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101.
Papanikolaou D Margadonna S Kosaka W Ohkoshi S Brunelli M Prassides K 《Journal of the American Chemical Society》2006,128(25):8358-8363
The effect of X-ray illumination on the structural properties of the mixed valence Prussian blue analogue CsFe(II)[Cr(III)(CN)6] has been studied by time-dependent high-resolution synchrotron X-ray diffraction. Abrupt isosymmetric phase transitions, accompanied by dramatic volume collapse, were found in the temperature range 245-265 K, induced by sudden Fe(II) spin transitions from the high spin (HS) (4t(2g)2e(g), S = 2) to the low spin (LS) (6t(2g)0e(g), S = 0) configuration. Absorption of X-ray photons generates photoexcited Fe(II)(LS) domains whose size rapidly grows with time until the percolation threshold is reached and the structure collapse is triggered. The persistent character of the optically excited spin crossover states derives from the strong electron-phonon coupling, associated with the large lattice relaxations, which accompany the internal spin rearrangements. It is thus possible to use X-ray light in a controllable and efficient way to induce photoswitching between the ground and hidden or inaccessible excited states in suitably selected multistable materials in the bulk. 相似文献
102.
O3‐NaFe1/2Co1/2O2 shows initial capacity of 160 mAh/g and an average operating voltage of 3.1 V (vs. Na) with good cyclability, and is a promising candidate of the cathode materials for sodium‐ion secondary batteries (SIBs). Here, we found that the cyclability of the slowly‐cooled sample is much worse than that of quenched one, even though the former sample keeps the O3‐type structure. The energy dispersive X‐ray spectroscopy (EDX) images suggest that the slow‐cooled sample (Nax Fe1–yCoy O2) is inhomogeneous in the Fe concentration (1 – y), perhaps triggered by the Na deficiency (1 – x). We ascribed the poor cyclability in the slowly‐cooled sample to the concentration inhomogeneity (Δy). The Δy is further responsible for the fluctuation of the lattice constants (a and c), as revealed by the Williamson–Hall plot. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim) 相似文献
103.
Jiaan Zheng Wataru Kobayashi Thomas Hamann Daniel Nürenberg Markus Lührmann Johannes A. L’huillier Richard Wallenstein Helmut Zacharias 《Applied physics. B, Lasers and optics》2014,116(3):549-560
We present a visually intuitive method for higher-order dispersion compensation based on multi-photon interpulse interference pulse scans. The dispersion values obtained from these scans are fed back as a correction to an acousto-optical programmable dispersive filter to compensate residual higher-order dispersions up to fifth order. This method is applied to the dispersion management of a non-collinear optical parametric chirped-pulse amplifier. A grism-pair stretcher is designed based on a global dispersion balance which provides a large stretching factor and supports a spectral bandwidth of up to 320 nm. It is implemented in a two-stage three-pass non-collinear optical parametric chirped-pulse amplifier and stretches 6-fs seed pulses to about 80 ps from 700 to 1,000 nm. The amplified pulses are compressed by material dispersion. Pulses of less than 10-fs duration with a pulse energy of 125 μJ are obtained at 20-kHz repetition rate. 相似文献
104.
An intramolecular σ-bond metathesis between carbon-carbon and silicon-silicon bonds took place on treatment of a disilane tethered to a cyclobutanone with a palladium(0) catalyst, furnishing a silaindane skeleton as well as an acylsilane functionality at once. 相似文献
105.
Muramatsu W Tanigawa S Takemoto Y Yoshimatsu H Onomura O 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(16):4850-4853
Nonprotected carbohydrates: The catalytic regioselective thiocarbonylation of carbohydrates by using organotin dichloride under mild conditions was demonstrated. The reaction afforded various deoxy saccharides in high yields and excellent regioselectivity in a minimum number of steps. The regioselectivity of the thiocarbonylation is attributed to the intrinsic character of the carbohydrates based on the stereorelationship of their hydroxy groups (see scheme). 相似文献
106.
Prof. Dr. Masahiro Sadakane Sachie Moroi Yoshifumi Iimuro Dr. Natalya Izarova Prof. Dr. Ulrich Kortz Prof. Dr. Shinjiro Hayakawa Kazuo Kato Dr. Shuhei Ogo Dr. Yusuke Ide Prof. Dr. Wataru Ueda Prof. Dr. Tsuneji Sano 《化学:亚洲杂志》2012,7(6):1331-1339
Ruthenium(III)‐substituted α‐Keggin‐type silicotungstates with pyridine‐based ligands, [SiW11O39RuIII(Py)]5?, (Py: pyridine ( 1 ), 4‐pyridine‐carboxylic acid ( 2 ), 4,4′‐bipyridine ( 3 ), 4‐pyridine‐acetamide ( 4 ), and 4‐pyridine‐methanol ( 5 )) were prepared by reacting [SiW11O39RuIII(H2O)]5? with the pyridine derivatives in water at 80 °C and then isolated as their hydrated cesium salts. These compounds were characterized using cyclic voltammetry (CV), UV/Vis, IR, and 1H NMR spectroscopy, elemental analysis, titration, and X‐ray absorption near‐edge structure (XANES) analysis (Ru K‐edge and L3‐edge). Single‐crystal X‐ray analysis of compounds 2 , 3 , and 4 revealed that RuIII was incorporated in the α‐Keggin framework and was coordinated by pyridine derivatives through a Ru? N bond. In the solid state, compounds 2 and 3 formed a dimer through π? π interaction of the pyridine moieties, whereas they existed as monomers in solution. CV indicated that the incorporated RuIII–Py was reversibly oxidized into the RuIV–Py derivative and reduced into the RuII–Py derivative. 相似文献
107.
T Takeguchi T Yamanaka K Asakura EN Muhamad K Uosaki W Ueda 《Journal of the American Chemical Society》2012,134(35):14508-14512
A randomly mixed monodispersed nanosized Pt-Ru catalyst, an ultimate catalyst for CO oxidation reaction, was prepared by the rapid quenching method. The mechanism of CO oxidation reaction on the Pt-Ru anode catalyst was elucidated by investigating the relation between the rate of CO oxidation reaction and the current density. The rate of CO oxidation reaction increased with an increase in unoccupied sites kinetically formed by hydrogen oxidation reaction, and the rate was independent of anode potential. Results of extended X-ray absorption fine structure spectroscopy showed the combination of N(Pt-Ru)/(N(Pt-Ru) + N(Pt-Pt)) ? M(Ru)/(M(Pt) + M(Ru)) and N(Ru-Pt)/(N(Ru-Pt) + N(Ru-Ru)) ? M(Pt)/(M(Ru) + M(Pt)), where N(Pt-Ru)(N(Ru-Pt)), N(Pt-Pt)(N(Ru-Ru)), M(Pt), and M(Ru) are the coordination numbers from Pt(Ru) to Ru(Pt) and Pt (Ru) to Pt (Ru) and the molar ratios of Pt and Ru, respectively. This indicates that Pt and Ru were mixed with a completely random distribution. A high-entropy state of dispersion of Pt and Ru could be maintained by rapid quenching from a high temperature. It is concluded that a nonelectrochemical shift reaction on a randomly mixed Pt-Ru catalyst is important to enhance the efficiency of residential fuel cell systems under operation conditions. 相似文献
108.
The parallel factor (PARAFAC) kernel matrix to analyze a sample system stimulated by more than one type of perturbation is described. PARAFAC kernel is a quantitative representation of the synchronicity and asynchronicity observed within the PARAFAC score matrices generated by carrying out two-dimensional (2D) correlation analyses. Thus, kernel matrix representation provides more intuitively understandable interpretation to the conventional PARAFAC trilinear model. In this study, the utility of PARAFAC kernel is demonstrated by the study of poly(lactic acid)-nanocomposite undergoing a structural change depending on the temperature as well as the clay content in the sample. Seemingly complicated variation of nuclear magnetic resonance (NMR) spectra induced by the change in the temperature and clay content are readily analyzed by the multiple-perturbation 2D correlation spectroscopy and PARAFAC kernel. PARAFAC kernel revealed that crystalline and amorphous structures of the PLA substantially undergo thermal deformation, and these variations are also influenced by the presence of the clay. 相似文献
109.
Prof. Makoto Moriya Hiro Kitaguchi Prof. Eiji Nishibori Prof. Hiroshi Sawa Prof. Wataru Sakamoto Prof. Toshinobu Yogo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(48):15305-15309
A novel trilithium compound, Li3[B(C6H4O2){O(CH2CH2O)3CH3}2][N(SO2CF3)2]2 ( 1 ‐2.0), with solid‐state ionic conductivity was synthesized. The crystal structure of 1 ‐2.0 consists of the one‐dimensional ionic conduction paths. The paths were afforded as a result of the self‐assembled stacking of the component molecules of 1 ‐2.0 with channel structures containing lithium ions. In this supramolecule, one lithium ion holds the component molecules in specific positions to construct a supramolecular structure with thermally stable ionic conduction paths and the others behave as carrier ions exhibiting selective lithium‐ion conductivity. Owing to the existence of both roles for the lithium ions, this electrolyte shows selective lithium‐ion conductivity. 相似文献