全文获取类型
收费全文 | 469篇 |
免费 | 28篇 |
专业分类
化学 | 305篇 |
晶体学 | 1篇 |
力学 | 21篇 |
数学 | 66篇 |
物理学 | 104篇 |
出版年
2023年 | 5篇 |
2022年 | 13篇 |
2021年 | 14篇 |
2020年 | 21篇 |
2019年 | 7篇 |
2018年 | 18篇 |
2017年 | 11篇 |
2016年 | 19篇 |
2015年 | 27篇 |
2014年 | 27篇 |
2013年 | 26篇 |
2012年 | 49篇 |
2011年 | 47篇 |
2010年 | 24篇 |
2009年 | 18篇 |
2008年 | 28篇 |
2007年 | 30篇 |
2006年 | 25篇 |
2005年 | 22篇 |
2004年 | 14篇 |
2003年 | 16篇 |
2002年 | 11篇 |
2001年 | 1篇 |
1999年 | 1篇 |
1998年 | 1篇 |
1996年 | 2篇 |
1995年 | 3篇 |
1994年 | 3篇 |
1992年 | 2篇 |
1989年 | 1篇 |
1988年 | 1篇 |
1987年 | 1篇 |
1984年 | 1篇 |
1982年 | 2篇 |
1980年 | 2篇 |
1979年 | 1篇 |
1977年 | 1篇 |
1976年 | 2篇 |
排序方式: 共有497条查询结果,搜索用时 15 毫秒
91.
Gunnlaugsson T Brougham DF Fanning AM Nieuwenhuyzen M O'Brien JE Viguier R 《Organic letters》2004,6(26):4805-4808
[reaction: see text] The macrocyclic cyclen conjugates 1-4 were synthesized with the aim of forming lanthanide ion-based macrocyclic conjugates possessing deep cavities, formed upon complexation to various lanthanide ions. These complexes all possess metal-bound water molecules, where the pKa of the water molecules depends on the nature of the cavity. 相似文献
92.
Richeter S Jeandon C Kyritsakas N Ruppert R Callot HJ 《The Journal of organic chemistry》2003,68(24):9200-9208
We describe the preparation of six diketones based on the frameworks of five bis-naphthoporphyrins and one perinaphthoporphyrin. All diketones derive from meso-tetraarylporphyrins having incorporated two carbonyl groups, each one connected to one beta-pyrrole carbon and one ortho carbon atom from a meso-aryl group. These compounds were all produced in good yield by intramolecular Friedel-Crafts acylation, either from porphyrins meso-substituted by o-carboxyphenyl or o,o'-dicarboxyphenyl substituents or from porphyrins bearing carboxy groups attached to the pyrrolic beta-positions. Although the former reaction does not show significant regioselectivity when run on nickel complexes, the opposite is true for the corresponding free bases. All diketones show a spectacular bathochromic shift of the UV-vis absorption, the longest wavelength bands absorbing in the 700-825 nm range. Two compounds were structurally characterized by X-ray diffraction. In the case of the diketone, whose carbonyl groups are attached to vicinal pyrrolic beta-positions, a significant intermolecular interaction between the two carbonyl groups and an aromatic hydrogen atom was detected. 相似文献
93.
94.
95.
Nicolas Gigant Laëtitia Chausset-Boissarie Romain Rey-Rodriguez Isabelle Gillaizeau 《Comptes Rendus Chimie》2013,16(4):358-362
Direct C(3) alkenylation of non-aromatic enamides through palladium(II)-catalyzed Fujiwara–Moritani cross-coupling was developed. The reaction scope includes a range of cyclic enamides as well as activated alkenes. The utility of this methodology is illustrated by the synthesis of octa- or tetrahydroquinoline cores obtained from conjugated enamides via Diels–Alder cycloaddition. 相似文献
96.
97.
Influence of the particle size of the MgCl2 support on the performance of Ziegler catalysts in the polymerization of ethylene to ultra‐high molecular weight polyethylene and the resulting polymer properties 下载免费PDF全文
An Philippaerts Richard Ensinck Nicolas Baulu Astrid Cordier Kersten Woike Romain Berthoud Gert De Cremer John R. Severn 《Journal of polymer science. Part A, Polymer chemistry》2017,55(16):2679-2690
A highly systematic size series of Ziegler catalysts with similar porosities and surface textures are synthesized by varying the stirring speed during the MgCl2 support synthesis. Besides the mean particle size, the only substantial difference observed between the various catalysts is the size and number of nodules per particle. Varying the mean diameter of the catalyst particles between 1.5 and 11.9 µm, leads to a pronounced impact on the activity in ultra‐high molecular weight polyethylene (UHMWPE) polymerization, while the Mw capabilities are only affected to a limited extend. In addition, it is observed that both the Mws as the polymer bulk density (BD) increases during the course of the polymerization. This particularity allows to optimize the Mw and/or BD at a set polymer size, by tuning the catalyst particle size. This is particularly interesting in UHMWPE production, as control of the morphological and structural properties of the UHMWPE reactor powders are critical for efficient processing as well as the performance of the final product. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2679–2690 相似文献
98.
Cassandre Piriou Lucas Viers Romain Lucas Fabien Bouzat Hatim Laadoua Yves Champavier Sylvie Foucaud Cristina Coelho Florence Babonneau 《应用有机金属化学》2018,32(9)
A hyperbranched polymer, a precursor of silicon carbide (SiC), was successfully synthesized using a hydrosilylation reaction with Karstedt's catalyst. This reaction was optimized with the use of a rheometer coupled with an infrared spectrometer. The polymeric precursor was characterized using NMR and Fourier transform infrared spectroscopies, and dynamic rheology. The polymerization reaction was followed in situ by combined rheological and infrared measurements, indicating a gel‐like behaviour for alkene conversions higher than 0.55. Overall second‐order kinetics was determined for the hydrosilylation reaction. Pyrolysis at 1400 °C led to porous materials with β‐SiC and free carbon. 相似文献
99.
Using CrCl2 in THF at room temperature, trichloromethyl carbinols and trichloromethylalkanes are readily transformed to the highly reactive α-chlorocarbenes, carbynes and α-chloro-α-chromium(III) vinylidene carbenoids. A mechanistic study is carried out to determine the nature of the intermediates. 相似文献
100.
A small library of squamocin analogues has been prepared and screened biologically (cytotoxicity, inhibition of mitochondrial complex I and complex III). To centre diversity on a crucial part of the molecule (i.e., the α,β-unsaturated lactone), an original and reliable lactone opening reaction has been discovered and exploited among other efficient reactions. 相似文献