全文获取类型
收费全文 | 3037篇 |
免费 | 91篇 |
国内免费 | 4篇 |
专业分类
化学 | 2195篇 |
晶体学 | 6篇 |
力学 | 39篇 |
数学 | 582篇 |
物理学 | 310篇 |
出版年
2021年 | 31篇 |
2020年 | 39篇 |
2019年 | 36篇 |
2018年 | 25篇 |
2016年 | 81篇 |
2015年 | 65篇 |
2014年 | 74篇 |
2013年 | 92篇 |
2012年 | 119篇 |
2011年 | 139篇 |
2010年 | 80篇 |
2009年 | 87篇 |
2008年 | 108篇 |
2007年 | 103篇 |
2006年 | 104篇 |
2005年 | 70篇 |
2004年 | 95篇 |
2003年 | 61篇 |
2002年 | 71篇 |
2001年 | 43篇 |
2000年 | 50篇 |
1999年 | 42篇 |
1998年 | 50篇 |
1997年 | 36篇 |
1996年 | 30篇 |
1995年 | 46篇 |
1994年 | 35篇 |
1993年 | 38篇 |
1992年 | 35篇 |
1991年 | 40篇 |
1990年 | 30篇 |
1989年 | 46篇 |
1988年 | 38篇 |
1987年 | 32篇 |
1986年 | 30篇 |
1985年 | 51篇 |
1984年 | 39篇 |
1983年 | 48篇 |
1982年 | 36篇 |
1981年 | 28篇 |
1980年 | 38篇 |
1979年 | 31篇 |
1978年 | 28篇 |
1977年 | 40篇 |
1976年 | 25篇 |
1975年 | 20篇 |
1973年 | 16篇 |
1971年 | 19篇 |
1934年 | 27篇 |
1933年 | 17篇 |
排序方式: 共有3132条查询结果,搜索用时 0 毫秒
91.
Dieter Seebach Georg Jaeschke Arkadius Pichota Laurent Audergon 《Helvetica chimica acta》1997,80(8):2515-2519
Two simple thiols derived from the parent TADDOL, α,α,α′,α′ tetraphenyl-2,2-dimethyl-1,3-clioxolan-4,5-dimethanol, are used to prepare Cu1 complexes C and D to catalyze (0.05 equiv.) 1,4-additions of Grignard reagents RMgCl to cyclic enones with enantioselectivities which are comparable to or better than previously reported (enantiomer ratios up to 92:8). 相似文献
92.
Similar to classical asphericity shifts, aspherical deformations of the electron density in the atomic core region can result in core asphericity shifts in refinements using a Hansen-Coppens multipolar model (HCM), especially when highly precise experimental datasets with resolutions far beyond sin(θ)/λ ≤ 1.0 Å−1 are employed. These shifts are about two orders of magnitude smaller than their counterparts caused by valence shell deformations, and their underlying deformations are mainly of dipolar character for 1st row atoms. Here, we analyze the resolution dependence of core asphericity shifts in α-boron. Based on theoretical structure factors, an appropriate Extended HCM (EHCM) is developed, which is tested against experimental high-resolution (sin(θ)/λ ≤ 1.6 Å−1) single-crystal diffraction data. Bond length deviations due to core asphericity shifts of α-boron in the order of 4–6·10−4 Å are small but significant at this resolution and can be effectively compensated by an EHCM, although the correlation of the additional model parameters with positional parameters prevented a free refinement of all core model parameters. For high quality, high resolution data, a proper treatment with an EHCM or other equivalent methods is therefore highly recommended. 相似文献
93.
Fernández-Sánchez C Tzanov T Gübitz GM Cavaco-Paulo A 《Bioelectrochemistry (Amsterdam, Netherlands)》2002,58(2):149-156
Six different compounds capable of mediating laccase-catalysed reactions have been tested by cyclic voltammetry. They exhibited quasi-reversible electrodic behaviour with formal redox potentials ranging from 150 to 800 mV (E(0)' vs. SCE). The immersion of a laccase-coated glassy carbon electrode (GCE) in mediator solutions generated large cathodic catalytic currents easily recorded by cyclic voltammetry at low-potential scan rates. This current showed two well-defined pH profiles, which correlated with the variation of the mediator redox potentials at the pH range tested. The relevant effect of temperature on the activity of laccase has been assessed here. Likewise, it was shown that the current record varied with the substrate concentration. This trend fitted Michaelis-Menten kinetics, which allowed us to give an estimation of the affinity of the fungal laccase for the different mediators. 相似文献
94.
95.
96.
Zhenpin Lu Henrik Quanz Julia Ruhl Georg Albrecht Christian Logemann Derck Schlettwein Peter R. Schreiner Hermann A. Wegner 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(13):4303-4307
We present a new concept to control the conformations of molecules in the excited state through harvesting negative hyperconjugation. The strategy was realized with the 2,3,1,4‐benzodiazadiborinane scaffold, which was prepared by a new synthetic procedure. Photochemical studies identified dual light emission, which was assigned to well‐defined conformers. The emission at longer wavelength can be switched off by restricting the rotational degrees of freedom in the solid state as well as by controlling the energy levels of the excited states through adjusting the solvent polarity. 相似文献
97.
Xing Huang Detre Teschner Maria Dimitrakopoulou Alexey Fedorov Benjamin Frank Ralph Kraehnert Frank Rosowski Harry Kaiser Stephan Schunk Christiane Kuretschka Robert Schlgl Marc‐Georg Willinger Annette Trunschke 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(26):8801-8805
The direct conversion of syngas to ethanol, typically using promoted Rh catalysts, is a cornerstone reaction in CO2 utilization and hydrogen storage technologies. A rational catalyst development requires a detailed structural understanding of the activated catalyst and the role of promoters in driving chemoselectivity. Herein, we report a comprehensive atomic‐scale study of metal–promoter interactions in silica‐supported Rh, Rh–Mn, and Rh–Mn–Fe catalysts by aberration‐corrected (AC) TEM. While the catalytic reaction leads to the formation of a Rh carbide phase in the Rh–Mn/SiO2 catalyst, the addition of Fe results in the formation of bimetallic Rh–Fe alloys, which further improves the selectivity and prevents the carbide formation. In all promoted catalysts, Mn is present as an oxide decorating the metal particles. Based on the atomic insight obtained, structural and electronic modifications induced by promoters are revealed and a basis for refined theoretical models is provided. 相似文献
98.
Hans Jagusch Markus Werner Oliver Werz Georg Pohnert 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(49):17805-17809
Arachidonic‐acid‐derived prostaglandins (PGs), specifically PGE2, play a central role in inflammation and numerous immunological reactions. The enzymes of PGE2 biosynthesis are important pharmacological targets for anti‐inflammatory drugs. Besides mammals, certain edible marine algae possess a comprehensive repertoire of bioactive arachidonic‐acid‐derived oxylipins including PGs that may account for food poisoning. Described here is the analysis of PGE2 biosynthesis in the red macroalga Gracilaria vermiculophylla that led to the identification of 15‐hydroperoxy‐PGE2, a novel precursor of PGE2 and 15‐keto‐PGE2. Interestingly, this novel precursor is also produced in human macrophages where it represents a key metabolite in an alternative biosynthetic PGE2 pathway in addition to the well‐established arachidonic acid‐PGG2‐PGH2‐PGE2 route. This alternative pathway of mammalian PGE2 biosynthesis may open novel opportunities to intervene with inflammation‐related diseases. 相似文献
99.
Synthesis and structure‐activity relationship of several aromatic ketone‐based two‐photon initiators
Zhiquan Li Marton Siklos Niklas Pucher Klaus Cicha Aliasghar Ajami Wolfgang Husinsky Arnulf Rosspeintner Eric Vauthey Georg Gescheidt Jürgen Stampfl Robert Liska 《Journal of polymer science. Part A, Polymer chemistry》2011,49(17):3688-3699
Several novel aromatic ketone‐based two‐photon initiators containing triple bonds and dialkylamino groups were synthesized and the structure‐activity relationships were evaluated. Branched alkyl chains were used at the terminal donor groups to improve the solubility in the multifunctional monomers. Because of the long conjugation length and good coplanarity, the evaluated initiators showed large two‐photon cross section values, while their fluorescence lifetimes and quantum yields strongly depend on the solvent polarity. All novel initiators exhibited high activity in terms of two‐photon‐induced microfabrication. This is especially true for fluorenone‐based derivatives, which displayed much broader processing windows than well‐known highly active initiators from the literature and commercially available initiators. While the new photoinitiators gave high reactivity in two‐photon‐induced photopolymerization at concentration as low as 0.1% wt, these compounds are surprisingly stable under one photon condition and nearly no photo initiation activity was found in classical photo DSC experiment. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011 相似文献
100.
Heinz‐Georg Nothofer Andreas Meisel Tzenka Miteva Dieter Neher Michael Forster Masao Oda Günter Lieser Dessislava Sainova Akio Yasuda Donald Lupo Wolfgang Knoll Ullrich Scherf 《Macromolecular Symposia》2000,154(1):139-148
A series of 9,9‐dialkyl‐poly(fluorene‐2,7‐diyl)s containing linear and branched alkyl substituents with a Mn of up to 200000 g/mol has been synthesized. Moreover, some of the polymers were end capped with a suitable hole transport functionality, such as a triphenylamine derivative, to improve their charge transport properties and to control the molecular weight. The thermal alignment of these novel polymers on a rubbed polyimide layer led to highly anisotropic film formation with dichroic ratios (absorption parallel and perpendicular to the rubbing direction) of up to 26 in absorption and 21 in emission. 相似文献