全文获取类型
收费全文 | 9964篇 |
免费 | 1391篇 |
国内免费 | 1407篇 |
专业分类
化学 | 5667篇 |
晶体学 | 85篇 |
力学 | 1497篇 |
综合类 | 65篇 |
数学 | 946篇 |
物理学 | 4502篇 |
出版年
2024年 | 24篇 |
2023年 | 112篇 |
2022年 | 272篇 |
2021年 | 290篇 |
2020年 | 386篇 |
2019年 | 337篇 |
2018年 | 324篇 |
2017年 | 400篇 |
2016年 | 420篇 |
2015年 | 404篇 |
2014年 | 544篇 |
2013年 | 818篇 |
2012年 | 634篇 |
2011年 | 675篇 |
2010年 | 529篇 |
2009年 | 611篇 |
2008年 | 569篇 |
2007年 | 629篇 |
2006年 | 530篇 |
2005年 | 556篇 |
2004年 | 468篇 |
2003年 | 395篇 |
2002年 | 353篇 |
2001年 | 342篇 |
2000年 | 282篇 |
1999年 | 252篇 |
1998年 | 229篇 |
1997年 | 184篇 |
1996年 | 170篇 |
1995年 | 162篇 |
1994年 | 131篇 |
1993年 | 97篇 |
1992年 | 86篇 |
1991年 | 79篇 |
1990年 | 68篇 |
1989年 | 45篇 |
1988年 | 50篇 |
1987年 | 35篇 |
1986年 | 31篇 |
1985年 | 35篇 |
1984年 | 34篇 |
1983年 | 12篇 |
1982年 | 26篇 |
1981年 | 17篇 |
1980年 | 19篇 |
1979年 | 21篇 |
1978年 | 10篇 |
1977年 | 22篇 |
1976年 | 14篇 |
1973年 | 9篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
151.
将改进的基本度量理论与热力学微扰理论相结合,提出了胶体/高分子系统排空相互作用的IRDFT理论。该理论解释了在实际胶体系统中起重要作用的排斥体积效应和高分子链内相关性的竞争机制。应用该IRDFT,分别以线性链状和环状结构的高分子及其单体为排空元,计算了不同排空元条件下的胶体间排空相互作用。研究表明:对于絮凝破坏,自由环状高分子具有更大的优势。 相似文献
152.
Tingmin Wang Jerald S. Bradshaw Janet C. Curtis Peter Huszthy Reed M. Izatt 《Journal of inclusion phenomena and macrocyclic chemistry》1993,16(2):113-122
Significant - interaction is found in the complexes of (S, S)-dimethylpyridino-18-crown-6 with (R)- and (S)-[-(1-naphthyl)ethyl]ammonium perchlorate. This finding is supported by the1H NOESY NMR spectral technique, greater chemical shift changes of aromatic protons in both host and guest molecules upon complexation, and by molecular mechanics calculations. Because of the flexibility of the ligand, the tripod hydrogen bonding causes13C relaxation times of all periphery carbons to decrease without significant selectivity. Rotational energy barrier calculations of the methyl groups of the complexed ligand also show that the (S, S)-host-(R)-guest is the more stable complex. 相似文献
153.
154.
A study was carried out to determine if rotational correlation time of spin-labeled hen egg lysozyme (HEL) interacting with ultrafiltration membranes could be used to infer protein-membrane interaction. Polysulfone and cellulosic membranes, which have notably different adsorption properties, and membranes with varying pore sizes were used in this study. Based on this study, it was determined that the rotational correlation time does reflect variations in protein adsorption and pore plugging on membranes. The rotational correlation times for the highly adsorbent polysulfone (2.82 × 10−8 s) were significantly higher than those obtained from proteins on cellulosic membranes (0.62 × 10−8 s) and from those in solution (0.17 × 10−8 s). Rotational correlation time was also increased due to steric hindrance associated with pore plugging, although it was not as significant as the adsorption effect. This study indicates that the rotational time constant can be used to infer the type of protein-membrane interaction. 相似文献
155.
Elena V. Parfenyuk Olga I. Davydova Nataliya Sh. Lebedeva 《Journal of solution chemistry》2004,33(1):1-10
Calorimetric titrations have been performed at 298.15 K in aqueous solutions to derive the stability constants and thermodynamic parameters of the interactions of D-maltose and sucrose with some amino acids (glycine, DL-alanine, DL-leucine, and L-serine). The apparent molal volumes of the disaccharides in dilute aqueous solutions of the amino acids have been determined from density measurements at 298.15 K. In contrast to D-maltose, sucrose was found to associate with the amino acids and these associated species are preferentially entropy stabilized. These results are interpreted in terms of the influence of the nature of the solutes, their specific conformations, and hydration, on the ability of the disaccharides to form associated complexes with the amino acids. 相似文献
156.
Excess Molar Volume and Viscosity of Isobutyric Acid + Water Binary Mixtures Near and Far Away from the Critical Temperature 总被引:1,自引:0,他引:1
The excess molar volume VE, shear viscosity deviation Δη and excess Gibbs energy of activation ΔG∗E of viscous flow have been investigated by using density (ρ) and shear viscosity (η) measurements for isobutyric acid + water (IBA+W) mixtures over the entire range of mole fractions at five different temperatures,
both near and close to the critical temperature (2.055K ≤ (T−Tc)≤ 13.055K). The results were also fitted with the Redlich–Kister equation. This system exhibited very large negative values
of VE and very large positive values of Δη due to increased hydrogen bonding interactions and correlation length between unlike molecules in the critical region and
to very large differences between the molar volumes of the pure components at low temperatures. The activation parameters
ΔH∗ and ΔS∗ have been also calculated and show that the critical region has an important effect on the volumetric properties. 相似文献
157.
Solvothermal Synthesis and Structure Characterization of a 3D Hydrogen-bonded Copper Compound [Cu(H_2dhpmc)_2]·2H_2O 总被引:2,自引:0,他引:2
1 INTRODUCTION The controlled assembly of inorganic and coordination polymers from simple building blocks is an important challenge in the design of high- dimensionality systems. In the crystal engineering 'toolbox'[1], hydrogen bonding moieties are perhaps the implements used the most in the design of such supramolecular systems[2], and have been particularly strongly applied towards the synthesis of molecular magnetic materials[3~6]. Copper complexes play an important role in catalyzin… 相似文献
158.
Jean -Paul Malrieu 《Theoretical chemistry accounts》1982,62(2):163-174
Using the canonical problem of N separate electron pairs, theN dependence of approximate multireference CI schemes is analyzed. When the DCI is taken as multireference space, the second order Quasi Degenerate Many Body Perturbation Theory (QD(MB)PT) gives twice the expected correction, while the CIPSI algorithm gives 66% of it, and the MRDCI a vanishing part of it. A modified QDPT effective hamiltonian, and a combination of CIPSI and QDPT algorithms seem to give better trends. 相似文献
159.
InteractionbetweenMetalinMetalloEnzymeandSmallBiologicalMolecules¥HuJie-Han;ShuZan-Yong;TaoLi-Mei;ChengGuo-Bao(DalianInstitut... 相似文献
160.
The interaction of a nonionic polymeric surfactant with an anionic surfactant at the oil–water interface has been studied
by its effects on the droplet size, stability and rheology of emulsions. Oil-in-water (o/w) emulsions were prepared using
isoparaffinic oil and mixtures of a nonionic polymeric surfactant with an anionic surfactant. The macro-molecular surfactant
was a graft copolymer with a backbone of polymethyl methacrylate and grafted polyethylene oxide (a graft copolymer with PEO
chains of MW=750). The anionic surfactant was sodium dodecyl sulfate (SDS). The stabiliza-tion of the emulsion droplets was
found to be different when using one or the other surfactant. The mechanism of stabilization of emulsion droplets by the macro-molecular
surfactant is of the steric type while the stabilization by anionic surfactant is of the electrostatic repulsion type. Emulsions
stabilized with mixtures present both types of stabilization. Other effects on the preparation and stabilization of emulsions
were found to be dependent on properties associated with the surfactant molecular weight such as the Marangoni effect and
Gibbs elasticity. The initial droplet size of the emulsions showed a synergistic effect of the surfactant combination, showing
a minimum for the mixtures compared to the pure components. Emulsion stability also shows a synergistic interaction of both
surfactants. Rheological measurements allow for the estimation of the interparticle interaction when measured as a function
of volume fraction. Most of the effects observed can be attributed to the differences in interfacial tension and droplet radius
produced by both surfactants and their mixtures. The elastic moduli are well explained on the basis of droplet deformation.
Ionic versus steric stabilization produce little difference in the observed rheology, the only important differences observed
concerned the extent of the linear viscoelasticity region.
Received: 22 November 1996 Accepted: 24 March 1997 相似文献