silicon bridge suppresses the π-conjugation, in accordance with the results of DFT calculations. The DFT calculations indicated also that the disilane-bridged biphenyl and siloxane-bridged bithiophene should have the low-lying HOMOs and LUMOs. The electron-transporting properties were evaluated by the performance of triple-layered OLEDs having vapor-deposited films of the Si-bridged compound, Alq3, and TPD, as the electron-transport, emitter, and hole-transport, respectively. Of these, the device with a disilane-bridged biphenyl exhibited the high performance with the maximum current density of 590 mA/cm2 at the applied electric field of 12 × 107 V/m (applied bias voltage = 13 V) and the maximum luminance of 22 000 cd/m2 at 13 × 107 V/m. 相似文献
135.
Equations of second order in time with quasilinear damping: existence in Orlicz spaces via convergence of a full discretisation 下载免费PDF全文
Etienne Emmrich David Šiška Aneta Wróblewska‐Kamińska 《Mathematical Methods in the Applied Sciences》2016,39(10):2449-2460
A nonlinear evolution equation of second order with damping is studied. The quasilinear damping term is monotone and coercive but exhibits anisotropic and nonpolynomial growth. The appropriate setting for such equations is that of monotone operators in Orlicz spaces. Global existence of solutions in the sense of distributions is shown via convergence of the backward Euler scheme combined with an internal approximation. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
136.
Agnieszka Pazik Beata Kami´nska Anna Skwierawska Sandra Nakonieczna Tadeusz Ossowski 《Chemical Papers》2016,70(3):253-264
The synthesis of a new chromogenic N,N′-phenyltetrazole receptor is reported here. The cationbinding properties of this receptor in solution were investigated by naked-eye colour change, electrochemical methods and UV-Vis spectroscopy in various solvents (CH3CN, dimethylsulphoxide (DMSO), DMSO/H2O, CH3CN/H2O and CH3CN/MeOH). In addition, the receptor was used as a sensing material in ion-selective membrane electrodes. The selectivity and sensitivity of these electrodes towards alkali, alkali-earth, transition and heavy metal cations in aqueous solution were tested. The relation between the carrier structure and membrane plasticisers was investigated. 相似文献
137.
Although both cis-diamminedichloroplatinum(II) (cisplatin or cis-DDP) and trans-diamminedichloroplatinum(II) bind to DNA, only cis-DDP is widely used as a chemotherapeutic agent; the stereoisomer trans-DDP is inactive. DNA, generally, is wound around the histone core in the nucleus of living cells and forms the nucleosome structure. To understand the essentially different anticancer activities of cis-DDP and trans-DDP, it is necessary to investigate the interaction of cis-DDP (or trans-DDP) with DNA around the histone in the nucleosome. Here, we used psiX174DNA-histone(LNCaP) complexes prepared by the reaction of psiX174DNA with histone(LNCaP) extracted from LNCaP cells. We first show that the ability of cis-DDP to dissociate the DNA from psiX174DNA-histone(LNCaP), as a nucleosome model, is much stronger than that of trans-DDP. As a result of the action of cis-DDP, the DNA in the nucleosome is rendered naked, and the naked DNA is vulnerable to cis-DDP (or other drugs). This study describes a new model showing that the difference in the activities of cis-DDP and trans-DDP is related to the difference in their abilities to dissociate the DNA from the nucleosome. 相似文献
138.
[reaction: see text] Allyl and propargyl ethers were effectively deallylated or depropargylated to the parent alcohols via a C-O bond cleavage catalyzed by a low-valent titanium reagent (LVT), Ti(O-i-Pr)4/TMSCl/Mg or Ti(O-i-Pr)4/MgBr2/Mg, under mild reaction conditions. Differentiation between the allyl and propargyl ethers was achieved by the reaction in the presence of AcOEt as an additive. The reagent also catalyzed intra- and intermolecular cyclotrimerization reactions of alkynes to substituted benzenes. 相似文献
139.
A novel and efficient avenue for the preparation of dimeric vancomycins is described, and the dimers exhibited excellent antibacterial activities in the murine infection model. 相似文献
140.