全文获取类型
收费全文 | 1516篇 |
免费 | 21篇 |
国内免费 | 13篇 |
专业分类
化学 | 892篇 |
晶体学 | 6篇 |
力学 | 23篇 |
数学 | 308篇 |
物理学 | 321篇 |
出版年
2021年 | 20篇 |
2020年 | 26篇 |
2019年 | 15篇 |
2018年 | 13篇 |
2016年 | 24篇 |
2015年 | 16篇 |
2014年 | 25篇 |
2013年 | 57篇 |
2012年 | 58篇 |
2011年 | 68篇 |
2010年 | 24篇 |
2009年 | 31篇 |
2008年 | 48篇 |
2007年 | 69篇 |
2006年 | 58篇 |
2005年 | 63篇 |
2004年 | 48篇 |
2003年 | 46篇 |
2002年 | 45篇 |
2001年 | 31篇 |
2000年 | 42篇 |
1999年 | 19篇 |
1998年 | 31篇 |
1997年 | 13篇 |
1996年 | 36篇 |
1995年 | 20篇 |
1994年 | 23篇 |
1993年 | 40篇 |
1992年 | 29篇 |
1991年 | 23篇 |
1990年 | 36篇 |
1989年 | 25篇 |
1988年 | 28篇 |
1987年 | 25篇 |
1986年 | 13篇 |
1985年 | 23篇 |
1984年 | 23篇 |
1983年 | 20篇 |
1982年 | 16篇 |
1981年 | 27篇 |
1980年 | 10篇 |
1979年 | 19篇 |
1978年 | 24篇 |
1977年 | 18篇 |
1976年 | 21篇 |
1975年 | 19篇 |
1974年 | 18篇 |
1973年 | 16篇 |
1969年 | 8篇 |
1968年 | 10篇 |
排序方式: 共有1550条查询结果,搜索用时 15 毫秒
121.
Koumi P Green HE Hartley S Jordan D Lahec S Livett RJ Tsang KW Ward DM 《Electrophoresis》2004,25(14):2227-2241
The demand for high-throughput DNA profiling has increased with the introduction of national DNA databases and has led to the development of automated methods of short tandem repeat (STR) profile production; however, a potential bottleneck still exists at the gel electrophoresis stage. Capillary electrophoresis sequencers capable of processing 96 samples with considerably reduced manual intervention are now available. In this paper, we compare the ABI Prism 377 slab-gel sequencer currently used by the Forensic Science Service with three leading capillary array electrophoresis instruments: the ABI Prism 3700, the Amersham MegaBACE 1000 and the 16-capillary ABI Prism 3100. We describe the experiments used to evaluate and validate these platforms for forensic use with the STR multiplex Ampf/STR SGMplus [1, 2], along with comparative data from the ABI Prism 377 sequencer. 相似文献
122.
123.
Solar Hydrogen from an Aqueous,Noble‐Metal‐Free Hybrid System in a Continuous‐Flow Sampling Reaction System 下载免费PDF全文
Dr. Xiaobo Li Dr. Antony J. Ward Prof. Anthony F. Masters Prof. Thomas Maschmeyer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(24):7345-7350
We introduce the visible‐light photocatalytic H2 evolution reaction as catalyzed by a cobaloxime/carbon nitride (C3N4) noble‐metal‐free hybrid photosystem by using a continuous‐flow sampling reaction system. The photocatalytic H2 evolution rate is highly dependent on the structure of C3N4, in which porous C3N4 shows the best activity compared with bulk C3N4 (lamellar) and C3N4 nanosheets. When using porous C3N4, the system is neither affected by the solution pH, nor the C3N4 concentration, nor the structure of the cobaloxime complex. 相似文献
124.
Regiospecific Formation and Unusual Optical Properties of 2,5‐Bis(arylethynyl)rhodacyclopentadienes: A New Class of Luminescent Organometallics 下载免费PDF全文
Dr. Andreas Steffen Dr. Richard M. Ward Dr. Meng Guan Tay Dr. Robert M. Edkins Dr. Fabian Seeler Magda van Leeuwen Dr. Lars‐Olof Pålsson Prof. Dr. Andrew Beeby Dr. Andrei S. Batsanov Prof. Dr. Judith A. K. Howard Prof. Dr. Todd B. Marder 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(13):3652-3666
A series of 2,5‐bis(arylethynyl)rhodacyclopentadienes has been prepared by a rare example of regiospecific reductive coupling of 1,4‐(p‐R‐phenyl)‐1,3‐butadiynes (R?H, Me, OMe, SMe, NMe2, CF3, CO2Me, CN, NO2, ?C?C‐(p‐C6H4?NHex2), ?C?C?(p‐C6H4?CO2Oct)) at [RhX(PMe3)4] ( 1 ) (X=?C?C?SiMe3 ( a ), ?C?C‐(p‐C6H4?NMe2) ( b ), ?C?C?C?C?(p‐C6H4?NPh2) ( c ) or ?C?C?{p‐C6H4‐C?C?(p‐C6H4‐N(C6H13)2)} ( d ) or Me ( e )), giving the 2,5‐bis(arylethynyl) isomer exclusively. The rhodacyclopentadienes bearing a methyl ligand in the equatorial plane (compound 1 e ) have been converted into their chloro analogues by reaction with HCl etherate. The rhodacycles thus obtained are stable to air and moisture in the solid state and the acceptor‐substituted compounds are even stable to air and moisture in solution. The photophysical properties of the rhodacyclopentadienes are highly unusual in that they exhibit, exclusively, fluorescence between 500–800 nm from the S1 state, with quantum yields of Φ=0.01–0.18 and short lifetimes (τ=0.45–8.20 ns). The triplet state formation (ΦISC=0.57 for 2 a ) is exceptionally slow, occurring on the nanosecond timescale. This is unexpected, because the Rh atom should normally facilitate intersystem crossing within femto‐ to picoseconds, leading to phosphorescence from the T1 state. This work therefore highlights that in some transition‐metal complexes, the heavy atom can play a more subtle role in controlling the photophysical behavior than is commonly appreciated. 相似文献
125.
Corrigendum: Combined Two‐Photon Excitation and d→f Energy Transfer in a Water‐Soluble IrIII/EuIII Dyad: Two Luminescence Components from One Molecule for Cellular Imaging 下载免费PDF全文
126.
127.
The synthesis of lairdinol A, a component of the host-selective phytotoxin depsilairdin, was achieved in 12 steps (18% overall yield) without the use of protecting groups starting with the Diels-Alder reaction of (R)-carvone with 3-trimethylsilyloxy-1,3-pentadiene. The key step established the trans ring fusion by preferential epoxidation of a trans-fused enone in an equilibrating mixture of the cis-fused and trans-fused diastereomers (i.e., equivalent to a dynamic kinetic resolution of these isomers). The synthesis confirms the absolute configurations of lairdinol A and its enantiomer, cyperusol C. 相似文献
128.
Jeffery M. Tharp Omer Ad Kazuaki Amikura Fred R. Ward Emma M. Garcia Jamie H. D. Cate Alanna Schepartz Dieter Sll 《Angewandte Chemie (International ed. in English)》2020,59(8):3122-3126
By transplanting identity elements into E. coli tRNAfMet, we have engineered an orthogonal initiator tRNA (itRNATy2) that is a substrate for Methanocaldococcus jannaschii TyrRS. We demonstrate that itRNATy2 can initiate translation in vivo with aromatic non‐canonical amino acids (ncAAs) bearing diverse sidechains. Although the initial system suffered from low yields, deleting redundant copies of tRNAfMet from the genome afforded an E. coli strain in which the efficiency of non‐canonical initiation equals elongation. With this improved system we produced a protein containing two distinct ncAAs at the first and second positions, an initial step towards producing completely unnatural polypeptides in vivo. This work provides a valuable tool to synthetic biology and demonstrates remarkable versatility of the E. coli translational machinery for initiation with ncAAs in vivo. 相似文献
129.
BoRa Lee Anthony C. Willis Jas S. Ward Warren T. Smith Ping Lan Martin G. Banwell 《化学:亚洲杂志》2020,15(19):3059-3081
Syntheses of a range of chemically well‐defined oligopyrrole/benzenoid hybrids are described using tandem Suzuki‐Miyaura cross‐coupling/bromo‐desilyation reaction sequences for linking borylated pyrroles, halogenated pyrroles and/or dibromobenzenes to one another. By such means, including iterative variants, a range of all α‐linked, all β‐linked oligopyrroles as well as certain combinations thereof have been assembled, some of them for the first time. The conductivities of iodine‐treated thin films formed from certain such systems have been determined. 相似文献
130.
Jonathan C. Golec Eve M. Carter John W. Ward William G. Whittingham Luis Simn Robert S. Paton Darren J. Dixon 《Angewandte Chemie (International ed. in English)》2020,59(40):17417-17422
A bifunctional iminophosphorane (BIMP)‐catalysed enantioselective synthesis of α,β‐unsaturated cyclohexenones through a facially selective 1,3‐prototropic shift of β,γ‐unsaturated prochiral isomers, under mild reaction conditions and in short reaction times, on a range of structurally diverse substrates, is reported. α,β‐Unsaturated cyclohexenone products primed for downstream derivatisation were obtained in high yields (up to 99 %) and consistently high enantioselectivity (up to 99 % ee). Computational studies into the reaction mechanism and origins of enantioselectivity, including multivariate linear regression of TS energy, were carried out and the obtained data were found to be in good agreement with experimental findings. 相似文献