全文获取类型
收费全文 | 860篇 |
免费 | 21篇 |
国内免费 | 12篇 |
专业分类
化学 | 439篇 |
晶体学 | 6篇 |
力学 | 40篇 |
数学 | 127篇 |
物理学 | 281篇 |
出版年
2023年 | 4篇 |
2022年 | 9篇 |
2021年 | 15篇 |
2020年 | 15篇 |
2019年 | 9篇 |
2018年 | 8篇 |
2017年 | 4篇 |
2016年 | 16篇 |
2015年 | 14篇 |
2014年 | 22篇 |
2013年 | 37篇 |
2012年 | 40篇 |
2011年 | 58篇 |
2010年 | 38篇 |
2009年 | 46篇 |
2008年 | 44篇 |
2007年 | 42篇 |
2006年 | 48篇 |
2005年 | 33篇 |
2004年 | 30篇 |
2003年 | 26篇 |
2002年 | 43篇 |
2001年 | 26篇 |
2000年 | 29篇 |
1999年 | 17篇 |
1998年 | 7篇 |
1997年 | 11篇 |
1996年 | 19篇 |
1995年 | 13篇 |
1994年 | 16篇 |
1993年 | 18篇 |
1992年 | 16篇 |
1991年 | 9篇 |
1990年 | 4篇 |
1989年 | 12篇 |
1988年 | 8篇 |
1987年 | 8篇 |
1986年 | 3篇 |
1985年 | 10篇 |
1984年 | 5篇 |
1983年 | 4篇 |
1982年 | 7篇 |
1981年 | 4篇 |
1980年 | 7篇 |
1979年 | 9篇 |
1977年 | 5篇 |
1976年 | 7篇 |
1975年 | 8篇 |
1974年 | 2篇 |
1972年 | 3篇 |
排序方式: 共有893条查询结果,搜索用时 15 毫秒
151.
152.
Dr. Wei Wei Ka Key Cheung Dr. Ran Lin Lam Cheung Kong Ka Lok Chan Dr. Herman H. Y. Sung Prof. Dr. Ian D. Williams Prof. Dr. Rongbiao Tong Prof. Dr. Zhenyang Lin Prof. Dr. Guochen Jia 《Angewandte Chemie (International ed. in English)》2023,62(36):e202307251
A unique benzannulation strategy for regioselective de novo synthesis of densely functionalized phenols is described. Through metal-mediated formal [2+2+1+1] cycloaddition of two different alkynes and two molecules of CO, a series of densely functionalized phenols were obtained. The benzannulation strategy allows efficient regioselective installation up to five different substituents on a phenol ring. The resulting phenols have a substitution pattern different from those obtained from Dötz and Danheiser benzannulations. 相似文献
153.
A reusable optical bioassay platform using permeability-controlled hydrogel pads for selective saccharide detection has been developed. An optical glucose detection assay based on fluorescence resonance energy transfer (FRET) between dye-labeled dextran and Concanavalin A (ConA) was incorporated into hydrogel pads by entrapment. The hydrogel pads are constructed from hemispherical hydrogel attached onto hydrophobic surfaces of a microtiter plate. The resulted hemispherical hydrogel pads entrapping the sensing biological materials were further surface coated with polyelectrolyte multilayers through a Layer-by-Layer (LbL) self-assembly process to create a permeability-controlled membrane with nanometer thickness. The selective permeable LbL film deposited on the hydrogel surface allows small molecular weight analytes to diffuse into the hydrogel pads while the large molecular weight sensing biological molecules are immobilized. An encapsulation efficiency of 75% for the ConA/Dextran complex within the coated hydrogel pads was achieved and no significant leakage of the complex was observed. Glucose calibration curve with linear range from 0 to 10 mM glucose was obtained. Selective permeability of the hydrogel pads has been demonstrated by measurement of saccharides with various molecular weights. The LbL hydrogel pads could selectively detect monosaccharides (glucose, MW = 180) and disaccharides (sucrose, MW = 342) while polysaccharides (dextran, MW ∼ 70 kDa) cannot diffuse through the LbL layer and are excluded. LbL hydrogel pads allow regeneration of the FRET system with good signal reproducibility of more than 90% to construct a reusable and reagentless optical bioassay platform. 相似文献
154.
Cheung DL 《The Journal of chemical physics》2008,128(19):194902
The structure of a model liquid crystalline fluid confined between two microstructured substrates is studied through Monte Carlo simulations. A simple model for a structured substrate, similar in spirit to those used for rough walls of walls with grafted polymers, is introduced. It is found that varying the structure of the substrate, a transition in the alignment of the confined fluid, from parallel to perpendicular, is induced. For particular substrate structures, it is possible to induce tilted alignment in the confined fluid, the tilt angle being temperature dependent. 相似文献
155.
This study demonstrates a versatile and fast method for patterning three-dimensional (3D) monolithic microstructures made of multiple (up to 24 demonstrated) types of materials, all spatially aligned, inside a microchannel. This technique uses confocal scanning or conventional fluorescence microscopy to polymerize selected regions of a photocurable material, and microfluidics to automate the delivery of a series of washes and photocurable reagents. Upon completion of lithographic cycles, the aligned 3D microstructures are suitable for microfluidic manipulation and analysis. We demonstrated the fabrication of composite 3D microstructures with various geometries, size scales (up to 1 mm2), spatial resolution (down to 3 microm), and materials. For a typical multi-cycle process, the total fabrication time was tens of minutes, compared to tens of hours for conventional methods. In the case of 3D hydrogels, a potential use is the direct patterning of inhomogeneous 3D microenvironments for studying cell behavior. 相似文献
156.
A series of catalysts have been prepared for use in the asymmetric transfer hydrogenation of ketones. The complexes were prepared using a [4 + 2] cycloaddition reaction at a key step in the reaction sequence. This provides a means for the synthesis of catalysts with modifications at specific sites. 相似文献
157.
Cheung CM Goldberg FW Magnus P Russell CJ Turnbull R Lynch V 《Journal of the American Chemical Society》2007,129(40):12320-12327
During the course of studies on the synthesis of diazonamide A 1, an unusual O-aryl into C-aryl rearrangement was discovered that allows partial control of the absolute stereochemistry of the C-10 quaternary stereogenic center. Treatment of 30 with TBAF/THF gave the O-tyrosine ethers 31 and 32 (1:1), which on heating each separately in chloroform at reflux rearranged to 33 and 34 in ratios of 84:16 and 56:44, respectively. This corresponds to a 70% yield of the correct C-10 stereoisomer 33 and a 30% yield of the wrong C-10 stereoisomer 34. Attempts to convert 34 into 33 by ipso-protonation and equilibration were unsuccessful. Confirmation of the stereochemical outcome of the rearrangement was obtained by converting 33 into 37, an advanced intermediate in the first synthesis of diazonamide A by Nicolaou et al. It was also found that the success of the above rearrangement is sensitive to the protecting group on both the tryptophan nitrogen atom and the tyrosine nitrogen atom. 相似文献
158.
159.
A new approach to (+)-cacospongionolide was developed to access conformationally restricted variants of the natural product. The flexible aliphatic region between the decalin and side chain portion of the natural product was replaced with alkenyl and alkynyl linkers to probe the influence of structural rigidity in the inhibition of secretary phospholipase A2 (sPLA2). It was found that when the aliphatic section is replaced with a Z-olefin or an alkyne, sPLA2 inhibitory activity suffered relative to the natural product; however, an E-olefin-containing analogue led to an enhanced activity. These results suggest that preferred sPLA2 binding conformation of the natural product is similar to the geometry of the E-olefin-containing analogue. 相似文献
160.
The kinetics of the reactions of 26 primary and secondary amines with benzhydrylium ions in water were investigated photometrically. Because the parallel reactions of the benzhydrylium ions with hydroxide and water are much slower, the second-order rate constants for the reactions of amines with benzhydrylium ions could be determined reliably. Reactivities of anilines were also studied in acetonitrile solution. Plots of log k2,N for these reactions vs the electrophilicity parameters E of the benzhydrylium ions were linear, which allowed us to derive the nucleophilicity parameters N and s for amines as defined by the equation log k(20 degrees C)=s(E+N). Because the slope parameters for the different amines are closely similar; the relative nucleophilicities are almost independent of the electrophiles and can be expressed by the nucleophilicity parameters N. The correlation between nucleophilicity N and pKaH values is poor, and it is found that secondary alkyl amines and anilines are considerably more nucleophilic, while ammonia is much less nucleophilic than expected on the basis of their pKaH values. 相似文献