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排序方式: 共有369条查询结果,搜索用时 17 毫秒
71.
Fujisawa K Ono T Ishikawa Y Amir N Miyashita Y Okamoto K Lehnert N 《Inorganic chemistry》2006,45(4):1698-1713
Copper(I) complexes with tripodal nitrogen-containing neutral ligands such as tris(3,5-diisopropyl-1-pyrazolyl)methane (L1') and tris(3-tertiary-butyl-5-isopropyl-1-pyrazolyl)methane (L3'), and with corresponding anionic ligands such as hydrotris(3,5-diisopropyl-1-pyrazolyl)borate (L1-) and hydrotris(3-tertiary-butyl-5-isopropyl-1-pyrazolyl)borate (L3-) were synthesized and structurally characterized. Copper(I) complexes [Cu(L1')Cl] (1), [Cu(L1')(OClO3)] (2), [Cu(L1')(NCMe)](PF6) (3a), [Cu(L1')(NCMe)](ClO4) (3b), [Cu(L1')(CO)](PF6) (4a), and [Cu(L1')(CO)](ClO4) (4b) were prepared using the ligand L1'. Copper(I) complexes [Cu(L3')Cl] (5) and [Cu(L3')(NCMe)](PF6) (6) with the ligand L3' were also synthesized. Copper(I) complexes [Cu(L1)(NCMe)] (7) and [Cu(L1)(CO)] (8) were prepared using the anionic ligand L1-. Finally, copper(I) complexes with anionic ligand L3- and acetonitrile (9) and carbon monoxide (10) were synthesized. The complexes obtained were fully characterized by IR, far-IR, 1H NMR, and 13C NMR spectroscopy. The structures of both ligands, L1' and L3', and of complexes 1, 2, 3a, 3b, 4a, 4b, 5, 6, 7, and 10 were determined by X-ray crystallography. The effects of the differences in (a) the fourth ligand and the counteranion, (b) the steric hindrance at the third position of the pyrazolyl rings, and most importantly, (c) the charge of the N3 type ligands, on the structures, spectroscopic properties, and reactivities of the copper(I) complexes are discussed. The observed differences in the reactivities toward O2 of the copper(I) acetonitrile complexes are traced back to differences in the oxidation potentials determined by cyclic voltammetry. A special focus is set on the carbonyl complexes, where the 13C NMR and vibrational data are presented. Density functional theory (DFT) calculations are used to shed light on the differences in CO bonding in the compounds with neutral and anionic N3 ligands. In correlation with the vibrational and electrochemical data of these complexes, it is demonstrated that the C-O stretching vibration is a sensitive probe for the "electron richness" of copper(I) in these compounds. 相似文献
72.
Murata Y Itoh S Morio K Sasaki T Mizobuchi H Shimizu K Yoshida S 《Magnetic resonance imaging》2004,22(3):435-439
We report a case of multiple hemorrhagic cerebral metastases from papillary thyroid cancer, with reference to T(2)*-weighted gradient echo (GRE) magnetic resonance imaging (MRI). Small metastatic nodules were recognized as round nodules with signal loss on T(2)*-weighted GRE MRI, and were more pronounced compared with other sequences. Lesions were later confirmed as hemorrhagic on T(1)- and T(2)-weighted MRI. T(2)*-weighted GRE MRI was a sensitive tool for early detection of metastases displaying hemorrhagic changes. 相似文献
73.
Quanling Yang Shuji Fujisawa Tsuguyuki Saito Akira Isogai 《Cellulose (London, England)》2012,19(3):695-703
Mechanical, thermal and oxygen barrier properties of regenerated cellulose films prepared from aqueous cellulose/alkali/urea
solutions can be markedly improved by controlling the drying conditions of the films. By pre-pressing followed by vacuum drying
under compression, the tensile strength, Young’s modulus, coefficient of thermal expansion and oxygen permeability of the
dried films reached 263 MPa, 7.3 GPa, 10.3 ppm K−1 and 0.0007 ml μm m−2 day−1 kPa−1, respectively. Thus, films produced in this way show the highest performance of regenerated cellulose films with no orientation
of cellulose chains reported to date. These improved properties are accompanied by a clear increase in cellulose II crystallinity
from 50 to 62% during pre-pressing/press-vacuum drying process. At the same time, the film density increased from 1.45 to
1.57 g cm−3, and the moisture content under equilibrium conditions decreased from 14.1 to 9.8%. Hence, the aqueous alkali/urea solvent
system has potential applications in producing new and environmentally friendly cellulose films with high performances through
control of the drying conditions. 相似文献
74.
Let cl(G) denote Ryjá?ek's closure of a claw‐free graph G. In this article, we prove the following result. Let G be a 4‐connected claw‐free graph. Assume that G[NG(T)] is cyclically 3‐connected if T is a maximal K3 in G which is also maximal in cl(G). Then G is hamiltonian. This result is a common generalization of Kaiser et al.'s theorem [J Graph Theory 48(4) (2005), 267–276] and Pfender's theorem [J Graph Theory 49(4) (2005), 262–272]. © 2011 Wiley Periodicals, Inc. J Graph Theory 相似文献
75.
On a synchronization queue with two finite buffers 总被引:1,自引:0,他引:1
In this paper, we consider a synchronization queue (or synchronization node) consisting of two buffers with finite capacities.
One stream of tokens arriving at the system forms a Poisson process and the other forms a PH-renewal process. The tokens are
held in the buffers until one is available from each flow, and then a group-token is instantaneously released as a synchronized
departure. We show that the output stream of a synchronization queue is a Markov renewal process, and that the time between
consecutive departures has a phase type distribution. Thus, we obtain the throughput of this synchronization queue and the
loss probabilities of each type of tokens. Moreover, we consider an extended synchronization model with two Poisson streams
where a departing group-token consists of several tokens in each buffer.
This revised version was published online in June 2006 with corrections to the Cover Date. 相似文献
76.
Fujisawa Kiyoshi Okano Mitsuki Martín-Pastor Manuel López-Sánchez Rubén Elguero José Alkorta Ibon 《Structural chemistry》2021,32(1):215-224
Structural Chemistry - Experimental multinuclear determination of the chemical shifts, especially 15N and 109Ag, of five silver(I) trinuclear pyrazolate complexes, (PzAg)3, coupled with ZORA... 相似文献
77.
78.
Chen P Root DE Campochiaro C Fujisawa K Solomon EI 《Journal of the American Chemical Society》2003,125(2):466-474
Magnetic, vibrational, and optical techniques are combined with density functional calculations to elucidate the electronic structure of the diamagnetic mononuclear side-on CuII-superoxo complex. The electronic nature of its lowest singlet/triplet states and the ground-state diamagnetism are explored. The triplet state is found to involve the interaction between the Cu xy and the superoxide pi v * orbitals, which are orthogonal to each other. The singlet ground state involves the interaction between the Cu xy and the in-plane superoxide pi v * orbitals, which have a large overlap and thus strong bonding. The ground-state singlet/triplet states are therefore fundamentally different in orbital origin and not appropriately described by an exchange model. The ground-state singlet is highly delocalized with no spin polarization. 相似文献
79.
80.
Abe I Utsumi Y Oguro S Morita H Sano Y Noguchi H 《Journal of the American Chemical Society》2005,127(5):1362-1363
A novel plant-specific type III polyketide synthase (PKS) that catalyzes formation of a pentaketide chromone, 5,7-dihydroxy-2-methylchromone, from five molecules of malonyl-CoA, was cloned and sequenced from aloe (Aloe arborescens). Site-directed mutagenesis revealed that Met207 (corresponding to Thr197 in CHS) determines the polyketide chain length and the product specificity of the enzyme; remarkably, replacement of a single amino acid residue, Met207, with Gly yielded a mutant enzyme that efficiently produces aromatic octaketides, SEK4 and SEK4b, the products of the minimal PKS for actinorhodin (act from Streptomyces coelicolor), from eight molecules of malonyl-CoA. This provided new insights into the catalytic functions and specificities of the CHS-superfamily type III PKS enzymes. 相似文献