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31.
Michael J. Redrup Gerald D. Risbridger Peter W. Skett 《Journal of mass spectrometry : JMS》1989,24(5):309-316
Moving belt LC/MS has been used to identify the degradation products of the slow calcium membrane channel inhibitor, Diproteverine, after storage at elevated temperature and humidity. The major products observed result from oxidation. Two of these products, both ketones, yield [M ? 14 + H]+ ions by chemical ionization. These unusual ions also occur for some simple aromatic ketones used as model compounds and are shown to arise by reduction of the carbonyl group to a methylene by the reagent gas. 相似文献
32.
Kumar D Hirao H de Visser SP Zheng J Wang D Thiel W Shaik S 《The journal of physical chemistry. B》2005,109(42):19946-19951
Density functional theory (DFT) is applied to the dark section of the catalytic cycle of the enzyme cytochrome P450, namely, the formation of the active species, Compound I (Cpd I), from the ferric-hydroperoxide species (Cpd 0) by a protonation-assisted mechanism. The chosen 96-atom model includes the key functionalities deduced from experiment: Asp(251), Thr(252), Glu(366), and the water channels that relay the protons. The DFT model calculations show that (a) Cpd I is not formed spontaneously from Cpd 0 by direct protonation, nor is the process very exothermic. The process is virtually thermoneutral and involves a significant barrier such that formation of Cpd I is not facile on this route. (b) Along the protonation pathway, there exists an intermediate, a protonated Cpd 0, which is a potent oxidant since it is a ferric complex of water oxide. Preliminary quantum mechanical/molecular mechanical calculations confirm that Cpd 0 and Cpd I are of similar energy for the chosen model and that protonated Cpd 0 may exist as an unstable intermediate. The paper also addresses the essential role of Thr(252) as a hydrogen-bond acceptor (in accord with mutation studies of the OH group to OMe). 相似文献
33.
The hydride transfer process between the isoalloxazine moiety of flavins and the nicotinamide moiety of NAD(P)H has been explored by using density functional theory based reactivity index in the 1-methylnicotinamide-lumiflavine model system. Based on crystallographic data available, we have found that the group softness index helps to locate and orientate reactive regions in these interacting molecules while the electrophilicity index successfully describes the reactivity pattern of this system. 相似文献
34.
Fürstner A Ackermann L Gabor B Goddard R Lehmann CW Mynott R Stelzer F Thiel OR 《Chemistry (Weinheim an der Bergstrasse, Germany)》2001,7(15):3236-3253
Exchange of one PCy3 unit of the classical Grubbs catalyst 1 by N-heterocyclic carbene (NHC) ligands leads to "second-generation" metathesis catalysts of superior reactivity and increased stability. Several complexes of this type have been prepared and fully characterized, six of them by X-ray crystallography. These include the unique chelate complexes 13 and 14 in which the NHC- and the Ru-CR entities are tethered to form a metallacycle. A particularly favorable design feature is that the reactivity of such catalysts can be easily adjusted by changing the electronic and steric properties of the NHC ligands. The catalytic activity also strongly depends on the solvent used; NMR investigations provide a tentative explanation of this effect. Applications of the "second-generation" catalysts to ring closing alkene metathesis and intramolecular enyne cycloisomerization reactions provide insights into their catalytic performance. From these comparative studies it is deduced that no single catalyst is optimal for different types of applications. The search for the most reactive catalyst for a specific transformation is facilitated by IR thermography allowing a rapid and semi-quantitative ranking among a given set of catalysts. 相似文献
35.
Boisguerin P Leben R Ay B Radziwill G Moelling K Dong L Volkmer-Engert R 《Chemistry & biology》2004,11(4):449-459
SPOT synthesis permits parallel synthesis and screening of thousands of cellulose membrane-bound peptides to study protein-protein interactions in a proteomic context. Recognition of C-terminal residues is one of the most common binding features of PDZ domains. Unfortunately, most solid support-bound peptide libraries lack a free C terminus due to C-terminal fixation on the solid support. To overcome this restriction, we developed a robust methodology based on our previous strategy for generating peptides with authentic C termini. To validate this improved method, we screened a human peptide library of 6223 C termini with the syntrophin PDZ domain. Furthermore, using the same library, new peptide ligands derived from membrane proteins and receptors were found for the ERBIN PDZ domain. Finally, we identified the protein kinase breakpoint cluster region, which is known as a negative regulator of cell proliferation and oncogenic transformation, as an ERBIN ligand. 相似文献
36.
Yun Liu A.P. Whichello Valeska Ting John D. Fitz Gerald 《Journal of solid state chemistry》2005,178(11):3389-3395
A combined synthesis, diffraction and dielectric properties investigation of the dependence (and effect) of Mn2+/Nb5+ ordering in Ba3MnNb2O9 (BMN) upon annealing atmosphere and processing conditions has been carried out. Annealing in different atmospheres was not found to significantly alter either nominal stoichiometry or structure type. The obtained structure type (disordered metrically cubic or ordered trigonal) as well as the measured electrical properties (in particular, the dielectric loss) were, however, found to be sensitive to the synthesis route. Samples obtained via solid-state reaction were found to be predominantly of 1:2 Mn2+/Nb5+ ordered, trigonal structure type whereas samples obtained via an aqueous solution route were found to be of a Mn2+/Nb5+ ‘disordered’, metrically cubic structure type. All solid-state synthesized samples showed reasonable dielectric properties. The microwave dielectric constant and dielectric quality factor, Q, at 8 GHz of an as-synthesized BMN sample were 38 and 100, respectively. By contrast, the dielectric loss of the metrically cubic, Mn2+/Nb5+ ‘disordered’ samples obtained via an aqueous solution synthesis process were significantly worse. 相似文献
37.
Jonathan A. Yoffe Gerald M. Maggiora A.Terry Amos 《Theoretical chemistry accounts》1981,58(2):137-144
Stieltjes conditions and the ratio test provide necessary but not sufficient conditions onS(-2k) dipole sums. If the dipole sums are accurate the associated [n, n –1] Padé approximant provides a better representation of (), the frequency-dependent dipole polarizability, than a truncated series expression and, in addition, should bound () below. It is shown how constraints on the dipole sums effect the form of the [2,1] Padé approximant and an additional constraint is derived that ensures the analyticity of the approximant on 0 < 1. There then follows a discussion of the reliability of available literature dipole sum values for small molecules containing H, C, N and O. 相似文献
38.
J. D. Petke Gerald M. Maggiora‡ Lester Shipman‡ Ralph E. CHRISTOFFERSEN‡ 《Photochemistry and photobiology》1979,30(2):203-223
Abstract— Ab initio configuration interaction wavefunctions and energies are reported for the ground state and many low-lying excited singlet and triplet states of ethyl pheophorbide a (Et-Pheo a) and ethyl chlorophyllide a (Et-Chl a), and are employed in an analysis of the electronic absorption spectra of these systems. In both molecules the visible spectrum is found to consist of transitions to the two lowest-lying 1(π, π*) states, S1 and S2. The configurational compositions of S1 and S2 in both molecules are similar, and are described qualitatively in terms of a four-orbital model. The S1← S0 transition in each case is predicted to be intense, and is largely in-plane y-polarized, while the S2← S0 transition is predicted to be extremely weak and in-plane polarized. The orientation of the S2← S0 transition dipole is not conclusively established in the present calculations. The Soret band in both molecules is composed of transitions to no less than ten states (S3-S12 in Et-Chl a and S3-S7S9-S12. and S14 in Et-Pheo a), which exhibit primarily (π, π*) character. The configurational compositions of these states are generally a complex mixture of excitations from both occupied macrocyclic π molecular orbitals and occupied orbitals with electron density in the cyclopen-tanone ring and the carbomethoxy chain. No clear correspondences are evident between respective Soret states of the two systems. Transitions to these states are generally intense and display a variety of in-plane polarizations. Two additional Soret states of Et-Pheo a, S8 and S13, exhibit primarily (n. π*) character. S8 is characterized by excitations from u and non-bonding regions of the carbomethoxy chain, while S13 is described by n →π* excitations involving the nitrogen atom of ring II. No corresponding (n, π*) states were found for Et-Chl a. In both molecules the lowest two triplet states, T1 and T2, are found to lie lower in energy than S1. while T, and S1 are approximately degenerate. The configurational compositions of T1-T4 of both molecules are nearly identical, and may be described by a four-orbital model. However, the compositions of T1-T4 differ sharply from those of S1 and S2. A number of higher-lying 3(π, π*) states of both molecules (T5-T13 in Et-Chi a and T8-T9, T11-T13 in Et-Pheo a) are found to have energies similar to the singlet Soret states, relative to S0. They are characterized by a complex mixture of configurations which do not include significant contributions involving the four-orbital model. In addition, two 3(n, π*) states of Et-Pheo a, T10 and T14, are found, which are somewhat analogous to S8 and S13. Additional data presented include the charge distributions and molecular dipole moments of the S0. S1, and T1 states of both molecules, as well as energies and oscillator strengths of computed Sn←S1 and Tn←1 transitions. 相似文献
39.
Recent advances in chiral separation principles in capillary electrophoresis and capillary electrochromatography 总被引:3,自引:0,他引:3
This review summarizes recent developments in chiral separation in capillary zone electrophoresis (CZE), electrokinetic chromatography (EKC), and capillary electrochromatography (CEC) covering literature published since the year 2000. New chiral selectors and innovative approaches for CE and CEC are introduced. Recent progress in column technology for CEC is highlighted and the development of new chiral stationary phases is discussed. This review is not dedicated to list applications but will focus on new developments. 相似文献
40.
Manning GS 《Journal of the American Chemical Society》2003,125(49):15087-15092
X-ray diffraction structures of the nucleosome core particle along with a variety of experiments are consistent with the idea that an important source of the free energy holding DNA to the superhelical ramp on the histone octamer surface is obtained from a relatively small amount of electrostatic neutralization of the DNA phosphate charge by positively charged histone groups, especially arginine residues. Here we present a theoretical analysis of a simple model that emphasizes the competition between the high degree of bending of the stiff DNA molecule required for its tight curvature on the histone octamer and the neutralization of the DNA phosphate charge by basic histone residues. Our calculation accounts for the strong influence of condensed counterions on the electrostatic interactions. We find that the minimum amount of free energy required to bend DNA into axial conformity with the superhelical ramp at physiological salt concentration can be provided by a scant 6% neutralization of the phosphate charge, in close correspondence to the stoichiometric neutralization of phosphate charge by the arginine side chain that intrudes into the inward-facing minor groove of each DNA double helical turn. 相似文献