全文获取类型
收费全文 | 82231篇 |
免费 | 8999篇 |
国内免费 | 7931篇 |
专业分类
化学 | 45342篇 |
晶体学 | 511篇 |
力学 | 5308篇 |
综合类 | 955篇 |
数学 | 18986篇 |
物理学 | 28059篇 |
出版年
2024年 | 172篇 |
2023年 | 944篇 |
2022年 | 1552篇 |
2021年 | 2885篇 |
2020年 | 2409篇 |
2019年 | 2427篇 |
2018年 | 1967篇 |
2017年 | 2161篇 |
2016年 | 2929篇 |
2015年 | 2800篇 |
2014年 | 3650篇 |
2013年 | 6226篇 |
2012年 | 4164篇 |
2011年 | 4680篇 |
2010年 | 4029篇 |
2009年 | 5085篇 |
2008年 | 5223篇 |
2007年 | 5483篇 |
2006年 | 4497篇 |
2005年 | 3442篇 |
2004年 | 2955篇 |
2003年 | 2842篇 |
2002年 | 4993篇 |
2001年 | 2436篇 |
2000年 | 2086篇 |
1999年 | 1750篇 |
1998年 | 1651篇 |
1997年 | 1252篇 |
1996年 | 1100篇 |
1995年 | 983篇 |
1994年 | 946篇 |
1993年 | 888篇 |
1992年 | 815篇 |
1991年 | 614篇 |
1990年 | 565篇 |
1989年 | 494篇 |
1988年 | 455篇 |
1987年 | 395篇 |
1986年 | 362篇 |
1985年 | 504篇 |
1984年 | 387篇 |
1983年 | 206篇 |
1982年 | 413篇 |
1981年 | 569篇 |
1980年 | 511篇 |
1979年 | 548篇 |
1978年 | 455篇 |
1977年 | 364篇 |
1976年 | 313篇 |
1973年 | 199篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
911.
Thomas Unnerstall 《Journal of statistical physics》1989,54(1-2):379-403
The irreversible macroscopic dynamics of the Josephson junction coupled to external wires acting as a current source is derived rigorously from the underlying microscopic Hamiltonian quantum mechanics. The external systems are treated in the singular coupling limit. The use of this limit is explicitly justified via an interpretation of the singular coupling limit in terms of the relative magnitudes of system, reservoir, and coupling energies. The qualitative behavior of the macroscopic dynamical equations is shown to depend sensitively and crucially on the interaction between the wires and the superconductors and on the size of the wires: the dc Josephson effect only happens when one lets Cooper pairs be driven into the junction by collective (i.e., small) reservoirs. 相似文献
912.
Claudio Albanese 《Journal of statistical physics》1989,55(1-2):297-309
The quantum, antiferromagnetic, spin-1/2 Heisenberg Hamiltonian on thed-dimensional cubic lattice
d
is considered for any dimensiond. First the anisotropic case is considered for small transversal coupling and a convergent expansion is given for a family of eigenprojections which is complete in all finite-volume truncations. Then the general case is considered, for which an upper bound to the ground-state energy is given which is optimal for strong enough anisotropy. This bound is expressed through a functional involving the statistical expectation value at finite temperature of a certain correlation function of an Ising model defined on the lattice
d
itself. 相似文献
913.
914.
M. A. Massiah V. Saraswat H. F. Azurmendi A. S. Mildvan 《Journal of Molecular Structure》2004,700(1-3):247-254
The MutT pyrophosphohydrolase from E. coli (129 residues) catalyzes the hydrolysis of nucleoside triphosphates (NTP), including 8-oxo-dGTP, by substitution at Pβ, to yield NMP and pyrophosphate. The product, 8-oxo-dGMP is an unusually tight binding, slowly exchanging inhibitor with a KD=52 nM, (ΔG°=−9.8 kcal/mol) which is 6.1 kcal/mol tighter than the binding of dGMP (ΔG°=−3.7 kcal/mol). The higher affinity for 8-oxo-dGMP results from a more favorable ΔHbinding (−32 kcal/mol) despite an unfavorable −TΔS°binding (+22 kcal/mol). The solution structure of the MutT–Mg2+-8-oxo-dGMP complex shows a narrowed, hydrophobic nucleotide-binding cleft with Asn-119 and Arg-78 among the few polar residues. The N119A, N119D, R78K and R78A single mutations, and the R78K+N119A double mutant all showed largely intact active sites, on the basis of small changes in the kinetic parameters of dGTP hydrolysis and in 1H–15N HSQC spectra. However, the N119A mutation profoundly weakened the active site binding of 8-oxo-dGMP by 4.3 kcal/mol (1650-fold). The N119D mutation also weakened 8-oxo-dGMP binding but only by 2.1 kcal/mol (37-fold), suggesting that Asn-119 functioned both as a hydrogen bond donor to C8=O, and a hydrogen bond acceptor from N7H of 8-oxo-dGMP, while aspartate at position −119 functioned as an acceptor of a single hydrogen bond. Much smaller weakening effects (0.3–0.4 kcal/mol) on the binding of dGMP and dAMP were found, indicating specific hydrogen bonding of Asn-119 to 8-oxo-dGMP. While formation of the wild type MutT–Mg2+-8-oxo-dGMP complex slowed the backbone NH exchange rates of 45 residues distributed throughout the protein, the same complex of the N119A mutant slowed the exchange rates of only 11 residues at or near the active site, indicating an increase in conformational flexibility of the N119A mutant. The R78K and R78A mutations weakened the binding of 8-oxo-dGMP by 1.7 and 1.1 kcal/mol, respectively, indicating a lesser role of Arg-78 than of Asn-119 in the selective binding of 8-oxo-dGMP, likely donating a single hydrogen bond to its C6=O. The R78K+N119A double mutant weakened the binding of 8-oxo-dGMP (KIslope=3.1 mM) by 6.5±0.2 kcal/mol which overlaps, within error with the sum of the effects of the two single mutants (6.0±0.3 kcal/mol). Such additive effects of the two single mutants in the double mutant are most simply explained by the independent functioning of Asn-119 and Arg-78 in the binding of 8-oxo-dGMP. Independent functioning of these two residues in nucleotide binding is consistent with their locations in the MutT–Mg2+-8-oxo-dGMP complex, on opposite sides of the active site cleft, with a distance of 8.4±0.5 Å between their side chain nitrogens. 相似文献
915.
An intrinsic principle of least action is presented for the intrinsic dynamism of chemical reactions. Then, as the stationary trajectory, a meta-IRC (intrinsic reaction coordinate) draws a geodesic curve in a rigged Riemannian space. This establishes a geodesic law for the intrinsic dynamism. Moreover, a diagrammatic perturbation theory is formulated for the intrinsic dynamism, and a dynamical interaction between a chemically reacting system and a background system is investigated. Then, the structural stability of the system is discussed using a new concept of the dynamical potential field. An example is given in order to elucidate the present theory.Dedicated to Prof. Hermann Hartmann on the occasion of his 65th birthday. 相似文献
916.
The preparation and mesomorphic properties of a substituted bis(dithiolene)nickel complex derived from 4, 4'-dimethoxybenzil are reported. The phase transition temperatures were based on data obtained by polarized light microscopy and differential scanning calorimetry. The mesogenic phase existed over the temperature range from 77 to 175 degrees C. A novel micropacked column (1.5 or 3 m x 1 mm i.d.) prepared from the slurry of bis[1,2-bis(4-n-undecyloxyphenyl)ethane-1,2-dithiolene] nickel(II) (5%, w/w), coated on Chromosorb W was applied for the separation of dialkyl sulfides. The non-linearity (discontinuity) of Van't Hoff plots suggests that the liquid crystal property existed even in the coated phase. Factors affecting the retention and the sample selectivity on the prepared column were examined by using a flame photometric detector (FPD). The separation might be based on the mechanism of ligand exchange, shape selectivity and polarity interaction besides the vapor pressure. LOD for the determination of dialkyl sulfides was below 1 ng for most of the analytes. 相似文献
917.
WU Xiu-Lan WANG Fen REN Qiang 《结构化学》2007,26(6):732-736
Homogeneous cordierite has been synthesized at low cost by talc-magnesite and coal gangue as the main raw materials. The mechanism of synthesizing cordierite under such a com- posing system of raw materials, and the effect of temperature on the crystal cell parameters and microstructure and thermal expansion coefficient of cordierite crystal have been studied via testing methods of XRD, SEM, etc. The result shows that the homogeneous cordierite can be synthesized by the systematic composing materials of “talc-magnesite—coal gangue—talc” with heat pre- servation at 1350 ℃ for 1 h; as the keeping time is prolonged, Al3+ and Mg2+ in cordierite crystal are replaced by a few impurity ions such as Fe3+, Fe2+, etc., and the crystal cell parameters of cordierite present an increase trend; as the high-temperature heat preservation is prolonged, the content of glassy phase in the sample is increased, its density is improved, and its thermal expansion coeffi- cient presents an increase trend. 相似文献
918.
Ar—Kr溶液扩散系数的分子动力学模拟及其与温度的关系 总被引:2,自引:1,他引:2
用分子动力学模拟方法研究确定Ar-Kr溶液的自扩散系数D1、D2和互扩散系数D12以及它们随温度变化的规律。结果表明,分别用Green-Kubo法和Einstein法得到的扩散系数在数值上一致;该溶液的3种扩散系数均满足D=D0e^E/RT关系。 相似文献
919.
Polyazido high-nitrogen compounds: hydrazo- and azo-1,3,5-triazine 总被引:13,自引:0,他引:13
Huynh MH Hiskey MA Hartline EL Montoya DP Gilardi R 《Angewandte Chemie (International ed. in English)》2004,43(37):4924-4928
920.
The nature of the 1,3 hydrogen rearrangement of formamidine (H2N-CH=NH) and the solvent effects on that reaction are studied with ab initio molecular orbital calculations on the basis of the supermolecule model. The reaction path and the motion of the migrating hydrogen atom are traced by using the concept of the intrinsic reaction coordinate (IRC). Four types of orientation of one water molecule to formamidine at the transition state of reaction are examined and the results are discussed from the standpoint of the orbital interactions. 相似文献