全文获取类型
收费全文 | 3960篇 |
免费 | 126篇 |
国内免费 | 34篇 |
专业分类
化学 | 2951篇 |
晶体学 | 33篇 |
力学 | 85篇 |
综合类 | 1篇 |
数学 | 536篇 |
物理学 | 514篇 |
出版年
2023年 | 15篇 |
2022年 | 24篇 |
2021年 | 31篇 |
2020年 | 55篇 |
2019年 | 54篇 |
2018年 | 33篇 |
2017年 | 39篇 |
2016年 | 89篇 |
2015年 | 90篇 |
2014年 | 99篇 |
2013年 | 212篇 |
2012年 | 206篇 |
2011年 | 321篇 |
2010年 | 120篇 |
2009年 | 126篇 |
2008年 | 256篇 |
2007年 | 259篇 |
2006年 | 257篇 |
2005年 | 251篇 |
2004年 | 224篇 |
2003年 | 162篇 |
2002年 | 158篇 |
2001年 | 41篇 |
2000年 | 48篇 |
1999年 | 40篇 |
1998年 | 37篇 |
1997年 | 42篇 |
1996年 | 60篇 |
1995年 | 35篇 |
1994年 | 43篇 |
1993年 | 45篇 |
1992年 | 35篇 |
1991年 | 36篇 |
1990年 | 24篇 |
1989年 | 22篇 |
1988年 | 24篇 |
1987年 | 16篇 |
1986年 | 18篇 |
1985年 | 46篇 |
1984年 | 39篇 |
1983年 | 30篇 |
1982年 | 54篇 |
1981年 | 43篇 |
1980年 | 41篇 |
1979年 | 32篇 |
1978年 | 40篇 |
1977年 | 32篇 |
1976年 | 24篇 |
1975年 | 31篇 |
1974年 | 19篇 |
排序方式: 共有4120条查询结果,搜索用时 7 毫秒
31.
32.
N-Alkoxycarbonyl- and N-carboxamido-oxaziridines are shown to react with aromatic alkenes to give epoxide, aziridine or hydro-oxidation products, in ratios depending on the oxaziridine structure. Chiral oxaziridines can effect epoxidation and hydro-oxidation with promising levels of asymmetric induction. 相似文献
33.
Treatment of [Ti(O-i-Pr)(2)Cl(2)] with NaL(OEt) (L(OEt)(-) = [CpCo[P(O)(OEt)(2)](3)](-), Cp = eta(5)-C(5)H(5)) afforded [L(OEt)Ti(O-i-Pr)(2)Cl] that reacted with HCl in ether to give [L(OEt)TiCl(3)] (1). The average Ti-O and Ti-Cl distances in 1 are 1.975 and 2.293 A, respectively. Reaction of titanyl sulfate with NaL(OEt) in water followed by addition of HBF(4) afforded [L(OEt)TiF(3)] (2), the Ti-O and Ti-F distances of which are 2.020(2) and 1.792(2) A, respectively. The Zr(IV) analogue [L(OEt)ZrF(3)] (3) was prepared similarly from zirconyl nitrate, NaL(Oet), and HBF(4) in water. The Zr-O and average Zr-F distances in 3 are 2.139(2) and 1.938(2) A, respectively. Treatment of 1 with tetrachlorocatechol (H(2)Cl(4)cat) afforded [L(OEt)Ti(Cl(4)cat)Cl] (4). The average Ti-O(P), Ti-O(C), and Ti-Cl distances in 4 are 1.972, 1.926, and 2.334 A, respectively. Hydrolysis of 4 in the presence of Et(3)N yielded the mu-oxo dimer [(L(OEt))(2)Ti(2)(Cl(4)cat)(2)(mu-O)] (5). The average Ti-O(P), Ti-O(C), and Ti-O(Ti) distances in 5 are 2.027, 1.926, and 1.7977(9) A. Treatment of 1 with 1,1'-binaphthol (BINOLH(2)) in the presence of Et(3)N afforded [(L(OEt))(2)Ti(2)(mu-O)(2)(mu-BINOL)] x 2BINOLH(2) (6.2BINOLH(2)). Complex 1 is capable of catalyzing ring opening of epoxides with Me(3)SiN(3) under solvent-free conditions presumably via a Ti-azide intermediate. 相似文献
34.
We show that evaporation from a quasistable molecular cluster may be treated as a kinetic problem involving the stochastically driven escape of a molecule from a potential of mean force. We derive expressions for the decay rate, and a relationship between the depth of the potential and the change in system free energy upon loss of a molecule from the cluster. This establishes a connection between kinetic and thermodynamic treatments of evaporation, but also reveals differences in the prefactor in the rate expression. We perform constant energy molecular dynamics simulations of cluster dynamics to calculate potentials of mean force, friction coefficients and effective temperatures for use in the kinetic analysis, and to compare the results with the directly observed escape rates. We also use the simulations to estimate the escape rates by a probabilistic analysis. It is much more efficient to calculate the decay rate by the methods we have developed than it is to monitor escape directly, making these approaches potentially useful for the assessment of molecular cluster stability. 相似文献
35.
The behaviour of the oxinates of niobium, tantalum and associated metals in the infra-red region was studied and a method developed for the determination of niobium and tantalum. Vanadium caused no interference, but other heavy metals, such as molybdenum, manganese and cobalt, which interfered were removed by preliminary treatment when the method was applied to the determination of niobium and tantalum in steels. 相似文献
36.
The PCILO (perturbative configuration interaction using localized orbitals) method for approximating the electronic structure of molecules has been used with some success for calculating intramolecular interactions in large molecules where intramolecular hydrogen bonding is involved. In this note we show that the PCILO method may be used to calculate the energy of interaction between two water molecules in selected configurations. 相似文献
37.
Barry SJ Carr RM Lane SJ Leavens WJ Monté S Waterhouse I 《Rapid communications in mass spectrometry : RCM》2003,17(6):603-620
A simple method has been developed for the pre-column derivatisation of low molecular weight primary and secondary amines and carboxylic acids using quaternary nitrogen compounds to enhance their detection by liquid chromatography/electrospray ionisation mass spectrometry (LC/ESI-MS). The synthesis of seven novel quaternary nitrogen reagents is described. The derivatives are designed to be relatively small molecules to avoid some of the steric hindrance problems that may be associated with larger derivatisation reagents. The compounds have amine and carboxylic acid functional groups with which to derivatise carboxylic acids and amines, respectively. Two of the compounds contain a bromine atom in order to assess the advantages of a bromine isotope pattern in the mass spectra. This acts as a simple marker for derivatisation and enables data processing by cluster analysis.Activation of the carboxylic acid group was achieved by the use of either 1-chloro-4-methylpyridinium iodide (CMPI) or the more reactive 1-fluoro-4-methylpyridinium p-toluenesulphonate (FMP).1 Using both of these active reagents, the degree of nucleophilic substitution was investigated for the derivatisation of a variety of small molecules. Whilst giving some increase in the ESI-MS response for the derivatised compounds, the FMP itself acted as a derivatising reagent in a competing reaction. In the light of this finding, FMP was reacted with the test compounds separately and gave positive results as a derivatising reagent. Detection of the 'pre-charged' derivatives of amines and carboxylic acids by LC/ESI-MS was investigated with respect to their ESI response and chromatography. 相似文献
38.
Ian R. Gould Jacques E. Moser Bruce Armitage Samir Farid 《Research on Chemical Intermediates》1995,21(7):793-806
The overall efficiencies of photoinduced electron transfer reactions in polar solvents are usually determined by the efficiency with which separated radical ions are formed from the initially formed geminate radical-ion pairs. These separation efficiencies are determined by the competition between retum electron transfer and separation within the geminate pairs. A method is described for determining whether variations in the quantum yields for formation of separated radical ions are due to changes in the reorganization parameters for the return electron transfer reactions, or to other factors. The use of the method is illustrated in studies of the effects of varying steric bulk and molecular size of the donors, and also in studies of the effect of using a charged sensitizer. 相似文献
39.
The influence of aryl substituents in dibenzylidene acetone (dba) ligands, for Pd(0) complexes, has been evaluated for Suzuki-Miyaura cross-coupling reactions. Electron-withdrawing substituents such as NO(2) or CF(3) deactivate the catalyst species whereas strongly donating substituents such as OMe increase catalytic activity over that of unsubstituted dba ligands. [reaction: see text] 相似文献
40.
Gianluca Pozzi Marco Cavazzini Orsolya Holczknecht Silvio Quici Ian Shepperson 《Tetrahedron letters》2004,45(22):4249-4251
A fluorous-tagged TEMPO radical has been prepared and its catalytic activity in the chemoselective oxidation of alcohols to carbonyl compounds has been investigated. The new fluorous radical proved to be an efficient, selective and easily recoverable catalyst, which can be conveniently used in standard organic solvents and then isolated and recycled by fluorous liquid-liquid extraction. 相似文献