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71.
The stable mononuclear Ni(III)-thiolate complexes [NiIII(L)(P(C6H3-3-SiMe3-2-S)3)]- (L = SePh (2), Cl (3), SEt (4), 2-S-C4H3S (5), CH2CN (7)) were isolated and characterized by UV-vis, EPR, IR, SQUID, CV, 1H NMR, and single-crystal X-ray diffraction. The increased basicity (electronic density) of the nickel center of complexes [NiIII(L)(P(C6H3-3-SiMe3-2-S)3)]- modulated by the monodentate ligand L and the substituted groups of the phenylthiolate rings promotes the stability and reactivity. In contrast to the irreversible reduction at -1.17 V (vs Cp2Fe/Cp2Fe+) for complex 3, the cyclic voltammograms of complexes [NiIII(SePh)(P(o-C6H4S)3)]-, 2, 4, and 7 display reversible NiIII/II redox processes with E(1/2) = -1.20, -1.26, -1.32, and -1.34 V (vs Cp2Fe/Cp2Fe+), respectively. Compared to complex 2 containing a phenylselenolate-coordinated ligand, complex 4 with a stronger electron-donating ethylthiolate coordinated to the Ni(III) promotes dechlorination of CH2Cl2 to yield complex 3 (kobs = (6.01 +/- 0.03) x 10-4 s-1 for conversion of complex 4 into 3 vs kobs = (4.78 +/- 0.02) x 10-5 s-1 for conversion of complex 2 into 3). Interestingly, addition of CH3CN into complex 3 in the presence of sodium hydride yielded the stable Ni(III)-cyanomethanide complex 7 with a NiIII-CH2CN bond distance of 2.037(3) A. The NiIII-SEt bond length of 2.273(1) A in complex 4 is at the upper end of the 2.12-2.28 A range for the NiIII-S bond lengths of the oxidized-form [NiFe] hydrogenases. In contrast to the inertness of complexes 3 and 7 under CO atmosphere, carbon monoxide triggers the reductive elimination of the monodentate chalcogenolate ligand of complexes 2, 4, and 5 to produce the trigonal bipyramidal complex [NiII(CO)(P(C6H3-3-SiMe3-2-S)3]- (6). 相似文献
72.
The sesquiterpene aureol (1) was isolated by chromatographic fractionation of a non-polar extract from Smenospongia sp. Methylation of aureol yielded 5'-O-methyl-aureol (2) while the prepared acylation products of aureol were 5'-O-acetyl-aureol (3), 5'-O-benzoyl-aureol (4), 5'-O-(4-fluoro-benzoyl)-aureol (5), 5'-O-(4-chlorobenzoyl)-aureol (6), 5'-O-(4-methylbenzoyl)-aureol (7), 5'-O-nicotinoyl-aureol (8), aureol-N,N-dimethylthiocarbamate (9), 5'-O-(2-furoylcarbonyl)-aureol (10), 5'-O-(2-thienoylcarbonyl-aureol (11). The structures of aureol as well as its ten derivatives were established through spectral analysis. The in vitro cytotoxic activities of the eleven compounds were evaluated against Hepa59T/VGH, KB and Hela tumor cell lines. 相似文献
73.
Bruce C. Berndt Heng Huat Chan Song Heng Chan Wen-Chin Liaw 《The Ramanujan Journal》2010,23(1-3):3-15
A survey of Ramanujan’s work on cranks in his lost notebook is given. We give evidence that Ramanujan was concentrating on cranks when he died, that is to say, the final problem on which Ramanujan worked was cranks—not mock theta functions. 相似文献
74.
In this note, we shall give a partition-theoretic interpretation which explains the non-negativity of the coefficients of some q-series arising from Ramanujan's Lost Notebook and prove the almost-increasingness of the coefficients via a vector partition generating function. 相似文献
75.
Based on theoretical calculations using the fragility concept and the nucleation theory for a model glass-forming system, we propose a dimensionless criterion, ?, expressed by Trg(ΔTx/Tg)a, with Trg, the reduced glass-transition temperature, ΔTx, the width of the supercooled liquid region when heating a glass, Tg, the glass transition temperature, and a, the exponent. The application of this simple criterion to various glasses, including network, metallic, and molecular glasses (except pure water), indicates an excellent correlation between the critical cooling rate Rc and ? in a Log Rc-? single master plot with a = 0.143. 相似文献
76.
Constanze Liaw 《Journal of statistical physics》2013,153(6):1022-1038
We develop a rather explicit approach concerning the extended states conjecture for the discrete random Schrödinger operator, or more generally for the so-called Anderson-type Hamiltonian. Our work is based on deep mathematical results by Jak?i?–Last (Duke Math. J. 133(1):185–204, 2006). Concretely, we suggest two new directions of research: We provide a formula which may lead the way to a rigorous proof of the conjecture, and an implementation of the proposed approach which yields numerical evidence in favor of the conjecture being true for the discrete random Schrödinger operator in dimension two. Not being based on scaling theory, this method eliminates problems due to boundary conditions, common to previous numerical methods in the field. At the same time, as with any numerical experiment, one cannot exclude finite-size effects with complete certainty. We numerically track the “bulk distribution” (here: the distribution of where we most likely find an electron) of a wave packet initially located at the origin, after iterative application of the discrete random Schrödinger operator. 相似文献
77.
AlGaN/GaN epitaxial layers were grown on 0°-tilt and 1°-tilt sapphire substrates by metalorganic chemical vapor deposition (MOCVD). With exactly the same growth conditions, it was found that dislocation density was smaller and crystal quality was better for the AlGaN/GaN epitaxial layers prepared on 1°-tilt sapphire substrate. We also found that AlGaN/GaN epitaxial layers on 1°-tilt sapphire substrate were grown with step growth mode while those on 0°-tilt substrate were grown with two-dimensional island growth. From the temperature-dependent mobility, it was found that crystal quality of the AlGaN/GaN epitaxial layer prepared on 1°-tilt sapphire substrate is better. 相似文献
78.
Low-velocity impact tests on cast acrylic (PMMA) plates were conducted using an instrumented drop-weight impact machine under various temperatures. Radial cracks were induced and the impact force histories were recorded. Results indicated that there was a glass transition temperature of cast acrylic between 185 and 200 °F. Ultrasonic assessments on the impacted acrylic plates were then performed using different transducers. Focused transducers provided more accurate results than flat ones. In addition, the higher the ultrasound frequency, the better the resolution. Finally, the drop-weight impact responses were simulated using LS-DYNA. Two node-splitting techniques, sudden releasing and stepwise releasing, based on maximum tensile stress failure criterion, were implemented for this study. The maximum tensile stress failure criterion was adopted to capture the onset of crack initiation and crack propagation. The node release methods enabled us to calculate the strain energy release rates of cast acrylic. Numerical simulations were compared with experimental results and good agreements were achieved. 相似文献
79.
Der‐Jang Liaw Tsang‐Pin Chen Ching‐Cheng Huang 《Journal of polymer science. Part A, Polymer chemistry》2005,43(18):4233-4247
Several random and block copolynorbornenes with side chains containing terminal hydroxyl, amino, methacryloyl or ammonium groups were derived from the functional alkyl ester‐containing norbornenes by ring‐opening metathesis polymerization (ROMP). The main chain of ROMP‐type polynorbornene had a more important role for glass‐transition temperature in comparison with vinyl addition polymerization. There is little effect on glass‐transition temperature (about ?39 °C) of polynorbornenes with different length of alkyl side chain. The organosoluble copolynorbornenes with active crosslinkable methylacryloyl side chains derived from functional hydroxyl group were prepared to improve the thermal stability of poly(methyl methacrylate) [decomposition temperature (Td)10% = 325 °C in nitrogen] by forming networked AB crosslinked polymer (T = 367 °C in nitrogen). The sizes of nanometer‐scale polymeric micelles of block copolymers having hydrophobic alkyl ester and hydrophilic ammonium groups were measured in the range of 11–25 nm by scanning electron microscopy. These polymeric materials with various functional groups or amphiphilic architectures are accessible by ROMP, whose topology makes them particularly attractive for application potential such as biomedical and photoelectric materials. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4233–4247, 2005 相似文献
80.
We have studied the influence of the arc melting procedure of Nb-containing Zr-based bulk metallic glasses (BMGs) on their thermal and mechanical properties. We found that the strength and plastic strain to failure, determined at room temperature, increases by the addition of a few percentage of Nb into the Zr-based BMGs. High-resolution transmission-electron microscopy results show that the addition of 2 at.% Nb introduces the formation of as-cast nanocrystals. At the same time, thermal analyses indicate an increase in glass forming ability with the small addition of Nb. Contrary to the reported results in other amorphous alloys, we found that the plastic strain increases further after heat-induced structural relaxation in the Zr-based BMGs. 相似文献