全文获取类型
收费全文 | 4272篇 |
免费 | 175篇 |
国内免费 | 32篇 |
专业分类
化学 | 3220篇 |
晶体学 | 24篇 |
力学 | 116篇 |
数学 | 526篇 |
物理学 | 593篇 |
出版年
2023年 | 38篇 |
2022年 | 56篇 |
2021年 | 79篇 |
2020年 | 100篇 |
2019年 | 102篇 |
2018年 | 71篇 |
2017年 | 57篇 |
2016年 | 138篇 |
2015年 | 121篇 |
2014年 | 152篇 |
2013年 | 227篇 |
2012年 | 299篇 |
2011年 | 366篇 |
2010年 | 162篇 |
2009年 | 131篇 |
2008年 | 322篇 |
2007年 | 315篇 |
2006年 | 306篇 |
2005年 | 253篇 |
2004年 | 216篇 |
2003年 | 192篇 |
2002年 | 155篇 |
2001年 | 34篇 |
2000年 | 34篇 |
1999年 | 37篇 |
1998年 | 36篇 |
1997年 | 41篇 |
1996年 | 56篇 |
1995年 | 31篇 |
1994年 | 28篇 |
1993年 | 24篇 |
1992年 | 21篇 |
1991年 | 25篇 |
1990年 | 25篇 |
1989年 | 13篇 |
1988年 | 12篇 |
1987年 | 12篇 |
1986年 | 8篇 |
1985年 | 22篇 |
1984年 | 27篇 |
1983年 | 11篇 |
1982年 | 14篇 |
1981年 | 13篇 |
1980年 | 18篇 |
1979年 | 10篇 |
1978年 | 16篇 |
1977年 | 12篇 |
1976年 | 13篇 |
1975年 | 8篇 |
1974年 | 10篇 |
排序方式: 共有4479条查询结果,搜索用时 15 毫秒
71.
We present a molecular model for ferrous-ferric electron transfer in an aqueous solution that accounts for electronic polarizability and exhibits spontaneous cation hydrolysis. An extended Lagrangian technique is introduced for carrying out calculations of electron-transfer barriers in polarizable systems. The model predicts that the diabatic barrier to electron transfer increases with increasing pH, due to stabilization of the Fe3+ by fluctuations in the number of hydroxide ions in its first coordination sphere, in much the same way as the barrier would increase with increasing dielectric constant in the Marcus theory. We have also calculated the effect of pH on the potential of mean force between two hydrolyzing ions in aqueous solution. As expected, increasing pH reduces the potential of mean force between the ferrous and ferric ions in the model system. The magnitudes of the predicted increase in diabatic transfer barrier and the predicted decrease in the potential of mean force nearly cancel each other at the canonical transfer distance of 0.55 nm. Even though hydrolysis is allowed in our calculations, the distribution of reorganization energies has only one maximum and is Gaussian to an excellent approximation, giving a harmonic free energy surface in the reorganization energy F(DeltaE) with a single minimum. There is thus a surprising amount of overlap in electron-transfer reorganization energies for Fe(2+)-Fe(H2O)6(3+), Fe(2+)-Fe(OH)(H2O)5(2+), and Fe(2+)-Fe(OH)2(H2O)+ couples, indicating that fluctuations in hydrolysis state can be viewed on a continuum with other solvent contributions to the reorganization energy. There appears to be little justification for thinking of the transfer rate as arising from the contributions of different hydrolysis states. Electronic structure calculations indicate that Fe(H2O)6(2+)-Fe(OH)n(H2O)(6-n)(3-n)+ complexes interacting through H3O2- bridges do not have large electronic couplings. 相似文献
72.
Stasko DJ Perzynski KJ Wasil MA Brodbeck JK Kirschbaum K Kim YW Lind C 《Inorganic chemistry》2004,43(13):3786-3788
The acid H(2)B(12)(OH)(12) can be isolated as a crystalline solid by protonation of the hydroxylated borane anion, B(12)(OH)(12)(2)(-). This acidic compound has low solubility in water, conducts protons in the solid state, and has thermal stability to a temperature of 400 degrees C. The conductivity mechanism is a Grotthuss mechanism with a low activation enthalpy (9-13 kcal/mol). This new acid represents an addition to the class of oxoacids, of which sulfuric and phosphoric acid are the most prominent examples. 相似文献
73.
Density functional theory (PBE and B3LYP) was used to study asymmetric hydrogenations of alkenes catalyzed by an iridium imidazolylidine oxazoline complex. The calculation predicts that the alkene preferentially coordinates to the site trans to the carbene. The coordinated alkene then reacts first with the H2 ligand, then with the hydride to form alkane. Finally, the alkane is released by equilibrating with extrinsic H2 and alkene. Enantioface selectivities for hydrogenations of trisubstituted alkenes seem to be driven primarily by steric interactions with the adamantyl part of the ligand; only the smallest substituents can adopt a site close to it. Application of this theoretical model leads to correct predictions regarding the experimentally observed sense and magnitude of the enantioselectivities. 相似文献
74.
Holliday JD Rodgers SL Willett P Chen MY Mahfouf M Lawson K Mullier G 《Journal of chemical information and computer sciences》2004,44(3):894-902
This paper evaluates the use of the fuzzy k-means clustering method for the clustering of files of 2D chemical structures. Simulated property prediction experiments with the Starlist file of logP values demonstrate that use of the fuzzy k-means method can, in some cases, yield results that are superior to those obtained with the conventional k-means method and with Ward's clustering method. Clustering of several small sets of agrochemical compounds demonstrate the ability of the fuzzy k-means method to highlight multicluster membership and to identify outlier compounds, although the former can be difficult to interpret in some cases. 相似文献
75.
Pd(0) was generated at preselected sites on an electrochemically addressable chip and then utilized to effect a Heck reaction. The Pd(0) was confined to the preselected electrodes with the use of allylmethyl carbonate. Unlike most mediated electrochemical reactions, the electrolysis in this case was not used to convert a stoichiometric process into a catalytic one by recycling the metal. Instead, the unique environment of the chip was used to interfere with a catalytic process to make it stoichiometric. This was done to gain spatial control over the reaction. The development of a strategy for conducting Pd(0)-catalyzed reactions on the chips should greatly expand the synthetic chemistry available for building chip-based libraries. 相似文献
76.
Chiral resolution of arginine (Arg) and Arg derivatives is demonstrated using electrospray ionization-tandem mass spectrometry (ESI-MS). Calcium ion (Ca(II))-mediated trimeric clusters are generated, which incorporate the analyte of interest and an enantiomerically pure reference molecule of similar metal ion affinity. Two methods, one based on the measurement of a competitive-dissociation-based branching ratio (R(chir)) by the kinetic method (KM) and one based on the measurement of a chiral recognition ratio (CR) by a similar method, are compared. Incorporating N-blocked Arg derivatives (Z-Arg and Boc-Arg) as chiral references provides chiral resolution greater than that previously reported for Arg enantiomers. In a reciprocal manner, pure Arg enantiomers can be used as references for discriminating enantiomers of these N-blocked Arg derivatives. Condensed-phase and gas-phase Ca(II) ion affinity relative to Arg is also addressed qualitatively for other acidic, basic, and neutral amino acids. In some cases, when only one offspring ion is observed (insufficient for KM analysis), the CR method can be applied as an alternative to obtain a measurable stereoselectivity value for the system. The results of these experiments demonstrate the applicability of, and the difference between, the KM and the CR method for improved quantitative analysis of enantiomeric excess for Arg. 相似文献
77.
Makoto OzawaTakaaki Taguchi Takayuki ItohYutaka Ebizuka Kevin I Booker-MilburnG.Richard Stephenson Koji Ichinose 《Tetrahedron》2003,59(44):8793-8798
A novel shunt product was isolated from a disruptant of the actVI-ORFA gene involved in the biosynthesis of actinorhodin (ACT) in Streptomyces coelicolor A3(2). Its structure was elucidated as 1,4-naphthoquinone-8-hydroxy-3-[3(S)-acetoxy-butyric acid], (S)-NHAB, based on NMR, MS, and CD spectroscopic data as well as a single crystal X-ray crystallographic analysis. The formation of (S)-NHAB involves a retro-Claisen type C-C bond cleavage of an ACT biosynthetic intermediate. Feeding experiments with [1-13C] and [2-13C] acetates indicated its biosynthetic origin as a single octaketide chain. The relevant gene product, Act-ORFA, which is a functionally unknown protein, is proposed to play a regulatory role related to the multi-enzymatic steps to ACT production, based on the metabolic profile of its disruptant and the wide distribution of actVI-ORFA homologues in the gene clusters for Streptomyces aromatic polyketides. 相似文献
78.
Photocycloadditlon of (+)-isoplperltenone and cyclobutene-1-carboxylic acid gives an adduct which upon reduction with NaCNBH3 followed by thermolysis yields an isomer of isoaristolactone in an overall yield of 26%. 相似文献
79.
Li S Bowerman D Marthandan N Klyza S Luebke KJ Garner HR Kodadek T 《Journal of the American Chemical Society》2004,126(13):4088-4089
We describe a novel photolithographic approach to the synthesis of peptoids (oligo-N-substituted glycines). This strategy enables the construction of a spatially addressable peptoid microarray, thus providing a potentially powerful tool for the discovery of protein ligands. 相似文献
80.
A norm on a group G is a function N mapping G into the set ofnon-negative real numbers such that for each x and y in G, N(xy1) N(x)+N(y) and N(e) = 0, where e is the identity element ofG. It is shown here that if F(X) is the free topological groupon any completely regular Hausdorff space X and H is a subgroupof F(X) generated by a finite subset of X, then any norm onH can be extended to a continuous norm on F(X). 相似文献