全文获取类型
收费全文 | 5457篇 |
免费 | 301篇 |
国内免费 | 21篇 |
专业分类
化学 | 4100篇 |
晶体学 | 15篇 |
力学 | 119篇 |
数学 | 724篇 |
物理学 | 821篇 |
出版年
2023年 | 56篇 |
2022年 | 47篇 |
2021年 | 91篇 |
2020年 | 112篇 |
2019年 | 115篇 |
2018年 | 70篇 |
2017年 | 65篇 |
2016年 | 229篇 |
2015年 | 200篇 |
2014年 | 195篇 |
2013年 | 303篇 |
2012年 | 382篇 |
2011年 | 402篇 |
2010年 | 247篇 |
2009年 | 226篇 |
2008年 | 338篇 |
2007年 | 288篇 |
2006年 | 300篇 |
2005年 | 294篇 |
2004年 | 260篇 |
2003年 | 181篇 |
2002年 | 202篇 |
2001年 | 100篇 |
2000年 | 96篇 |
1999年 | 83篇 |
1998年 | 66篇 |
1997年 | 95篇 |
1996年 | 81篇 |
1995年 | 70篇 |
1994年 | 53篇 |
1993年 | 54篇 |
1992年 | 43篇 |
1991年 | 29篇 |
1990年 | 24篇 |
1989年 | 32篇 |
1988年 | 18篇 |
1987年 | 20篇 |
1986年 | 21篇 |
1985年 | 22篇 |
1984年 | 16篇 |
1983年 | 17篇 |
1982年 | 14篇 |
1981年 | 15篇 |
1979年 | 11篇 |
1978年 | 25篇 |
1976年 | 10篇 |
1975年 | 15篇 |
1974年 | 24篇 |
1973年 | 19篇 |
1967年 | 11篇 |
排序方式: 共有5779条查询结果,搜索用时 15 毫秒
31.
Timerbaev AR Aleksenko SS Polec-Pawlak K Ruzik R Semenova O Hartinger CG Oszwaldowski S Galanski M Jarosz M Keppler BK 《Electrophoresis》2004,25(13):1988-1995
Characterizing how platinum metallocomplexes bind to human serum albumin (HSA) is essential in evaluating anticancer drug candidates. Using cisplatin as a reference complex, the application of capillary electrophoresis (CE) to reliably assess drug/HSA interactions was validated. Since this complex is small compared to the size of the protein, the binding response could only be recognized when applying CE coupled to a (platinum) metal-specific mode of detection, namely inductively coupled plasma-mass spectrometry (ICP-MS). This coupling allowed for confirmation of a specific affinity of cisplatin and novel Pt complexes to HSA, measurement of the kinetics of binding reactions, and determination of the number of drug molecules attached to the protein. As the cisplatin/HSA molar ratio increased, the reaction rate became faster with a maximum on the kinetic curve appearing at about 50 h of incubation at 20 times excess of cisplatin. The reaction was characterized as a pseudo-first order reaction with the rate constant k = 0.003 min(-1) at 37 degrees C. When incubated with a 20-fold excess of cisplatin, HSA bound up to 10 mol of Pt per mol of the protein. This is indicative for a strong metal-protein coordination occurring at several HSA sites other than the only protein cysteine residue. Structural analogs of cisplatin, bearing aminoalcohol ligands, showed comparable protein binding reactivity and stoichiometry but a common equilibrium was not reached even after one week of incubation. Also apparent was a two-step mechanism of the binding reaction. Results demonstrated the suitability of CE-ICP-MS as a rapid assay for high-throughput studying of drug/HSA interactions. 相似文献
32.
33.
The adsorption, diffusion and desorption of chlorine on and from stoichiometric, reduced and partially reduced (defective) rutile TiO2{110} are investigated using ab initio density functional theory (DFT) calculations. Theoretical results are compared with experimental investigations, and microkinetic simulations based on DFT values are then used to verify the diffusion mechanisms assumed in the experimental investigations. 相似文献
34.
Le Guennic B Neugebauer J Reiher M Autschbach J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(5):1677-1686
The experimental 13C NMR chemical shift of the central carbon atom in the octahedral [(Ph3PAu)6C]2+ cluster was investigated on the basis of relativistic density functional calculations. In order to arrive at independent model conclusions regarding the value of the chemical shift, a systematic study of the dependence of the cluster structure on the phosphine ligands, the chosen density functionals, and the basis set size was conducted. The best structures obtained were then used in the NMR calculations. Because of the cage-like cluster structure a pronounced deshielding of the central carbon nucleus could have been expected. However, upon comparison with the 13C NMR properties of the related complex [C{Au[P(C6H5)2(p-C6H4NMe2)]}6]2+, Schmidbaur et al. have assigned a signal at delta=135.2 ppm to the interstitial carbon atom. Our calculations confirm this value in the region of the aromatic carbon atoms of the triphenylphosphine ligands. The close-lying signals of the 108 phenyl carbon atoms can explain the difficulties of assigning them experimentally. 相似文献
35.
Bulk properties and free interfaces of mixtures of charged platelike colloids and salt are studied within the density-functional theory. The particles are modeled by hard cuboids with their edges constrained to be parallel to the Cartesian axes corresponding to the Zwanzig model. The charges of the particles are concentrated in their center. The density functional is derived by functional integration of an extension of the Debye-Hückel pair distribution function with respect to the interaction potential. For sufficiently small macroion charges, the bulk phase diagrams exhibit one isotropic and one nematic phase separated by a first-order phase transition. With increasing platelet charge, the isotropic and nematic binodals are shifted to higher densities. The Donnan potential between the coexisting isotropic and nematic phases is inferred from bulk structure calculations. Nonmonotonic density and nematic order parameter profiles are found at a free interface interpolating between the coexisting isotropic and nematic bulk phases. Moreover, electrically charged layers form at the free interface leading to monotonically varying electrostatic potential profiles. Both the widths of the free interfaces and the bulk correlation lengths are approximately given by the Debye length. For fixed salt density, the interfacial tension decreases upon increasing the macroion charge. 相似文献
36.
37.
38.
Heilemann M Tinnefeld P Sanchez Mosteiro G Garcia Parajo M Van Hulst NF Sauer M 《Journal of the American Chemical Society》2004,126(21):6514-6515
We demonstrate the synthesis and spectroscopic characterization of an unidirectional photonic wire based on four highly efficient fluorescence energy-transfer steps (FRET) between five spectrally different chromophores covalently attached to double-stranded DNA. The DNA-based modular conception enables the introduction of various chromophores at well-defined positions and arbitrary interchromophore distances. While ensemble fluorescence measurements show overall FRET efficiencies between 15 and 30%, single-molecule spectroscopy performed on four spectrally separated detectors easily uncovers subpopulations that exhibit overall FRET efficiencies of up to approximately 90% across a distance of 13.6 nm and a spectral range of approximately 200 nm. Fluorescence trajectories of individual photonic wires show five different fluorescence intensity patterns which can be ascribed to successive photobleaching events. 相似文献
39.
Coordination of dinitrogen to Sellmann-type iron (II) complexes in a sulfur-dominated coordination sphere, which emulates
the environment of iron centers in the FeMo-cofactor of nitrogenase, is analyzed with respect to spin states, spin barriers,
and the effect of trans-ligands. Such detailed investigations became only recently feasible when the reliability of density functional methods, which
are the only quantum chemical methods capable of describing large transition metal complexes, could significantly be improved
for the calculation of energies for states of different spin. It is found that the actual binding energy of dinitrogen is
of sufficient magnitude for a reasonably strong fixation of N2 by Sellmann-type coordination compounds. However, potential fixation is determined by additional factors which reduce the
binding energy. One factor is the change in spin state of the N2-free metal fragment, which lowers the total energy and quenches the thermodynamic stabilization effect of the binding energy.
In addition, the metal fragment rearranges and gains even more stabilization energy for the un-coordinated state. Apart from
these thermodynamical effects, the existence of spin barriers, which must be overcome upon binding of dinitrogen, leads to
kinetical effects, which cannot be neglected. 相似文献
40.
Cushman M Yang D Gerhardt S Huber R Fischer M Kis K Bacher A 《The Journal of organic chemistry》2002,67(16):5807-5816
A series of 6-carboxyalkyl and 6-phosphonoxyalkyl derivatives of 7-oxo-8-D-ribityllumazine were synthesized as inhibitors of both Escherichia coli riboflavin synthase and Bacillus subtilis lumazine synthase. The compounds were designed to bind to both the ribitylpurine binding site and the phosphate binding site of lumazine synthase. In the carboxyalkyl series, maximum activity against both enzymes was observed with the 3'-carboxypropyl compound 22. Lengthening or shortening the chain linking the carboxyl group to the lumazine by one carbon resulted in decreased activity. In the phosphonoxyalkyl series, the 3'-phosphonoxypropyl compound 33 was more potent than the 4'-phosphonoxybutyl derivative 39 against lumazine synthase, but it was less potent against riboflavin synthase. Molecular modeling suggested that the terminal carboxyl group of 6-(3'-carboxypropyl)-7-oxo-8-D-ribityllumazine (22) may bind to the side chains of Arg127 and Lys135 of the enzyme. A hypothetical molecular model was also constructed for the binding of 6-(2'-carboxyethyl)-7-oxolumazine (15) in the active site of E. coli riboflavin synthase, which demonstrated that the active site could readily accommodate two molecules of the inhibitor. 相似文献