全文获取类型
收费全文 | 5100篇 |
免费 | 108篇 |
国内免费 | 34篇 |
专业分类
化学 | 3506篇 |
晶体学 | 59篇 |
力学 | 73篇 |
数学 | 339篇 |
物理学 | 1265篇 |
出版年
2022年 | 35篇 |
2021年 | 39篇 |
2020年 | 45篇 |
2019年 | 73篇 |
2018年 | 52篇 |
2017年 | 36篇 |
2016年 | 70篇 |
2015年 | 104篇 |
2014年 | 93篇 |
2013年 | 303篇 |
2012年 | 255篇 |
2011年 | 284篇 |
2010年 | 166篇 |
2009年 | 187篇 |
2008年 | 283篇 |
2007年 | 314篇 |
2006年 | 307篇 |
2005年 | 263篇 |
2004年 | 206篇 |
2003年 | 185篇 |
2002年 | 209篇 |
2001年 | 111篇 |
2000年 | 129篇 |
1999年 | 81篇 |
1998年 | 50篇 |
1997年 | 52篇 |
1996年 | 84篇 |
1995年 | 49篇 |
1994年 | 38篇 |
1993年 | 56篇 |
1992年 | 74篇 |
1991年 | 51篇 |
1990年 | 54篇 |
1989年 | 49篇 |
1988年 | 66篇 |
1987年 | 48篇 |
1986年 | 55篇 |
1985年 | 79篇 |
1984年 | 71篇 |
1983年 | 34篇 |
1982年 | 53篇 |
1981年 | 46篇 |
1980年 | 48篇 |
1979年 | 44篇 |
1978年 | 42篇 |
1977年 | 52篇 |
1976年 | 27篇 |
1975年 | 36篇 |
1974年 | 32篇 |
1973年 | 33篇 |
排序方式: 共有5242条查询结果,搜索用时 0 毫秒
71.
A rhodium-catalyzed isomerization of alpha-arylpropargyl alcohols to indanones has been developed under mild conditions. Considering the ease of preparation of these propargyl alcohols (terminal alkynes + aromatic aldehydes), this method provides a new way of constructing indanones with high efficiency. By the mechanistic investigations using deuterium-labeled substrates, it has also been demonstrated that the reaction goes through an unexpected cascade, with a 1,4-hydrogen shift being the turnover-limiting step of the catalytic cycle. 相似文献
72.
73.
Sulphoximides (Ia–Ie) were found to react with dimethyl diazomalonate (DDM) in the presence of a catalytic amount of Cu-salts affording the corresponding oxosulphonium ylides in moderate yields. The reaction did not proceed at all under irradiation of UV light. (?)-Methylphenyloxosulphonium bis(methoxycarbonyl)-methylide ((?)-IIb) was obtained from (+)-(S)-methylphenylsulphoximide ((+)-(S)-Ib) together with (?)-(S)-methyl phenyl sulphoxide ((?)-(S)-IIIb) by this reaction. Hydrolysis of (?)-IIb gave (+)-methylphenyloxosulphonium methoxycarbonylmethylide ((+)-IIf) which was converted to (?)-(S)-IIIb upon treatment with dibenzoylethylene. Stereochemical cycle starting from (+)-(S)-Ib to (?)-(S)-IIIb was established and the absolute configurations of both ylides, (?)-IIb and (+)-IIf were assigned as (R)-configuration. The stereochemical courses, namely from (+)-(S)-Ib or (?)-(S)-IIIb to (?)-(R)-IIb or (+)-(R)-IIf to (?)-(S)-IIIb were determined as retention processes. The optical purities of the oxosulphonium ylides obtained from both reactions, (+)-(S)-Ib→(?)-(R)-IIb and (?)-(S)-IIIb→(?)-(R)-IIb, were almost equal. These results indicate that the mechanism of the reaction of sulphoximides with carbenes (or carbenoids) involves the initial formation of the sulphoxides which react subsequently with carbenes to afford the final products. 相似文献
74.
Yasuhiro Takahashi Yusuke Ozaki Minoru Takase W. R. Krigbaum 《Journal of Polymer Science.Polymer Physics》1993,31(9):1135-1143
Redetermination of the crystal structure of poly(p-benzamide) was made by using newly collected intensity data. The molecular conformation is TCTC, where the internal rotation angles about the N? C bond of the amide group and about the virtual bond of N-phenyl-C are T (trans) and C (cis) conformations, respectively. Two molecular chains pass through a rectangular unit cell with dimension, a = 7.75 Å, b = 5.30 Å, c (fiber axis) = 12.87 Å, and the space group, P212121-D. The reflection observed at the spacing of 010 may be attributed to the reflection due to another crystal polymorph or the diffuse scattering due to disorder. © 1993 John Wiley & Sons, Inc. 相似文献
75.
The reaction of glycine with NBD-F (4-fluoro-7-nitrobenzo-2-oxa-1,3-diazole) is investigated to establish conditions that provide a high formation rate of NBD-glycine and a low hydrolysis rate of the reagent. The reaction rate increases with higher temperature, larger contents of organic solvent and a sodium borate buffer. The use of borate buffer decreases ther ate of hydrolysis of the reagent. For low-molecular-weight amines, condition for a suitable liquid chromatographic postcolumn reactor include a high content of acetonitrile and 0.1 M sodium borate (pH 8.0–8.5). For proteins, separated by molecular-exclusion chromatography, water is needed for sensitive reactions. Suitable postcolumn reactor conditions include borate buffer (pH 7.9) containing 0.1 M potassium chloride, a 0.02% (w/v) NBD-F solution in acetonitrile with reaction at 50°C for about 45 s. The detection limits for human serum albumin, β-lactoglobulin and myoglobin are 6.6 pmol, 8.4 pmol and 11 pmol, respectively. 相似文献
76.
77.
Katsuyuki Ogura Kunio Sanada Kazumasa Takahashi Hirotada Iida 《Tetrahedron letters》1982,23(39):4035-4038
Ethyl 2-acetylalkanoate gave ethyl 2-(methyl- or phenylthio)alkanoate in high yield on treatment wiht CH3SSO2CH3, PhSSO2Ph, or PhSSPh in the presence of small excess of EtONa in EtOH. Application of the present method to synthesis of pellitorine and the queen substance is also described. 相似文献
78.
127I M?ssbauer spectra of good quality were obtained at 20 K using a Zn127mTe source produced by high flux neutron irradiation of 66Zn-126Te at reactor core. The M?ssbauer spectra for KI and some iodine(III) compounds with absorption intensity of about 5% suggest that the 127I M?ssbauer spectroscopy is useful in elucidating the bonding nature of the iodine compounds. Preparative method of the M?ssbauer source and experimental technique are reported in detail. 相似文献
79.
Raman spectra of stilbene mono- and di-negative ions in tetrahydrofuran solution were obtained by Ar+ laser exciting lines. A considerable frequency shift was observed for several vibrations in the successive steps: stilbene → (stilbene)? → (stilbene)2?. The observed shift is discussed in a simple VB scheme, particularly in comparison with the results on anthracene negative ions. The resonance Raman effect was striking for both ions with intensity maxima at the exciting wavelengths close to the absorption maxima. 相似文献
80.
Kazuhiro Matsuo 《Journal of statistical physics》1978,18(6):535-555
A projection operator method is presented, which provides the most efficient way for calculating the stationary behavior of nonlinear Brownian motion. A continued-fraction expansion of the Fourier-Laplace transform of the displacement correlation function or the spectral density is used. This method utilizes a successive optimization procedure on the nonlinear terms and includes the method of statistical linearization as the lowest order approximation. A systematic way to calculate the continued fraction numerically up to sufficient order for convergence is developed, which enables us to obtain the spectral density of a system previously uncomputable.Numerical computations of the spectral density of a nonlinear oscillator with a double-well potential are presented and compared with the results obtained by statistical linearization.This work was supported in part by the National Science Foundation under Grant CHE 75-20624. 相似文献