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41.
A generator of chemical structures (CONGEN) has been utilized to investigate two aspects of the structural isomerism of mono- and sesquiterpenoid skeletons: (1) the scope of possible isomers under various structural constraints; and (2) the scope of possible isomers based on a mechanistic model which allows interactive exploration of reactions of formation and interconversion. The possibilities, even under severe constraints, are many more than the structural types commonly encountered in natural. These results indicate the potential danger of structural assignment based in part on biogenic grounds. 相似文献
42.
Amashukeli X Gruhn NE Lichtenberger DL Winkler JR Gray HB 《Journal of the American Chemical Society》2004,126(47):15566-15571
Inner-sphere electron-transfer reorganization energies of Zn(protoporphyrin IX) and Zn(octaethylporphyrin) are determined from band-shape analyses of the first ionization obtained by gas-phase valence photoelectron spectroscopy. The experimentally determined total inner-sphere reorganization energies for self-exchange (120-140 meV) indicate that structural changes upon oxidation are largely confined to the porphyrin ring, and substituents on the ring or solvent and other environmental factors make smaller contributions. Computational estimates by different models vary over a wide range and are sensitive to numerical precision factors for these low reorganization energies. Of current computational models that are widely available and practical for molecules of this size, functionals that contain a mixture of Hartree-Fock exchange and DFT exchange-correlation appear to be the most applicable. 相似文献
43.
Understanding molecular orientation on a metal surface is key to designing molecular electronic device junctions. Though platinum device electrodes are of particular interest as a more stable alternative to the often used gold electrodes, the chemisorption of conducting molecules onto platinum surfaces has not been thoroughly studied. We present herein the first detailed study of the ability and manner in which soluble oligothiophene isocyanides, of lengths ranging from 2 to 7 nm, chemisorb onto platinum surfaces and nanoparticles. It was found that these oligothiophene isocyanides stand at a 41 degrees angle from the platinum surface normal, suggesting their applicability in molecule-bridged platinum electrode devices. 相似文献
44.
The cyclic sulfones1,2, and3 are lithiated in benzene with n-butyllithium. Lithiation is demonstrated to lead to α-mono, α,α′-di and/or α,α-di and α,α,α′ trimetallation. The lithiated sulfones are chlorinated with hexachloroethane (HCE). Some mechanistic aspects of the reaction of the lithiosulfones with vicinal dihalides are discussed. 相似文献
45.
Chiral fluorous imidazolidinone catalyst 2 provides consistently high enantioselectivities in Diels–Alder reactions of dienes and ,β-unsaturated aldehydes. The catalyst can be readily separated from the reaction products by fluorous solid-phase extraction, and recovered in excellent purity for direct reuse. 相似文献
46.
Rajapakshe A Gruhn NE Lichtenberger DL Basta R Arif AM Ernst RD 《Journal of the American Chemical Society》2004,126(43):14105-14116
Molecules of the form Cp(6,6-dmch)ZrX(2) (Cp = eta(5)-cyclopentadienyl, X = Cl, Br, I; 6,6-dmch = eta(5)-6,6-dimethylcyclohexadienyl) have been synthesized, and the molecular and electronic structures have been investigated. These molecules allow direct comparison of the bonding and properties of pentadienyl and cyclopentadienyl ligands in the same high-oxidation-state metal complexes. Unlike the well-known Cp(2)ZrX(2) analogues, these Cp(6,6-dmch)ZrX(2) molecules are intensely colored, indicating significantly different relative energies of the frontier orbitals. Also unusual, the average Zr-C distances to the 6,6-dmch pentadienyl ligand are about 0.1 A longer than the average Zr-C distances to the cyclopentadienyl ligand for these Zr(IV) complexes, opposite of what is observed for the Zr(II) complex Cp(2,6,6-tmch)Zr(PMe(3))(2) (tmch = eta(5)-2,6,6-trimethylcyclohexadienyl), reflecting a dramatic reversal in the favorability of the bonding depending on the metal oxidation state. The experimental and computational results indicate that the color of the Cp(6,6-dmch)ZrX(2) complexes is due to a 6,6-dmch ligand-to-metal charge-transfer band. Compared to the Cp(2)ZrX(2) analogues, the Cp(6,6-dmch)ZrX(2) molecules have a considerably less stable HOMO that is pentadienyl-based and an essentially unchanged metal-based LUMO. Also, the lowest unoccupied orbital of pentadienyl is stabilized relative to cyclopentadienyl and becomes a better potential delta electron acceptor, thus contributing to the differences in structure and reactivity of the low-valent and high-valent metal complexes. 相似文献
47.
A technique is formulated to determine both thickness and refractive indices of free-standing films with biaxial symmetry from polarized transmission spectra. The films must be transparent and show little dispersion in refractive indices in the wavelength range where the transmission spectra are collected. Methods are proposed to correct the errors caused by imperfect polarization of incident radiation and thickness variation across the sampling area. Anisotropic refractive indices and thickness of poly(biphenyl dianhydride-p-phenylenediamine) films which exhibit uniaxial optical anisotropy are determined from polarized transmission spectra. The refractive index and thickness values compare well to those obtained from waveguide prism coupler and profilometer measurements. 相似文献
48.
The isomeric chlorosulfones 3, 4 and 5 are prepared by 1,4-addition of sulfonyl chlorides to isoprene, Dehydrohalogenation affords the corresponding 2- and 3-methylbutadienyl sulfones in a configuration which is dependent on the configuration of the chlorosulfone. Pure Z-2-methylbutadienyl sulfones 1 are obtained by displacement of primary halides by the Z-sulfinate anion 2. The Z-sulfones 1 are isomerized to E/Z-mixtures. The E/Z-mixtures are separated into their components and the configuration of the isomers is established by the NMR-NOE technique. 相似文献
49.
Hydroxy sulfoxide 1 reacts with SO2Cl2 to give the (Z)-C5 terpene building block 3b via cyclic alkoxy oxosulfonium salt 2. The conversion of 1 via the corresponding sulfone 4 leads to the (E) isomer 6b. An explanation is offered for the stereoselective course of the reactions. 相似文献
50.