全文获取类型
收费全文 | 875篇 |
免费 | 11篇 |
国内免费 | 3篇 |
专业分类
化学 | 623篇 |
晶体学 | 9篇 |
力学 | 23篇 |
数学 | 86篇 |
物理学 | 148篇 |
出版年
2021年 | 25篇 |
2020年 | 12篇 |
2019年 | 12篇 |
2018年 | 10篇 |
2017年 | 6篇 |
2016年 | 24篇 |
2015年 | 11篇 |
2014年 | 9篇 |
2013年 | 62篇 |
2012年 | 41篇 |
2011年 | 39篇 |
2010年 | 40篇 |
2009年 | 37篇 |
2008年 | 58篇 |
2007年 | 53篇 |
2006年 | 45篇 |
2005年 | 50篇 |
2004年 | 41篇 |
2003年 | 29篇 |
2002年 | 49篇 |
2001年 | 12篇 |
2000年 | 10篇 |
1999年 | 9篇 |
1998年 | 8篇 |
1997年 | 12篇 |
1996年 | 15篇 |
1995年 | 11篇 |
1994年 | 11篇 |
1993年 | 13篇 |
1992年 | 4篇 |
1991年 | 6篇 |
1990年 | 7篇 |
1989年 | 11篇 |
1988年 | 4篇 |
1987年 | 3篇 |
1986年 | 5篇 |
1985年 | 8篇 |
1984年 | 7篇 |
1983年 | 6篇 |
1982年 | 9篇 |
1981年 | 9篇 |
1980年 | 11篇 |
1979年 | 8篇 |
1978年 | 10篇 |
1977年 | 5篇 |
1976年 | 6篇 |
1975年 | 3篇 |
1973年 | 4篇 |
1971年 | 2篇 |
1968年 | 2篇 |
排序方式: 共有889条查询结果,搜索用时 15 毫秒
31.
(R)-Phenylglycinol is shown to be an efficient building block for the synthesis of chiral amino diols in pure diastereomeric form by epoxide ring-opening reactions. The reaction with rac-trans-stilbene oxide gives [HOCH(2)-(R)-PhCH]NH[(S)-PhCH-(R)-PhCHOH] [2(R)-3(R)-4(S)-HNO(2)H(2)] in 32% yield, which can be methylated at nitrogen to give enantiomerically pure [HOCH(2)-(R)-PhCH]NCH(3)[(S)-PhCH-(R)-PhCHOH] [2(R)-3(R)-4(S)-MeNO(2)H(2)]. These amino diol ligands have been used to prepare chiral dioxomolybdenyl complexes of the formula N(R)-2(R)-3(R)-4(S)-(HNO(2))MoO(2) (1) and N(R)-2(R)-3(R)-4(S)-(MeNO(2))MoO(2) (2). The absolute configuration at each stereocenter in the Mo(VI) complexes has been established by (1)H NOESY spectroscopy. The configuration determined for 1 has been confirmed by an X-ray analysis. Crystal data: orthorhombic P2(1)2(1)2(1), a =7.620(3), b = 13.589(2), c = 20.339(3) ?, Z = 4, R = 0.0336. The structure consists of a polymeric chain of N(R)-2(R)-3(R)-4(S)-(HNO(2))MoO(2) molecules connected through unsymmetrical Mo=O --> Mo bridges. Each metal center is coordinated in a distorted octahedral geometry by a cis dioxo unit and by two trans alkoxo atoms. The coordination polyhedron is completed by a nitrogen atom and by a bridging oxo oxygen atom from an adjacent molecule. Compound 2 catalyzes the oxidation of PPh(3) to OPPh(3) by DMSO through a mechanism that involves the intermediacy of a Mo(IV) species. 相似文献
32.
33.
Gabriella Ieronimo Alessandro Mondelli Francesco Tibiletti Angelo Maspero Giovanni Palmisano Simona Galli Stefano Tollari Norberto Masciocchi Kenneth M. Nicholas Silvia Tagliapietra Giancarlo Cravotto Andrea Penoni 《Tetrahedron》2013
The thermal reaction between nitrosoarenes and alkynes under alkylating conditions produces N-alkoxyindoles as the major products in moderate to good yields and excellent regioselectivity. Various electrophiles are used affording different N–O-protected hydroxyindoles in a multi-component fashion. Privileged acetylenic substrates used in reactions with substituted nitrosoarenes are arylalkynes or propiolates. Potentially bioactive compounds and other classes of highly functionalizable indole products were prepared. Reactions between o-carbomethoxy-nitrosoarenes and arylacetylenes provided tricyclic compounds containing an acylaziridine indoline skeleton. 相似文献
34.
Giancarlo De Santis Luigi Fabbrizzi Maurizio Licchelli Piersandro Pallavicini Angelo Perotti Antonio Poggi 《Supramolecular chemistry》2013,25(2):115-125
Abstract The new ferrocene-containing water-soluble ligands 1 and 2 were synthesized and their protonation and complexation properties toward NiII and CuII studied as a function of pH, by means of potentiometric titration experiments. Electrochemical measurements were performed in aqueous solution on pure 1 and 2 and in the presence of NiII and CuII cations, in the pH range 2–12, allowing us to determine the redox potential values relative to the ferrocene oxidation in the free ligands and in their NiII and CuII complexes. 1 and 2 behave as redox switchable ligands, the former enhancing, the latter decreasing its binding ability upon oxidation of the appended ferrocene function. Besides, the CuII complex of ligand 1 and the NiII complex of ligand 2 behave as two-centre two-electron redox systems, the complexed metal cation being subject to further oxidation to MIII. 相似文献
35.
Oriano Francescangeli Bin Yang Emo Chiellini Giancarlo Galli Annino Sante Angeloni Michele Laus 《Liquid crystals》2013,40(4):981-990
Abstract An X-ray study is performed on powder specimens and on stretched oriented fibres of two liquid crystalline polyacrylates containing the azobenzene mesogenic unit with either a 4′-n-pentyloxy (sample 1–4) or 4′-n-hexyloxy (sample 1–5) substituent. The X-ray diffraction patterns of both samples showed the presence of a bilayer smectic C mesophase with the mesogneic groups tilted by an angle β ~ 45° (1–4) or β ~ 38° (1–5) with respect to the layer normal. The electron density profile p(z) along the direction normal to the smectic layers was calculated by Fourier inversion and possible structural models of the smectic mesophase are discussed. A partial interdigitation of the terminal alkyloxy substituents appears to occur. 相似文献
36.
37.
38.
39.
Elena Molteni Giovanni Onida Giancarlo Cappellini 《The European Physical Journal B - Condensed Matter and Complex Systems》2016,89(4):98
We study the electronic properties of the Si(001):Uracil, Si(001):Thymine, andSi(001):5-Fluorouracil systems, focusing on the Si dimer-bridging configuration withadsorption governed by carbonyl groups. While the overall structural and electronicproperties are similar, with small differences due to chemical substitutions, much largereffects on the surface band dispersion and bandgap show up as a function of the molecularorientation with respect to the surface. An off-normal orientation of the molecular planesis favored, showing larger bandgap and lower total energy than the upright position. Wealso analyze the localization of gap-edge occupied and unoccupied surface states. 相似文献
40.