全文获取类型
收费全文 | 3924篇 |
免费 | 103篇 |
国内免费 | 23篇 |
专业分类
化学 | 2857篇 |
晶体学 | 43篇 |
力学 | 105篇 |
数学 | 473篇 |
物理学 | 572篇 |
出版年
2023年 | 17篇 |
2022年 | 27篇 |
2021年 | 38篇 |
2020年 | 59篇 |
2019年 | 54篇 |
2018年 | 49篇 |
2017年 | 37篇 |
2016年 | 106篇 |
2015年 | 83篇 |
2014年 | 87篇 |
2013年 | 212篇 |
2012年 | 254篇 |
2011年 | 293篇 |
2010年 | 117篇 |
2009年 | 107篇 |
2008年 | 271篇 |
2007年 | 289篇 |
2006年 | 271篇 |
2005年 | 266篇 |
2004年 | 189篇 |
2003年 | 170篇 |
2002年 | 151篇 |
2001年 | 52篇 |
2000年 | 54篇 |
1999年 | 38篇 |
1998年 | 40篇 |
1997年 | 42篇 |
1996年 | 58篇 |
1995年 | 35篇 |
1994年 | 40篇 |
1993年 | 29篇 |
1992年 | 33篇 |
1991年 | 31篇 |
1990年 | 38篇 |
1989年 | 24篇 |
1988年 | 20篇 |
1987年 | 12篇 |
1986年 | 18篇 |
1985年 | 25篇 |
1984年 | 41篇 |
1983年 | 30篇 |
1982年 | 38篇 |
1981年 | 31篇 |
1980年 | 22篇 |
1979年 | 17篇 |
1978年 | 25篇 |
1977年 | 16篇 |
1976年 | 14篇 |
1974年 | 17篇 |
1973年 | 13篇 |
排序方式: 共有4050条查询结果,搜索用时 0 毫秒
81.
As a consequence of the wide-ranging significance of beta-lactams (e.g., use as drugs and as chiral building blocks), a great deal of effort has been dedicated to the development of methods for their stereoselective synthesis. Although considerable progress has been achieved, nearly all of the approaches that have been described are based on the use of chiral precursors; direct catalytic enantioselective routes to beta-lactams are rare as well as limited in scope. In this communication, we establish that, using a new C2-symmetric planar-chiral bis(azaferrocene) ligand, we can generate beta-lactams with very good enantiomeric excess and cis diastereoselection via catalytic enantioselective Kinugasa reactions (couplings of alkynes with nitrones). Appealing attributes of this process include the ready availability of the starting materials, the functional-group tolerance of the reaction, and the convergency of the approach. 相似文献
82.
We use molecular dynamics simulations to investigate the structure of the hydrated Na-Nafion membranes. The membrane is "prepared" by starting with the Nafion chains placed on a cylinder having the water inside it. Minimizing the energy of the system leads to a filamentary hydrophilic domain whose structure depends on the degree of hydration. At 5 wt % water the system does not have enough water molecules to solvate all the ions that could be formed by the dissociation of the -SO3Na groups. As a result, the -SO3Na groups aggregate with the water to form very small droplets that do not join into a continuous phase. The size of the droplets is between 5 and 8 A. As the amount of water present in the membrane is increased, the membrane swells, and SO3Na has an increasing tendency to dissociate into ions. Furthermore, a transition to a percolating hydrophilic network is observed. In the percolating structure, the water forms irregular curvilinear channels branching in all directions. The typical dimension of the cross section of these channels is about 10-20 A. Calculated neutron scattering from the simulated system is in qualitative agreement with experiment. In all simulations, the pendant sulfonated perfluorovinyl side chains of the Nafion hug the walls of the hydrophilic channel, while the sulfonate groups point toward the center of the hydrophilic phase. The expulsion of the side chains from the hydrophilic domain is favored because it allows better interaction between the water molecules. We have also examined the probability of finding water molecules around the Na+ and the -SO3(-) ions as well as the probability of finding other water molecules next to a given water molecule. These probabilities are much broader than those found in bulk water or for one ion in bulk water (calculated with the potentials used in the present simulation). This is due to the highly inhomogeneous nature of the material contained in the small hydrophilic pores. 相似文献
83.
Gregory J. S. Fowler Wim Crielaardt† Ronald W. Visschers Rienk van Grondelle C. Neil Hunter 《Photochemistry and photobiology》1993,57(1):2-5
The present study describes the construction of a Rhodobacter sphaeroides light-harvesting (LH2) mutant in which the charged residue βSLys23 is changed by site-directed mutagenesis to a Gin residue, and the characterization of the resulting mutant complex by a range of spectroscopic techniques. In the 77 K absorption spectrum of the mutant, the peak equivalent to the 850 nm peak in the wild-type membrane is blue-shifted by approximately 18 nm to 837 nm; except for this blue-shift, the 77 K. fluorescence excitation and emission spectra and the circular dichroism spectrum of the mutant are very similar to the equivalent spectra from the wild-type membranes, suggesting that the mutation βLys23 → Gin probably does not cause any major changes in the conformation or aggregation state of these membranes. Possible causes of the 18 nm blue-shift in the absorption spectrum are discussed. 相似文献
84.
Wu LQ Lee K Wang X English DS Losert W Payne GF 《Langmuir : the ACS journal of surfaces and colloids》2005,21(8):3641-3646
Nanoscale particles offer a variety of interesting properties, and there is growing interest in their assembly into higher ordered structures. We report that the pH-responsive aminopolysaccharide chitosan can mediate the electrodeposition of model nanoparticles. Chitosan is known to electrodeposit at the cathode surface in response to a high localized pH. To demonstrate that chitosan can mediate nanoparticle deposition, we suspended fluorescently labeled latex nanoparticles (100 nm diameter spheres) in a chitosan solution (1%) and performed electrodeposition (0.05 mA/cm2 for several minutes). Results demonstrate that chitosan is required for nanoparticle electrodeposition; chitosan confers spatial selectivity to electrodeposition; and nanoparticles distribute throughout the electrodeposited chitosan film. Additionally, we observed that the deposited films reversibly swell upon rehydration. This work indicates that chitosan provides a simple means to assemble nanoparticles at addressable locations and provides further evidence that stimuli-responsive biological materials may facilitate fabrication at the microscale. 相似文献
85.
Previously a new universal lambda-integration path and associated methodology was developed for the calculation of "exact" surface and interfacial free energies of solids. Such a method is in principle applicable to any intermolecular potential function, including those based on ab initio methods, but in previous work the method was only tested using a relatively simple embedded atom method iron potential. In this present work we apply the new methodology to the more sophisticated and more accurate modified embedded atom method (MEAM) iron potential, where application of other free- energy methods would be extremely difficult due to the complex many-body nature of the potential. We demonstrate that the new technique simplifies the process of obtaining "exact" surface free energies by calculating the complete set of these properties for the low index surface faces of bcc and fcc solid iron structures. By combining these data with further calculations of liquid surface tensions we obtain the first complete set of exact surface free energies for the solid and liquid phases of a realistic MEAM model system. We compare these predictions to various experimental and theoretical results. 相似文献
86.
A polarizable molecular dynamics model for adiabatic electron transfer across the electrode|electrolyte interface is presented. The electronic polarizability of the water and of the metal electrode is accounted for by a dynamical fluctuating charge algorithm, image charges, and the Ewald summation adapted for a conducting interface. The effects of the solvent electronic polarizability are studied by computing the diabatic and adiabatic free energy curves for both polarizable and non-polarizable water models. This represents the first effort to compute the adiabatic free energy curves from simulation for a fully polarizable electrochemical system. 相似文献
87.
The paper analyses the convergence of sequences of control polygons produced by a binary subdivision scheme of the form
相似文献
88.
89.
90.
|