全文获取类型
收费全文 | 921篇 |
免费 | 29篇 |
国内免费 | 7篇 |
专业分类
化学 | 675篇 |
晶体学 | 8篇 |
力学 | 20篇 |
数学 | 138篇 |
物理学 | 116篇 |
出版年
2023年 | 6篇 |
2022年 | 8篇 |
2021年 | 13篇 |
2020年 | 18篇 |
2019年 | 13篇 |
2018年 | 12篇 |
2017年 | 14篇 |
2016年 | 14篇 |
2015年 | 19篇 |
2014年 | 24篇 |
2013年 | 57篇 |
2012年 | 70篇 |
2011年 | 61篇 |
2010年 | 38篇 |
2009年 | 12篇 |
2008年 | 47篇 |
2007年 | 58篇 |
2006年 | 50篇 |
2005年 | 42篇 |
2004年 | 46篇 |
2003年 | 47篇 |
2002年 | 31篇 |
2001年 | 11篇 |
2000年 | 13篇 |
1998年 | 5篇 |
1997年 | 10篇 |
1996年 | 12篇 |
1995年 | 13篇 |
1994年 | 12篇 |
1993年 | 4篇 |
1992年 | 11篇 |
1991年 | 11篇 |
1990年 | 8篇 |
1989年 | 6篇 |
1988年 | 4篇 |
1987年 | 7篇 |
1985年 | 4篇 |
1984年 | 9篇 |
1982年 | 7篇 |
1981年 | 7篇 |
1980年 | 6篇 |
1979年 | 5篇 |
1978年 | 13篇 |
1977年 | 8篇 |
1976年 | 12篇 |
1975年 | 9篇 |
1974年 | 7篇 |
1973年 | 8篇 |
1972年 | 6篇 |
1970年 | 7篇 |
排序方式: 共有957条查询结果,搜索用时 15 毫秒
861.
The Diels–Alder cycloaddition reaction has become established as a fundamental approach for the preparation of complex natural products; however, successful application of the intermolecular Diels–Alder cycloaddition reaction to the synthesis of particularly congested scaffolds remains surprisingly problematic. Inspired by the terpenoid spiroketal natural product leonuketal, a challenging telescoped reaction sequence has been realized to access the core [2.2.2]‐bicyclic lactone ring system and its [3.2.1] isomer. Our four‐step, protecting‐group‐free process required detailed investigation to circumvent the problems of adduct fragmentation and intermediate instability. Successful solution of these practical issues, along with unambiguous structural determination of the target structures, provide useful insights that will facilitate future applications of the Diels–Alder cycloaddition reaction to challenging, highly congested molecular scaffolds and ongoing synthetic efforts towards this natural product. 相似文献
862.
Dale PJ Kijlstra J Vincent B 《Langmuir : the ACS journal of surfaces and colloids》2005,21(26):12250-12256
The temperature stability of aqueous dispersions of hydrophobic monodisperse silica particles stabilized with nonionic surfactants has been investigated. Adsorption isotherms in conjunction with surface tension measurements showed that the surfactant formed a monolayer on the surface of the particles, where the adsorbed amount depended on the molecular weight of the ethylene oxide headgroup. The temperature stability of these dispersions has been measured by a standard turbidimetric technique and visual observations in terms of their critical flocculation temperature (CFT). Parameters controlling the CFT of the individual dispersions stabilized with a monolayer of surfactant include the thickness of the steric layer, the particle size, and the volume fraction of the particles. Calculations show that the van der Waals attraction between the particles with adsorbed polymer layers increases as the temperature of the dispersion increases, and this largely accounts for the observed CFT behavior. 相似文献
863.
Fox PA Griffin ST Reichert WM Salter EA Smith AB Tickell MD Wicker BF Cioffi EA Davis JH Rogers RD Wierzbicki A 《Chemical communications (Cambridge, England)》2005,(29):3679-3681
Readily prepared imidazole-based boronium ions form stable, hydrophobic, room-temperature ionic liquids (RTIL) with unique electronic and spectroscopic characteristics. 相似文献
864.
Boone HW Athey PS Mullins MJ Philipp D Muller R Goddard WA 《Journal of the American Chemical Society》2002,124(30):8790-8791
Since the advent of Ziegler-Natta polymerization of ethylene, attempts have been made to extend coordination polymerization to commercially important monomers with polar functionality. In this study we examined the copolymerization of perdeuterated vinyl chloride (VC) and perdeuterated vinyl acetate (VA) with ethylene using a tridentate Fe(II) dichloride pyridine diimine metal catalyst. The resulting ethylene oligomers were examined by GC/MS and 2H NMR spectroscopy. It was shown that VC was inserted once for every approximately 180 ethylene monomers and VA was inserted once for every approximately 350 ethylene monomers. VC and VA behave as comonomers for coordination/insertion polymerizations with ethylene. However, we find that insertion with either monomer leads to termination of the growing chain via beta-elimination processes. The deuterium atoms are exclusively located at the olefin terminus for each of the monomers. 相似文献
865.
We present near-cellular-resolution magnetic resonance (MR) images of an unanesthetized animal, the blowfly Sarcophaga bullata. Immobilized flies were inserted into a home-built gradient probe in a 14.1-T magnet, and images of voxel size (20-40 microm)(3)--comparable to the diameter of many neuronal cell bodies in the fly's brain--were obtained in several hours. Use of applied field gradients on the order of 60 G/cm allowed minimally distorted images to be produced, despite significant susceptibility differences across the specimen. The images we obtained have exceptional contrast-to-noise levels; comparison with histology-based anatomical information shows that the MR microscopy faithfully represents patterns of nervous tissue and allows distinct brain regions to be clearly identified. Even at the highest resolutions we explored, morphological detail was pronounced in the apparent absence of instabilities or movement-related artifacts frequently observed during imaging of live animal specimens. This work demonstrates that the challenges of noninvasive in vivo MR microscopy can be overcome in a system amenable to studies of brain structure and physiology. 相似文献
866.
867.
In this paper we develop a first-order system of conservation laws for finite deformation in solids, describe its characteristic structure, and use this analysis to develop a second-order numerical method for problems involving finite deformation and plasticity. The equations of mass, momentum, and energy conservation in Lagrangian and Eulerian frames of reference are combined with kinetic equations of state for the stress and with caloric equations of state for the internal energy, as well as with auxiliary equations representing equality of mixed partial derivatives of the deformation gradient. Particular attention is paid to the influence of a curl constraint on the deformation gradient, so that the characteristic speeds transform properly between the two frames of reference. Next, we consider models in rate-form for isotropic elastic-plastic materials with work-hardening, and examine the circumstances under which these models lead to hyperbolic systems for the equations of motion. In spite of the fact that these models violate thermodynamic principles in such a way that the acoustic tensor becomes nonsymmetric, we still find that the characteristic speeds are always real for elastic behavior, and essentially always real for plastic response. These results allow us to construct a second-order Godunov method for the computation of three-dimensional displacement in a one-dimensional material viewed in the Lagrangian frame of reference. We also describe a technique for the approximate solution of Riemann problems in order to determine numerical fluxes in this algorithm. Finally, we present numerical examples of the results of the algorithm. 相似文献
868.
869.
Zheng X Aniol K Armstrong DS Averett TD Bertozzi W Binet S Burtin E Busato E Butuceanu C Calarco J Camsonne A Cates GD Chai Z Chen JP Choi S Chudakov E Cusanno F Leo RD Deur A Dieterich S Dutta D Finn JM Frullani S Gao H Gao J Garibaldi F Gilad S Gilman R Gomez J Hansen JO Higinbotham DW Hinton W Horn T De Jager CW Jiang X Kaufman L Kelly J Korsch W Kramer K LeRose J Lhuillier D Liyanage N Margaziotis DJ Marie F Markowitz P McCormick K Meziani ZE Michaels R Moffit B Nanda S Neyret D Phillips SK 《Physical review letters》2004,92(1):012004
We have measured the neutron spin asymmetry A(n)(1) with high precision at three kinematics in the deep inelastic region at x=0.33, 0.47, and 0.60, and Q(2)=2.7, 3.5, and 4.8 (GeV/c)(2), respectively. Our results unambiguously show, for the first time, that A(n)(1) crosses zero around x=0.47 and becomes significantly positive at x=0.60. Combined with the world proton data, polarized quark distributions were extracted. Our results, in general, agree with relativistic constituent quark models and with perturbative quantum chromodynamics (PQCD) analyses based on the earlier data. However they deviate from PQCD predictions based on hadron helicity conservation. 相似文献
870.
Schaldach CM Bourcier WL Paul PH Wilson WD 《Langmuir : the ACS journal of surfaces and colloids》2004,20(24):10744-10750
We have developed a method of calculation of the dielectrophoretic force on a nanoparticle in a fluid environment where variations in the electric field and electric field gradients are on the same nanoscale as the particle. The Boundary Element Dielectrophoretic Force (BEDF) method involves constructing a solvent-accessible or molecular surface surrounding the particle, calculating the normal component of the electric field at the surface boundary elements, and then solving a system of linear equations for the induced surface polarization charge on each element. Different surface elements of the molecule may experience quite different polarizing electric fields, unlike the situation in the point dipole approximation. A single 100-A-radius ring test configuration is employed to facilitate comparison with the well-known point dipole approximation (PDA). We find remarkable agreement between the forces calculated by the BEDF and PDA methods for a 1 A polarizable sphere. However, for larger particles, the differences between the methods become qualitative as well as quantitative; the character of the force changes from attractive at the origin of the ring for a 50-A sphere, to repulsive for a 75-A sphere. Equally dramatic differences are found in a more complex electrical environment involving two sets of 10 rings. 相似文献