全文获取类型
收费全文 | 60141篇 |
免费 | 20990篇 |
国内免费 | 2173篇 |
专业分类
化学 | 67087篇 |
晶体学 | 231篇 |
力学 | 3075篇 |
综合类 | 105篇 |
数学 | 4444篇 |
物理学 | 8362篇 |
出版年
2024年 | 425篇 |
2023年 | 4316篇 |
2022年 | 2060篇 |
2021年 | 3147篇 |
2020年 | 5265篇 |
2019年 | 3016篇 |
2018年 | 2861篇 |
2017年 | 1179篇 |
2016年 | 6345篇 |
2015年 | 6305篇 |
2014年 | 5879篇 |
2013年 | 6350篇 |
2012年 | 4735篇 |
2011年 | 2515篇 |
2010年 | 4411篇 |
2009年 | 4299篇 |
2008年 | 2087篇 |
2007年 | 1751篇 |
2006年 | 1032篇 |
2005年 | 916篇 |
2004年 | 658篇 |
2003年 | 558篇 |
2002年 | 542篇 |
2001年 | 439篇 |
2000年 | 376篇 |
1999年 | 453篇 |
1998年 | 373篇 |
1997年 | 419篇 |
1996年 | 399篇 |
1995年 | 416篇 |
1994年 | 312篇 |
1993年 | 413篇 |
1992年 | 261篇 |
1991年 | 206篇 |
1990年 | 216篇 |
1989年 | 189篇 |
1988年 | 192篇 |
1980年 | 204篇 |
1979年 | 187篇 |
1978年 | 189篇 |
1977年 | 312篇 |
1976年 | 361篇 |
1975年 | 456篇 |
1974年 | 471篇 |
1973年 | 285篇 |
1972年 | 369篇 |
1971年 | 355篇 |
1970年 | 541篇 |
1969年 | 413篇 |
1968年 | 456篇 |
排序方式: 共有10000条查询结果,搜索用时 11 毫秒
911.
912.
Zhenhui Qi Dr. Changzhu Wu Dr. Paula Malo de Molina Han Sun Andrea Schulz Prof. Christian Griesinger Prof. Michael Gradzielski Prof. Rainer Haag Prof. Marion B. Ansorge‐Schumacher Prof. Christoph A. Schalley 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(31):10150-10159
A new and versatile, crown ether appended, chiral supergelator has been designed and synthesized based on the bis‐urea motif. The introduction of a stereogenic center improved its gelation ability significantly relative to its achiral analogue. This low‐molecular‐weight gelator forms supramolecular gels in a variety of organic solvents. It is sensitive to multiple chemical stimuli and the sol–gel phase transitions can be reversibly triggered by host–guest interactions. The gel can be used to trap enzymes and release them on demand by chemical stimuli. It stabilizes the microparticles in Pickering emulsions so that enzyme‐catalyzed organic reactions can take place in the polar phase inside the microparticles, the organic reactants diffusing through the biphasic interface from the surrounding organic phase. Because of the higher interface area between the organic and polar phases, enzyme activity is enhanced in comparison with simple biphasic systems. 相似文献
913.
914.
Gadolinium‐Decorated Silica Microspheres as Redox‐Responsive MRI Probes for Applications in Cell Therapy Follow‐Up 下载免费PDF全文
Dr. Monica Muñoz Úbeda Dr. Fabio Carniato Dr. Valeria Catanzaro Sergio Padovan Dr. Cristina Grange Dr. Stefano Porta Dr. Carla Carrera Prof. Lorenzo Tei Dr. Giuseppe Digilio 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(23):7716-7720
The redox microenvironment within a cell graft can be considered as an indicator to assess whether the graft is metabolically active or hypoxic. We present a redox‐responsive MRI probe based on porous silica microparticles whose surface has been decorated with a Gd‐chelate through a disulphide bridge. Such microparticles are designed to be interspersed with therapeutic cells within a biocompatible hydrogel. The onset of reducing conditions within the hydrogel is paralleled by an increased clearance of Gd, that can be detected by MRI. 相似文献
915.
Synthesis and Rearrangement of P‐Nitroxyl‐Substituted PIII and PV Phosphanes: A Combined Experimental and Theoretical Case Study 下载免费PDF全文
Tobias Heurich Dr. Zheng‐Wang Qu Dr. Senada Nožinović Dr. Gregor Schnakenburg Dr. Hideto Matsuoka Prof. Dr. Stefan Grimme Prof. Dr. Olav Schiemann Prof. Dr. Rainer Streubel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(29):10102-10110
Low‐temperature generation of P‐nitroxyl phosphane 2 (Ph2POTEMP), which was obtained by the reaction of Ph2PH ( 1 ) with two equivalents of TEMPO, is presented. Upon warming, phosphane 2 decomposed to give P‐nitroxyl phosphane P‐oxide 3 (Ph2P(O)OTEMP) as one of the final products. This facile synthetic protocol also enabled access to P‐sulfide and P‐borane derivatives 7 and 13 , respectively, by using Ph2P(S)H ( 6 ) or Ph2P(BH3)H ( 11 ) and TEMPO. Phosphane sulfide 7 revealed a rearrangement to phosphane oxide 8 (Ph2P(O)STEMP) in CDCl3 at ambient temperature, whereas in THF, thermal decomposition of sulfide 7 yielded salt 10 ([TEMP‐H2][Ph2P(S)O]). As well as EPR and detailed NMR kinetic studies, indepth theoretical studies provided an insight into the reaction pathways and spin‐density distributions of the reactive intermediates. 相似文献
916.
Reactivity of [M2(μ‐Cl)2(cod)2] (M=Ir,Rh) and [Ru(Cl)2(cod)(CH3CN)2] with Na[H2B(bt)2]: Formation of Agostic versus Borate Complexes 下载免费PDF全文
K. Bakthavachalam K. Yuvaraj Mohammad Zafar Prof. Dr. Sundargopal Ghosh 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(48):17291-17297
Treatment of [M2(μ‐Cl)2(cod)2] (M=Ir and Rh) with Na[H2B(bt)2] (cod=1,5‐cyclooctadiene and bt=2‐mercaptobenzothiazolyl) at low temperature led to the formation of dimetallaheterocycles [(Mcod)2(bt)2], 1 and 2 ( 1 : M=Ir and 2 : M=Rh) and a borate complex [Rh(cod){κ2‐S,S′‐H2B(bt)2}], 3 . Compounds 1 and 2 are structurally characterized metal analogues of 1,5‐cyclooctadiene. Metal–metal bond distances of 3.6195(9) Å in 1 and 3.6749(9) Å in 2 are too long to consider as bonding. In an attempt to generate the Ru analogue of 1 and 2 , that is [(Rucod)2(bt)2], we have carried out the reaction of [Ru(Cl)2(cod)(CH3CN)2] with Na[H2B(bt)2]. Interestingly, the reaction yielded agostic complexes [Ru(cod)L{κ3‐H,S,S′‐H2B(bt)2}], 4 and 5 ( 4 : L=Cl; 5 : L=C7H4NS2). One of the key differences between 4 and 5 is the presence of different ancillary ligands at the metal center. The natural bond orbital (NBO) analysis of 1 and 2 shows that there is four lone pairs of electrons on each metal center with a significant amount of d character. Furthermore, the electronic structures and the bonding of these complexes have been established on the ground of quantum‐chemical calculations. All of the new compounds were characterized by IR, 1H, 11B, 13C NMR spectroscopy, and X‐ray crystallographic analysis. 相似文献
917.
Dr. Bernd M. Schmidt Dr. Takafumi Osuga Dr. Tomohisa Sawada Dr. Manabu Hoshino Prof. Dr. Makoto Fujita 《Angewandte Chemie (International ed. in English)》2016,55(4):1561-1564
Self‐assembled coordination cages can be employed as a molecular press, where the bowl‐shaped guest corannulene (C20H10) is significantly flattened upon inclusion within the hydrophobic cavity. This is demonstrated by the pairwise inclusion of corannulene with naphthalene diimide as well as by the dimer inclusion of bromocorannulene inside the box‐like host. The compressed corannulene structures are unambiguously revealed by single‐crystal X‐ray analysis. 相似文献
918.
919.
New Experimental Insight into the Nature of Metal−Metal Bonds in Digallium Compounds: J Coupling between Quadrupolar Nuclei 下载免费PDF全文
Dr. Libor Kobera Scott A. Southern Dr. Gyandshwar Kumar Rao Prof. Dr. Darrin S. Richeson Prof. Dr. David L. Bryce 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(28):9565-9573
Multiple bonding between atoms is of ongoing fundamental and applied interest. Here, we report a multinuclear (1H, 13C, and 71Ga) solid‐state magnetic resonance spectroscopic study of digallium compounds which have been proposed, albeit somewhat controversially, to contain single, double, and triple Ga?Ga bonds. Of particular relevance to the nature of these bonds, we have carried out two‐dimensional 71Ga J/D‐resolved NMR experiments which provide a direct measurement of J(71Ga,71Ga) spin–spin coupling constants across the gallium?gallium bonds. When placed in the context of clear‐cut experimental data for analogous singly, doubly, and triply bonded carbon spin pairs or boron spin pairs, the 71Ga NMR data clearly support the notion of a different bonding paradigm in the gallium systems. Our findings are consistent with an increasing role across the purported gallane–gallene–gallyne series for classical and/or slipped π‐type bonding orbitals. 相似文献
920.
Effect of Headgroups on Small‐Ion Permeability across Archaea‐Inspired Tetraether Lipid Membranes 下载免费PDF全文
Takaoki Koyanagi Dr. Geoffray Leriche Alvin Yep David Onofrei Prof. Gregory P. Holland Prof. Michael Mayer Prof. Jerry Yang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(24):8074-8077
This paper examines the effects of four different polar headgroups on small‐ion membrane permeability from liposomes comprised of Archaea‐inspired glycerolmonoalkyl glycerol tetraether (GMGT) lipids. We found that the membrane‐leakage rate across GMGT lipid membranes varied by a factor of ≤1.6 as a function of headgroup structure. However, the leakage rates of small ions across membranes comprised of commercial bilayer‐forming 1‐palmitoyl‐2‐oleoyl‐sn‐glycerol (PO) lipids varied by as much as 32‐fold within the same series of headgroups. These results demonstrate that membrane leakage from GMGT lipids is less influenced by headgroup structure, making it possible to tailor the structure of the polar headgroups on GMGT lipids while retaining predictable leakage properties of membranes comprised of these tethered lipids. 相似文献