全文获取类型
收费全文 | 722篇 |
免费 | 30篇 |
国内免费 | 7篇 |
专业分类
化学 | 540篇 |
晶体学 | 3篇 |
力学 | 35篇 |
数学 | 93篇 |
物理学 | 88篇 |
出版年
2022年 | 16篇 |
2021年 | 14篇 |
2020年 | 16篇 |
2019年 | 17篇 |
2018年 | 8篇 |
2017年 | 14篇 |
2016年 | 28篇 |
2015年 | 22篇 |
2014年 | 17篇 |
2013年 | 43篇 |
2012年 | 33篇 |
2011年 | 56篇 |
2010年 | 34篇 |
2009年 | 38篇 |
2008年 | 48篇 |
2007年 | 41篇 |
2006年 | 41篇 |
2005年 | 23篇 |
2004年 | 26篇 |
2003年 | 25篇 |
2002年 | 13篇 |
2001年 | 9篇 |
2000年 | 11篇 |
1999年 | 11篇 |
1998年 | 8篇 |
1997年 | 14篇 |
1996年 | 7篇 |
1995年 | 4篇 |
1994年 | 5篇 |
1992年 | 8篇 |
1991年 | 3篇 |
1990年 | 3篇 |
1989年 | 7篇 |
1987年 | 3篇 |
1985年 | 8篇 |
1984年 | 5篇 |
1983年 | 3篇 |
1982年 | 3篇 |
1981年 | 7篇 |
1980年 | 6篇 |
1979年 | 10篇 |
1978年 | 6篇 |
1977年 | 3篇 |
1976年 | 3篇 |
1975年 | 4篇 |
1973年 | 3篇 |
1972年 | 3篇 |
1971年 | 5篇 |
1969年 | 3篇 |
1967年 | 3篇 |
排序方式: 共有759条查询结果,搜索用时 0 毫秒
31.
Enolate Stabilization by Anion–π Interactions: Deuterium Exchange in Malonate Dilactones on π‐Acidic Surfaces 下载免费PDF全文
François N. Miros Dr. Yingjie Zhao Dr. Gevorg Sargsyan Marion Pupier Dr. Céline Besnard Dr. César Beuchat Dr. Jiri Mareda Dr. Naomi Sakai Prof. Stefan Matile 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(8):2648-2657
Of central importance in chemistry and biology, enolate chemistry is an attractive topic to elaborate on possible contributions of anion–π interactions to catalysis. To demonstrate the existence of such contributions, experimental evidence for the stabilization of not only anions but also anionic intermediates and transition states on π‐acidic aromatic surfaces is decisive. To tackle this challenge for enolate chemistry with maximal precision and minimal uncertainty, malonate dilactones are covalently positioned on the π‐acidic surface of naphthalenediimides (NDIs). Their presence is directly visible in the upfield shifts of the α‐protons in the 1H NMR spectra. The reactivity of these protons on π‐acidic surfaces is measured by hydrogen–deuterium (H–D) exchange for 11 different examples, excluding controls. The velocity of H–D exchange increases with π acidity (NDI core substituents: SO2R>SOR>H>OR>OR/NR2>SR>NR2). The H–D exchange kinetics vary with the structure of the enolate (malonates>methylmalonates, dilactones>dithiolactones). Moreover, they depend on the distance to the π surface (bridge length: 11–13 atoms). Most importantly, H–D exchange depends strongly on the chirality of the π surface (chiral sulfoxides as core substituents; the crystal structure of the enantiopure (R,R,P)‐macrocycle is reported). For maximal π acidity, transition‐state stabilizations up to ?18.8 kJ mol?1 are obtained for H–D exchange. The Brønsted acidity of the enols increases strongly with π acidity of the aromatic surface, the lowest measured pKa=10.9 calculates to a ΔpKa=?5.5. Corresponding to the deprotonation of arginine residues in neutral water, considered as “impossible” in biology, the found enolate–π interactions are very important. The strong dependence of enolate stabilization on the unprecedented seven‐component π‐acidity gradient over almost 1 eV demonstrates quantitatively that such important anion–π activities can be expected only from strong enough π acids. 相似文献
32.
Dr. Jorge Pascual Dr. Diego Di Girolamo Marion A. Flatken Mahmoud H. Aldamasy Guixiang Li Dr. Meng Li Prof. Antonio Abate 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(12):e202103919
In 2020 dimethyl sulfoxide (DMSO), the ever-present solvent for tin halide perovskites, was identified as an oxidant for SnII. Nonetheless, alternatives are lacking and few efforts have been devoted to replacing it. To understand this trend it is indispensable to learn the importance of DMSO on the development of tin halide perovskites. Its unique properties have allowed processing compact thin-films to be integrated into tin perovskite solar cells. Creative approaches for controlling the perovskite crystallization or increasing its stability to oxidation have been developed relying on DMSO-based inks. However, increasingly sophisticated strategies appear to lead the field to a plateau of power conversion efficiency in the range of 10–15 %. And, while DMSO-based formulations have performed in encouraging means so far, we should also start considering their potential limitations. In this concept article, we discuss the benefits and limitations of DMSO-based tin perovskite processing. 相似文献
33.
Cyclometalated Iridium(III) and Rhodium(III) Complexes Containing Naphthyridine Ligands: Synthesis,Characterization and Biological Studies 下载免费PDF全文
The synthesis, crystal structure, and biological activity of new bis‐cyclometalated compounds [M(ptpy)2(4‐chloro‐2‐methyl‐1,8‐naphthyridine)]PF6 [M = Rh ( 1 ); M = Ir ( 2 ); ptpy = 2‐(p‐tolyl)pyridinato] and [M(ptpy)2(2‐methyl‐1,8‐naphthyridine)]PF6 [M = Rh ( 3 ); M = Ir ( 4 )] are described. The new compounds were prepared by the reaction of [{M(μ‐Cl)(ptpy)2}2] (M = Rh, Ir) with the corresponding naphthyridine ligands. The molecular structures of compounds 1 , 3 , and 4 were confirmed by single‐crystal X‐ray diffraction studies. 相似文献
34.
Cyclometalated Iridium(III) Complexes Containing Semicarbazone Ligands: Synthesis,Characterization, Photophysical and Biological Studies 下载免费PDF全文
Marion Graf Yvonne Gothe Nils Metzler‐Nolte Rafał Czerwieniec Karlheinz Sünkel 《无机化学与普通化学杂志》2015,641(10):1798-1802
The synthesis, crystal structure, photophysical properties, and biological activity of the novel bis‐cyclometalated complexes [Ir(ptpy)2(vnsc)] ( 2 ) and [Ir(ptpy)2(acsc)] ( 3 ) [ptpy = 2‐(p‐tolyl)pyridinato, vnsc = vanillin semicarbazone, acsc = acetone semicarbazone] are described. The new compounds were prepared by the reaction of [{Ir(μ‐Cl)(ptpy)2}2] ( 1 ) with the corresponding semicarbazone ligands under basic conditions. The molecular structure of compound 3 was confirmed by a single‐crystal X‐ray diffraction study. The complex crystallized from chloroform as a mono‐ solvate in the orthorhombic space group Pcab with eight molecules in the unit cell. 相似文献
35.
Prasain JK Patel R Kirk M Wilson L Botting N Darley-Usmar VM Barnes S 《Journal of mass spectrometry : JMS》2003,38(7):764-771
Electrospray ionization combined with tandem mass spectrometry was applied to a study of some representative chlorinated and nitrated isoflavones-potential metabolites of isoflavones in inflammatory cells. Upon collision-induced dissociation of deprotonated [M - H](-) ions of these compounds, a number of structurally characteristic product ions were produced. The product ion analysis of 3'- and 8-chlorodaidzein in the tandom mass spectra led to ready differentiation of these isomers. 3-Nitro derivatives of both genistein and daidzein have product ions due to the losses of HNO(2) and two OH groups. Chlorinated derivatives of isoflavones were detected in cell-based experiments and their structures were proposed by comparing the tandem mass spectra of their product ions with those of standards. This work provides a suitable analytical basis to aid the characterization of chlorinated and nitrated metabolites in studies in vivo and in vitro. 相似文献
36.
37.
38.
39.
40.