全文获取类型
收费全文 | 25328篇 |
免费 | 600篇 |
国内免费 | 156篇 |
专业分类
化学 | 16852篇 |
晶体学 | 191篇 |
力学 | 644篇 |
综合类 | 1篇 |
数学 | 4373篇 |
物理学 | 4023篇 |
出版年
2021年 | 153篇 |
2020年 | 213篇 |
2019年 | 285篇 |
2018年 | 232篇 |
2017年 | 207篇 |
2016年 | 442篇 |
2015年 | 345篇 |
2014年 | 455篇 |
2013年 | 1324篇 |
2012年 | 1192篇 |
2011年 | 1508篇 |
2010年 | 780篇 |
2009年 | 624篇 |
2008年 | 1365篇 |
2007年 | 1417篇 |
2006年 | 1409篇 |
2005年 | 1411篇 |
2004年 | 1238篇 |
2003年 | 992篇 |
2002年 | 881篇 |
2001年 | 293篇 |
2000年 | 248篇 |
1999年 | 196篇 |
1998年 | 207篇 |
1997年 | 258篇 |
1996年 | 332篇 |
1995年 | 285篇 |
1994年 | 270篇 |
1993年 | 279篇 |
1992年 | 265篇 |
1991年 | 232篇 |
1990年 | 223篇 |
1989年 | 236篇 |
1988年 | 259篇 |
1987年 | 246篇 |
1986年 | 240篇 |
1985年 | 383篇 |
1984年 | 435篇 |
1983年 | 320篇 |
1982年 | 425篇 |
1981年 | 401篇 |
1980年 | 337篇 |
1979年 | 325篇 |
1978年 | 346篇 |
1977年 | 330篇 |
1976年 | 274篇 |
1975年 | 270篇 |
1974年 | 260篇 |
1973年 | 240篇 |
1972年 | 143篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
71.
Adding a Structural Context to the Deprotometalation and Trans‐Metal Trapping Chemistry of Phenyl‐Substituted Benzotriazole 下载免费PDF全文
Dr. M. Ángeles Fuentes Dr. Alan R. Kennedy Prof. Robert E. Mulvey Dr. John A. Parkinson Dr. Toni Rantanen Dr. Stuart D. Robertson Prof. Victor Snieckus 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(42):14812-14822
Organometallic bases are becoming increasingly complex, because mixing components can lead to bases superior to single‐component bases. To better understand this superiority, it is useful to study metalated intermediate structures prior to quenching. This study is on 1‐phenyl‐1H‐benzotriazole, which was previously deprotonated by an in situ ZnCl2 ? TMEDA/LiTMP (TMEDA=N,N,N′,N′‐tetramethylethylenediamine; TMP=2,2,6,6‐tetramethylpiperidide) mixture and then iodinated. Herein, reaction with LiTMP exposes the deficiency of the single‐component base as the crystalline product obtained was [{4‐R‐1‐(2‐lithiophenyl)‐1H‐benzotriazole ? 3THF}2], [R=2‐C6H4(Ph)NLi], in which ring opening of benzotriazole and N2 extrusion had occurred. Supporting lithiation by adding iBu2Al(TMP) induces trans‐metal trapping, in which C?Li bonds transform into C?Al bonds to stabilise the metalated intermediate. X‐ray diffraction studies revealed homodimeric [(4‐R′‐1‐phenyl‐1H‐benzotriazole)2], [R′=(iBu)2Al(μ‐TMP)Li], and its heterodimeric isomer [(4‐R′‐1‐phenyl‐1H‐benzotriazole){2‐R′‐1‐phenyl‐1H‐benzotriazole}], whose structure and slow conformational dynamics were probed by solution NMR spectroscopy. 相似文献
72.
One‐Pot Cannizzaro Cascade Synthesis of ortho‐Fused Cycloocta‐2,5‐dien‐1‐ones from 2‐Bromo(hetero)aryl Aldehydes 下载免费PDF全文
Dr. Laurence Burroughs Lee Eccleshare John Ritchie Omkar Kulkarni Prof. Dr. Barry Lygo Prof. Dr. Simon Woodward Dr. William Lewis 《Angewandte Chemie (International ed. in English)》2015,54(36):10648-10651
An intramolecular Cannizzaro‐type hydride transfer to an in situ prepared allene enables the synthesis of ortho‐fused 4‐substituted cycloocta‐2,5‐dien‐1‐ones with unprecedented technical ease for an eight‐ring carboannulation. Various derivatives could be obtained from commercially available (hetero)aryl aldehydes, trimethylsilylacetylene, and simple propargyl chlorides in good yields. 相似文献
73.
Rebecca A. Green Prof. John F. Hartwig 《Angewandte Chemie (International ed. in English)》2015,54(12):3768-3772
The nickel‐catalyzed amination of aryl chlorides to form primary arylamines occurs with ammonia or ammonium sulfate and a well‐defined single‐component nickel(0) precatalyst containing a Josiphos ligand and an η2‐bound benzonitrile ligand. This system also catalyzes the coupling of aryl chlorides with gaseous amines in the form of their hydrochloride salts. 相似文献
74.
Prof. Dr. Robin B. Bedford John G. Bowen Russell B. Davidson Dr. Mairi F. Haddow Annabelle E. Seymour‐Julen Dr. Hazel A. Sparkes Dr. Ruth L. Webster 《Angewandte Chemie (International ed. in English)》2015,54(22):6591-6594
Palladium(II) acetate is readily converted into [Pd3(μ2‐OH)(OAc)5] ( 1 ) in the presence of water in a range of organic solvents and is also slowly converted in the solid state. Complex 1 can also be formed in nominally anhydrous solvents. Similarly, the analogous alkoxide complexes [Pd3(μ2‐OR)(OAc)5] ( 3 ) are easily formed in solutions of palladium(II) acetate containing a range of alcohols. An examination of a representative Wacker‐type oxidation shows that the Pd‐OH complex 1 and a related Pd‐oxo complex 4 can be excluded as potential catalytic intermediates in the absence of exogenous water. 相似文献
75.
Synthesis of an [(NHC)2Pd(SiMe3)2] Complex and Catalytic cis‐Bis(silyl)ations of Alkynes with Unactivated Disilanes 下载免费PDF全文
Melvyn B. Ansell Dr. Debbie E. Roberts Prof. F. Geoffrey N. Cloke Dr. Oscar Navarro Dr. John Spencer 《Angewandte Chemie (International ed. in English)》2015,54(19):5578-5582
The novel complex cis‐[(ITMe)2Pd(SiMe3)2 (ITMe=1,3,4,5‐tetramethylimidazol‐2‐ylidene) has been synthesized by mild oxidative cleavage of Me3SiSiMe3 using [(ITMe)2Pd0]. The use of this complex as precatalyst for the cis‐bis(silyl)ation of alkynes using unactivated disilanes is reported. 相似文献
76.
Nicholle G. A. Bell Adam A. L. Michalchuk John W. T. Blackburn Dr. Margaret C. Graham Dr. Dušan Uhrín 《Angewandte Chemie (International ed. in English)》2015,54(29):8382-8385
Humic substances, the main component of soil organic matter, could form an integral part of green and sustainable solutions to the soil fertility problem. However, their global‐scale application is hindered from both scientific and regulatory perspectives by the lack of understanding of the molecular make‐up of these chromatographically inseparable mixtures containing thousands of molecules. Here we show how multidimensional NMR spectroscopy of isotopically tagged molecules enables structure characterization of humic compounds. We illustrate this approach by identifying major substitution patterns of phenolic aromatic moieties of a peat soil fulvic acid, an operational fraction of humic substances. Our methodology represents a paradigm shift in the use of NMR active tags in structure determination of small molecules in complex mixtures. Unlike previous tagging methodologies that focused on the signals of the tags, we utilize tags to directly probe the identity of the molecules they are attached to. 相似文献
77.
Zachary D. Miller Ruth Dorel Prof. John Montgomery 《Angewandte Chemie (International ed. in English)》2015,54(31):9088-9091
Methods for the highly stereoselective and regiodivergent hydrosilylation of 1,3‐disubstituted allenes have been developed. The synthesis of E allylsilanes is accomplished with palladium NHC catalysts, and trisubstituted Z alkenylsilanes are accessed with nickel NHC catalysts. Unsymmetrically substituted allenes are well tolerated with nickel catalysis and afford Z alkenylsilanes. Evidence for a plausible mechanism was obtained through an isotopic double‐labeling crossover study. 相似文献
78.
Dr. Colm Browne William J. Ramsay Dr. Tanya K. Ronson John Medley‐Hallam Prof. Jonathan R. Nitschke 《Angewandte Chemie (International ed. in English)》2015,54(38):11122-11127
The subcomponent self‐assembly of a bent dialdehyde ligand and different cationic and anionic templates led to the formation of two new metallosupramolecular architectures: a FeII4L6 molecular rectangle was isolated following reaction of the ligand with iron(II) tetrafluoroborate, and a M5L6 trigonal bipyramidal structure was constructed from either zinc(II) tetrafluoroborate or cadmium(II) trifluoromethanesulfonate. The spatially constrained arrangement of the three equatorial metal ions in the M5L6 structures was found to induce small‐molecule transformations. Atmospheric carbon dioxide was fixed as carbonate and bound to the equatorial metal centers in both the Zn5L6 and Cd5L6 assemblies, and sulfur dioxide was hydrated and bound as the sulfite dianion in the Zn5L6 structure. Subsequent in situ oxidation of the sulfite dianion resulted in a sulfate dianion bound within the supramolecular pocket. 相似文献
79.
Dr. Luke A. Clifton Dr. Stephen A. Holt Dr. Arwel V. Hughes Dr. Emma L. Daulton Dr. Wanatchaporn Arunmanee Dr. Frank Heinrich Dr. Syma Khalid Damien Jefferies Dr. Timothy R. Charlton Dr. John R. P. Webster Dr. Christian J. Kinane Prof. Jeremy H. Lakey 《Angewandte Chemie (International ed. in English)》2015,54(41):11952-11955
Gram‐negative bacteria are an increasingly serious source of antibiotic‐resistant infections, partly owing to their characteristic protective envelope. This complex, 20 nm thick barrier includes a highly impermeable, asymmetric bilayer outer membrane (OM), which plays a pivotal role in resisting antibacterial chemotherapy. Nevertheless, the OM molecular structure and its dynamics are poorly understood because the structure is difficult to recreate or study in vitro. The successful formation and characterization of a fully asymmetric model envelope using Langmuir–Blodgett and Langmuir–Schaefer methods is now reported. Neutron reflectivity and isotopic labeling confirmed the expected structure and asymmetry and showed that experiments with antibacterial proteins reproduced published in vivo behavior. By closely recreating natural OM behavior, this model provides a much needed robust system for antibiotic development. 相似文献
80.
Tandem Chemoselective Suzuki–Miyaura Cross‐Coupling Enabled by Nucleophile Speciation Control 下载免费PDF全文
Ciaran P. Seath James W. B. Fyfe John J. Molloy Dr. Allan J. B. Watson 《Angewandte Chemie (International ed. in English)》2015,54(34):9976-9979
Control of boronic acid speciation is presented as a strategy to achieve nucleophile chemoselectivity in the Suzuki–Miyaura reaction. Combined with simultaneous control of oxidative addition and transmetalation, this enables chemoselective formation of two C? C bonds in a single operation, providing a method for the rapid preparation of highly functionalized carbogenic frameworks. 相似文献