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81.
Sokolow JD Trzop E Chen Y Tang J Allen LJ Crabtree RH Benedict JB Coppens P 《Journal of the American Chemical Society》2012,134(28):11695-11700
The binding of carboxylate- and acetylacetonate-linked chromophores to homodisperse polyoxotitanate nanoclusters with 17 Ti atoms or more are surveyed and found to be limited to chelate-bidentate and the bridging modes, the former being dominant for the acetylacetonate-linked chromophores, the latter for the carboxylate linkers. Chromophores with acetylacetonate linking groups invariably bind in the chelate mode, whereas carboxylic acid terminated chromophores more frequently are observed to have the bridging mode, with the exception of three cases in which a strong electron-donating substituent is present on two different sensitizers. The calculations for isonicotinateand nitrophenylacetylacetonate functionalized Ti17 clusters show the observed binding modes to correspond to the lower energy functionalized clusters, but do not predict the difference between the cinnamic acid and dimethylaminocinnamic acid binding to Ti17, which are bridging and chelate respectively. Both binding modes were never observed to occur for a single chromophore, even when synthetic conditions were varied. Density of state calculations show broadening and splitting of the chromophore LUMO on complexation due to interaction with the cluster's conduction band, as well as frequent penetration of sensitizer orbitals into the bandgap of the functionalized nanoparticle. 相似文献
82.
Hintermair U Hashmi SM Elimelech M Crabtree RH 《Journal of the American Chemical Society》2012,134(23):9785-9795
Real-time monitoring of light scattering and UV-vis profiles of four different Cp*Ir(III) precursors under various conditions give insight into nanoparticle formation during oxidation catalysis with NaIO(4) as primary oxidant. Complexes bearing chelate ligands such as 2,2'-bipyridine, 2-phenylpyridine, or 2-(2'-pyridyl)-2-propanolate were found to be highly resistant toward particle formation, and oxidation catalysis with these compounds is thus believed to be molecular in nature under our conditions. Even with the less stable hydroxo/aqua complex [Cp*(2)Ir(2)(μ-OH)(3)]OH, nanoparticle formation strongly depended on the exact conditions and elapsed time. Test experiments on the isolated particles and comparison of UV-vis data with light scattering profiles revealed that the formation of a deep purple-blue color (~580 nm) is not indicative of particle formation during oxidation catalysis with molecular iridium precursors as suggested previously. 相似文献
83.
TJ Pugh SD Weeraratne TC Archer DA Pomeranz Krummel D Auclair J Bochicchio MO Carneiro SL Carter K Cibulskis RL Erlich H Greulich MS Lawrence NJ Lennon A McKenna J Meldrim AH Ramos MG Ross C Russ E Shefler A Sivachenko B Sogoloff P Stojanov P Tamayo JP Mesirov V Amani N Teider S Sengupta JP Francois PA Northcott MD Taylor F Yu GR Crabtree AG Kautzman SB Gabriel G Getz N Jäger DT Jones P Lichter SM Pfister TM Roberts M Meyerson SL Pomeroy YJ Cho 《Nature》2012,488(7409):106-110
84.
Caroline C. Womack Kyle N. Crabtree Laura McCaslin Oscar Martinez Robert W. Field John F. Stanton Michael C. McCarthy 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(16):4173-4176
Carbenes are reactive molecules of the form R1 C̈ R2 that play a role in topics ranging from organic synthesis to gas‐phase oxidation chemistry. We report the first experimental structure determination of dihydroxycarbene (HO C̈ OH), one of the smallest stable singlet carbenes, using a combination of microwave rotational spectroscopy and high‐level coupled‐cluster calculations. The semi‐experimental equilibrium structure derived from five isotopic variants of HO C̈ OH contains two very short CO single bonds (ca. 1.32 Å). Detection of HO C̈ OH in the gas phase firmly establishes that it is stable to isomerization, yet it has been underrepresented in discussions of the CH2O2 chemical system and its atmospherically relevant isomers: formic acid and the Criegee intermediate CH2OO. 相似文献
85.
The onset of specific magnetic structures associated with the formation of extended current filaments is observed in YBCO
single crystals in a rotating magnetic field. Like current filaments in a plasma, they are unstable and decay into current
macrovortices. The appearance of filaments is explained by the formation of closed flux rings along magnetization-reversal
fronts and collapse of these rings with formation of Meissner cylinders. The total current along the surface and in the vortex
shell of the cylinder (the latter current dominates in high-T
c
superconductors) exceeds the critical current in the same volume located far from a filament.
Pis’ma Zh. éksp. Teor. Fiz. 65, No. 3, 253–257 (10 February 1997) 相似文献
86.
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89.
Imidazolium salts blocked at C2 with methyl or benzyl groups unexpectedly react with silver oxide to give N-heterocyclic carbene complexes of silver via an oxidative carbon-carbon bond cleavage. 相似文献
90.
Chen H Tagore R Das S Incarvito C Faller JW Crabtree RH Brudvig GW 《Inorganic chemistry》2005,44(21):7661-7670
A series of complexes with the formula [Mn(III/IV)2(mu-O)2(L)2(X)2]3+ have been prepared in situ from Mn(II)LCl2 precursors by a general preparative method (L = terpy, Cl-terpy, Br-terpy, Ph-terpy, tolyl-terpy, mesityl-terpy, t Bu3-terpy, EtO-terpy, py-phen, dpya, Me2N-terpy, or HO-terpy, and X = a labile ligand such as water, chloride, or sulfate). The parent complex, where L = terpy and X = water, is a functional model for the oxygen-evolving complex of photosystem II (Limburg, et al. J. Am. Chem. Soc. 2001, 123, 423-430). Crystals of Mn(II)(dpya)Cl2, Mn(II)(Ph-terpy)Cl2, Mn(II)(mesityl-terpy)Cl2, and an organic-soluble di-mu-oxo di-aqua dimanganese complex, [Mn(III/)(IV)2(mu-O)2(mesityl-terpy)2(OH2)2](NO3)3, were obtained and characterized by X-ray crystallography. Solutions of the in situ-formed di-mu-oxo dimanganese complexes were characterized by electrospray mass spectrometry, EPR spectroscopy, and UV-visible spectroscopy, and the rates of catalytic oxygen-evolving activity were assayed. The use of Mn(II)LCl2 precursors leads to higher product purity of the Mn dimers while achieving the 1:1 ligand to Mn stoichiometry appropriate for catalytic activity assay. These methods can be used to screen the catalytic activity of other di-mu-oxo dimanganese complexes generated by using a ligand library. 相似文献