全文获取类型
收费全文 | 5749篇 |
免费 | 152篇 |
国内免费 | 42篇 |
专业分类
化学 | 4279篇 |
晶体学 | 34篇 |
力学 | 158篇 |
数学 | 639篇 |
物理学 | 833篇 |
出版年
2022年 | 41篇 |
2021年 | 73篇 |
2020年 | 85篇 |
2019年 | 75篇 |
2018年 | 55篇 |
2017年 | 54篇 |
2016年 | 106篇 |
2015年 | 96篇 |
2014年 | 99篇 |
2013年 | 231篇 |
2012年 | 358篇 |
2011年 | 436篇 |
2010年 | 205篇 |
2009年 | 166篇 |
2008年 | 364篇 |
2007年 | 352篇 |
2006年 | 384篇 |
2005年 | 402篇 |
2004年 | 301篇 |
2003年 | 248篇 |
2002年 | 263篇 |
2001年 | 88篇 |
2000年 | 97篇 |
1999年 | 65篇 |
1998年 | 64篇 |
1997年 | 53篇 |
1996年 | 94篇 |
1995年 | 70篇 |
1994年 | 56篇 |
1993年 | 45篇 |
1992年 | 43篇 |
1991年 | 46篇 |
1990年 | 29篇 |
1989年 | 29篇 |
1988年 | 28篇 |
1987年 | 29篇 |
1986年 | 23篇 |
1985年 | 42篇 |
1984年 | 46篇 |
1983年 | 39篇 |
1982年 | 36篇 |
1981年 | 48篇 |
1980年 | 43篇 |
1979年 | 24篇 |
1978年 | 47篇 |
1977年 | 30篇 |
1976年 | 34篇 |
1975年 | 43篇 |
1974年 | 31篇 |
1973年 | 31篇 |
排序方式: 共有5943条查询结果,搜索用时 15 毫秒
951.
Daniel J. Scott Dr. Nicholas A. Phillips Joshua S. Sapsford Arron C. Deacy Dr. Matthew J. Fuchter Dr. Andrew E. Ashley 《Angewandte Chemie (International ed. in English)》2016,55(47):14738-14742
Despite the rapid development of frustrated Lewis pair (FLP) chemistry over the last ten years, its application in catalytic hydrogenations remains dependent on a narrow family of structurally similar early main‐group Lewis acids (LAs), inevitably placing limitations on reactivity, sensitivity and substrate scope. Herein we describe the FLP‐mediated H2 activation and catalytic hydrogenation activity of the alternative LA iPr3SnOTf, which acts as a surrogate for the trialkylstannylium ion iPr3Sn+, and is rapidly and easily prepared from simple, inexpensive starting materials. This highly thermally robust LA is found to be competent in the hydrogenation of a number of different unsaturated functional groups (which is unique to date for main‐group FLP LAs not based on boron), and also displays a remarkable tolerance to moisture. 相似文献
952.
This paper describes our synthesis of the A-E subunit of gambieric acid (GA) in addition to the synthesis of the A-ring and the C-E tricycle. The use of an enol ether-olefin RCM strategy to couple the A and C-E subunits and, in the process, generate the B-ring is noteworthy. 相似文献
953.
954.
955.
We report the microfluidic fabrication of robust and fluid tethered bilayer arrays within a poly(dimethylsiloxane) (PDMS) chip, and demonstrate its addressability and biosensing by incorporating the GM1 receptor into the bilayer framework for detection of cholera toxin. Rapid optimization of the experimental conditions is achieved by using nanoglassified surfaces in combination with surface plasmon resonance. The ultrathin glassy film on gold mimics glass surfaces employed in microfluidics, allowing real-time monitoring of multiple assembly steps and therefore permitting rapid prototyping of microfluidic arrays. The tethered bilayer array utilizes a covalently immobilized biotinylated protein for generation of well-defined capture zones where a streptavidin link is employed for the immobilization of biotinylated vesicles. Fusion of captured vesicles is accomplished using a concentrated PEG solution, and the lateral diffusion of the tethered bilayer membrane is characterized by fluorescence recovery after photobleaching methods. The tethered membrane arrays demonstrate marked stability and high mobility, which provide an ideal host environment for membrane-associated proteins and open new avenues for high-throughput analysis of these proteins. 相似文献
956.
957.
Phase equilibria of binary mixtures of liquid crystal and multiarm star acrylate derivatives have been established as a function of the number of acrylate arms by means of cloud point determination. Equilibrium phase diagrams of liquid crystal/multiarm acrylate derivatives have been calculated self-consistently in the framework of combined Flory-Huggins free energy of liquid-liquid demixing and Maier-Saupe free energy of nematic ordering. It was found experimentally that the phase diagram of the branched/star molecule/solvent shifts to elevated temperatures with an increasing number of acrylate arms. This movement of the coexistence line is attributed to the architectural effect contributing to the athermal entropic part of the chi interaction parameter. The present self-consistent solution has been tested satisfactorily with the observed phase diagrams of liquid crystal/acrylate systems. 相似文献
958.
Crystal polymorphism of protein GB1 examined by solid-state NMR spectroscopy and X-ray diffraction 总被引:1,自引:0,他引:1
Schmidt HL Sperling LJ Gao YG Wylie BJ Boettcher JM Wilson SR Rienstra CM 《The journal of physical chemistry. B》2007,111(51):14362-14369
The study of micro- or nanocrystalline proteins by magic-angle spinning (MAS) solid-state NMR (SSNMR) gives atomic-resolution insight into structure in cases when single crystals cannot be obtained for diffraction studies. Subtle differences in the local chemical environment around the protein, including the characteristics of the cosolvent and the buffer, determine whether a protein will form single crystals. The impact of these small changes in formulation is also evident in the SSNMR spectra; however, the changes lead only to correspondingly subtle changes in the spectra. Here, we demonstrate that several formulations of GB1 microcrystals yield very high quality SSNMR spectra, although only a subset of conditions enable growth of single crystals. We have characterized these polymorphs by X-ray powder diffraction and assigned the SSNMR spectra. Assignments of the 13C and 15N SSNMR chemical shifts confirm that the backbone structure is conserved, indicative of a common protein fold, but side chain chemical shifts are changed on the surface of the protein, in a manner dependent upon crystal packing and electrostatic interactions with salt in the mother liquor. Our results demonstrate the ability of SSNMR to reveal minor structural differences among crystal polymorphs. This ability has potential practical utility for studying the formulation chemistry of industrial and therapeutic proteins, as well as for deriving fundamental insights into the phenomenon of single-crystal growth. 相似文献
959.
The palladium-catalyzed cross-coupling reaction of potassium (4-methoxyphenyl)dimethylsilanolate (K+1−) with aryl bromides has been demonstrated using triphenylphosphine oxide as a stabilizing ligand. Unsymmetrical biaryls can be prepared from a variety of aryl bromides in good yield with short reaction times. Qualitative kinetic studies compared effects of different phosphine oxides on the rate of cross-coupling and established the beneficial effect of these ligands in the reaction of electron-rich arylsilanolates. The improved yield and reproducibility of the cross-coupling of several bromides was demonstrated by direct comparison of reactions performed with and without triphenylphosphine oxide under non-rigorous exclusion of oxygen. 相似文献
960.
Hong-yu Li Yan Wang Arindam Chatterjee Sreenivasa R. Mundla Matthew Voss J. Scott Sawyer 《Tetrahedron》2007,63(47):11763-11770
A simple and efficient synthesis of dihydropyrrolopyrazole boronic acid intermediate (5) has been developed. Utilization of a three-component Suzuki-Miyaura/etherification with microwave heating led to advanced compound 11 in high yield and with easy purification. Reaction of compound 11 with methanesulfonyl chloride at room temperature furnished the 1,3 O-N rearranged product (12), which is postulated to proceed via an intramolecular mechanism. The outlined synthesis provides a highly efficient and high-yielding route that is amenable to rapid analog synthesis. 相似文献