全文获取类型
收费全文 | 3854篇 |
免费 | 87篇 |
国内免费 | 12篇 |
专业分类
化学 | 2901篇 |
晶体学 | 12篇 |
力学 | 65篇 |
数学 | 530篇 |
物理学 | 445篇 |
出版年
2023年 | 24篇 |
2022年 | 34篇 |
2021年 | 29篇 |
2020年 | 48篇 |
2019年 | 38篇 |
2018年 | 24篇 |
2017年 | 22篇 |
2016年 | 102篇 |
2015年 | 78篇 |
2014年 | 73篇 |
2013年 | 146篇 |
2012年 | 168篇 |
2011年 | 255篇 |
2010年 | 127篇 |
2009年 | 128篇 |
2008年 | 238篇 |
2007年 | 194篇 |
2006年 | 201篇 |
2005年 | 178篇 |
2004年 | 179篇 |
2003年 | 125篇 |
2002年 | 118篇 |
2001年 | 69篇 |
2000年 | 69篇 |
1999年 | 48篇 |
1998年 | 45篇 |
1997年 | 65篇 |
1996年 | 55篇 |
1995年 | 58篇 |
1994年 | 72篇 |
1993年 | 66篇 |
1992年 | 37篇 |
1991年 | 52篇 |
1990年 | 43篇 |
1989年 | 46篇 |
1988年 | 54篇 |
1987年 | 39篇 |
1986年 | 40篇 |
1985年 | 54篇 |
1984年 | 38篇 |
1983年 | 40篇 |
1982年 | 41篇 |
1981年 | 49篇 |
1980年 | 31篇 |
1979年 | 28篇 |
1978年 | 21篇 |
1977年 | 24篇 |
1976年 | 32篇 |
1975年 | 28篇 |
1973年 | 22篇 |
排序方式: 共有3953条查询结果,搜索用时 15 毫秒
101.
Horinek D Serr A Bonthuis DJ Boström M Kunz W Netz RR 《Langmuir : the ACS journal of surfaces and colloids》2008,24(4):1271-1283
Much is written about "hydrophobic forces" that act between solvated molecules and nonpolar interfaces, but it is not always clear what causes these forces and whether they should be labeled as hydrophobic. Hydrophobic effects roughly fall in two classes, those that are influenced by the addition of salt and those that are not. Bubble adsorption and cavitation effects plague experiments and simulations of interacting extended hydrophobic surfaces and lead to a strong, almost irreversible attraction that has little or no dependence on salt type and concentration. In this paper, we are concerned with hydrophobic interactions between single molecules and extended surfaces and try to elucidate the relation to electrostatic and ion-specific effects. For these nanoscopic hydrophobic forces, bubbles and cavitation effects play only a minor role and even if present cause no equilibration problems. In specific, we study the forced desorption of peptides from nonpolar interfaces by means of molecular dynamics simulations and determine the adsorption potential of mean force. The simulation results for peptides compare well with corresponding AFM experiments. An analysis of the various contributions to the total peptide-surface interactions shows that structural effects of water as well as van der Waals interactions between surface and peptide are important. Hofmeister ion effects are studied by separately determining the effective interaction of various ions with hydrophobic surfaces. An extension of the Poisson-Boltzmann equation that includes the ion-specific potential of mean force yields surface potentials, interfacial tensions, and effective interactions between hydrophobic surfaces. There, we also analyze the energetic contributions to the potential of mean force and find that the most important factor determining ion-specific adsorption at hydrophobic surfaces can best be described as surface-modified ion hydration. 相似文献
102.
The rates of the epoxidation reactions of aldehydes, of the aziridination reactions of aldimines, and of the cyclopropanation reactions of α,β-unsaturated ketones with aryl-stabilized dimethylsulfonium ylides have been determined photometrically in dimethyl sulfoxide (DMSO). All of these sulfur ylide-mediated cyclization reactions as well as the addition reactions of stabilized carbanions to N-tosyl-activated aldimines have been shown to follow a second-order rate law, where the rate constants reflect the (initial) CC bond formation between nucleophile and electrophile. The derived second-order rate constants (log k(2)) have been combined with the known nucleophilicity parameters (N, s(N)) of the aryl-stabilized sulfur ylides 4a,b and of the acceptor-substituted carbanions 4c-h to calculate the electrophilicity parameters E of aromatic and aliphatic aldehydes (1a-i), N-acceptor-substituted aromatic aldimines (2a-e), and α,β-unsaturated ketones (3a-f) according to the linear free-energy relationship log k(2) = s(N)(N + E) as defined in J. Am. Chem. Soc.2001, 123, 9500-9512. The data reported in this work provide the first quantitative comparison of the electrophilic reactivities of aldehydes, imines, and simple Michael acceptors in DMSO with carbocations and cationic metal-π complexes within our comprehensive electrophilicity scale. 相似文献
103.
Audorff H Walker R Kador L Schmidt HW 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(45):12722-12728
This paper reports on the synthesis and the thermal and optical properties of photochromic low-molecular-weight compounds, especially with respect to the formation of holographic volume gratings in the pure materials and in binary blends with polystyrene. Its aim is to provide a basic understanding of the holographic response with regard to the molecular structure, and thus to show a way to obtain suitable rewritable materials with high sensitivity for holographic data storage. The photoactive low-molecular-weight compounds consist of a central core with three or four azobenzene-based arms attached through esterification. Four different cores were investigated that influence the glass transition temperature and the glass-forming properties. Additional structural variations were introduced by the polar terminal substituent at the azobenzene chromophore to fine-tune the optical properties and the holographic response. Films of the neat compounds were investigated in holographic experiments, especially with regard to the material sensitivity. In binary blends of the low-molecular-weight compounds with polystyrene, the influence of a polymer matrix on the behavior in holographic experiments was studied. The most promising material combination was also investigated at elevated temperatures, at which the holographic recording sensitivity is even higher. 相似文献
104.
Covalent functionalization of 1,4-benzenedicarboxylate (bdc) with methoxyethoxy groups induces conformational freedom in this molecule. Applying these 2,5-disubstituted bdc derivatives in metal-organic framework synthesis together with 4,4'-bipyridine as coligand yields novel honeycomb-like structures. The cylindrical channels of these materials are populated with flexible groups, which act as molecular gates for guest molecules. This allows highly selective sorption of CO(2) over N(2) and CH(4). 相似文献
105.
Rosenthal D Widmer R Wagner R Gille P Armbrüster M Grin Y Schlögl R Gröning O 《Langmuir : the ACS journal of surfaces and colloids》2012,28(17):6848-6856
The intermetallic PdGa is a highly selective and potent catalyst in the semihydrogenation of acetylene, which is attributed to the surface stability and isolated Pd atom ensembles. In this context PdGa single crystals of form B with (111) orientation were investigated by means of X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), scanning tunneling microscopy (STM), X-ray photoelectron diffraction (XPD), and low-energy electron diffraction (LEED) to study the electronic and geometric properties of this surface. UPS and thermal desorption spectroscopy (TDS) were used to probe the chemisorption behavior of CO. The PdGa(111) surface exhibits a (1 × 1) LEED and a pronounced XPD pattern indicating an unreconstructed bulk-truncated surface. Low-temperature STM reveals a smooth surface with a (1 × 1) unit cell. No segregation occurs, and no impurities are detected by XPS. The electronic structure and the CO adsorption properties reveal PdGa(111) to be a bulk-truncated intermetallic compound with Pd-Ga partial covalent bonding. 相似文献
106.
107.
Roland Jakob‐Roetne Helmut Jacobsen 《Angewandte Chemie (International ed. in English)》2009,48(17):3030-3059
Mind how you go : The current strategies for the development of therapies for Alzheimer's disease are very diverse. Particular attention is given to the search for inhibitors (see picture for two examples) of the proteolytic enzyme β‐ and γ‐secretase, which inhibits the cleavage of the amyloid precursor proteins into amyloid β peptides, from which the disease‐defining deposits of plaque in the brains of Alzheimer's patients originates.
108.
Pratibha Srivastava Inder Pal Singh Kapoor Gurdip Singh Roland Fröhlich 《Journal of Thermal Analysis and Calorimetry》2010,100(1):233-238
Phenylenediammonium dibromide (PDADBr) salts have been prepared and characterized by X-ray crystallography. The thermal decomposition of PDADBr has been studied by thermogravimetry (TG) and differential thermal analysis (DTA). Kinetic parameters have been evaluated using model fitting and isoconversional methods. The thermolytic pathways have also been suggested which involve proton transfer as a primary step to regenerate parent amine and HBr. Interaction between amine and HBr at higher temperature yields gaseous products. 相似文献
109.
Bauer RE Enkelmann V Wiesler UM Berresheim AJ Müllen K 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(17):3858-3864
A series of first-generation polyphenylene dendrimers based on three different cores were prepared by Diels-Alder cycloaddition and their single-crystal structures were determined. Consisting exclusively of interlocked, twisted phenyl rings, these polyphenylene nanostructures have exciting structural and dynamic properties. Single crystals of dendrimers, suitable for X-ray structure analysis, were grown from different solvent mixtures by slow evaporation at room temperature. It should be pointed out that one of the described polyphenylene dendrimers represents up to now the biggest oligophenylene nanostructure from which crystallographic data is available. 相似文献
110.
Roland S. Gohlke Fred W. McLafferty 《Journal of the American Society for Mass Spectrometry》1993,4(5):367-371
Spectroscopy Laboratory, The Dow Chemical Company, Midland, Michigan, USA In December 1955 or thereabouts, the authors coupled a homemade gas chromatograph to a research time-of-flight mass spectrometer constructed by W. C. Wiley, I. H. McLaren, and D. B. Harrington. This unique gas chromatography/mass spectrometry (GC/MS) instrument generated mass spectra at a lo-kHz rate for display on an oscilloscope; eluted gas chromate graphic components, such as methanol, acetone, benzene, toluene, and carbon tetrachloride, could be visually identified immediately from the oscilloscope display. Many years of further research and development in many laboratories worldwide were necessary, however, to make continuous on-line GC/MS the uniquely valuable analytical tool that it is today. 相似文献