全文获取类型
收费全文 | 2217篇 |
免费 | 18篇 |
国内免费 | 11篇 |
专业分类
化学 | 1552篇 |
晶体学 | 13篇 |
力学 | 34篇 |
数学 | 360篇 |
物理学 | 287篇 |
出版年
2021年 | 11篇 |
2020年 | 19篇 |
2019年 | 7篇 |
2018年 | 15篇 |
2017年 | 14篇 |
2016年 | 20篇 |
2015年 | 19篇 |
2014年 | 32篇 |
2013年 | 114篇 |
2012年 | 94篇 |
2011年 | 115篇 |
2010年 | 73篇 |
2009年 | 57篇 |
2008年 | 118篇 |
2007年 | 129篇 |
2006年 | 138篇 |
2005年 | 144篇 |
2004年 | 118篇 |
2003年 | 98篇 |
2002年 | 83篇 |
2001年 | 24篇 |
2000年 | 21篇 |
1999年 | 26篇 |
1998年 | 21篇 |
1997年 | 34篇 |
1996年 | 34篇 |
1995年 | 16篇 |
1994年 | 38篇 |
1993年 | 33篇 |
1992年 | 16篇 |
1991年 | 24篇 |
1990年 | 25篇 |
1989年 | 21篇 |
1988年 | 23篇 |
1987年 | 19篇 |
1986年 | 19篇 |
1985年 | 33篇 |
1984年 | 32篇 |
1983年 | 18篇 |
1982年 | 52篇 |
1981年 | 40篇 |
1980年 | 36篇 |
1979年 | 34篇 |
1978年 | 31篇 |
1977年 | 36篇 |
1976年 | 25篇 |
1975年 | 18篇 |
1974年 | 19篇 |
1973年 | 13篇 |
1971年 | 8篇 |
排序方式: 共有2246条查询结果,搜索用时 93 毫秒
121.
Bromonitromethane, triethyl orthoformate and aniline react together, in a one-flask procedure, to afford the title compound. 相似文献
122.
Brecht Van Hooreweder David Moens Rene Boonen Jean-Pierre Kruth Paul Sas 《Polymer Testing》2013,32(5):972-981
This paper describes the influence of dynamic tension/compression loading on notched and unnotched nylon specimens fabricated by Injection Molding (IM) and Selective Laser Sintering (SLS). The main objective of this work is to analyze and describe the differences in material structure and fatigue properties of as-built nylon parts produced by IM and SLM from the same polyamide 12 powder. The differences in dimensional quality, density, surface roughness, crystal structure and crystallinity are systematically measured and linked to the mechanical fatigue properties. The fatigue properties of the unnotched SLS specimens are found to be equal to those of the unnotched IM specimens. The presence of pores in the sintered samples does not lead to rapid failure, and the microvoid coalescence failure mechanism is delayed. The notched specimens show more brittle failure and increased fatigue resistance which is caused by local notch-strengthening. The results enable improved understanding of the difference in material structure and fatigue behavior of selective laser sintered and injection molded polyamide. 相似文献
123.
Cecile Canlet Bing M. Fung Frederick Roussel Karine Leblanc Philippe Berdague Jean-Pierre Bayle 《Liquid crystals》2013,40(5):635-641
Mesogenic compounds containing four rings in the core usually have very high melting points. However, when two identical lateral benzyloxy groups are introduced on the same side of one of the central rings, the melting point is lowered dramatically and a large nematic range is retained. This range is affected by the bulkiness of the para-substituents in the lateral rings. Methyl groups can be introduced in the ortho- or meta-positions with a consequent decrease in the melting temperature without much affecting the nematic range. These compounds exhibit a rich solid polymorphism which is certainly related to the effect of the conformations of the lateral substituent on the molecular arrangment in the solid phase. Some preliminary NMR experiments on the nematic phase indicate that the molecular long axis coincides with the core axis, whereas the para-axis of the lateral fragment makes an angle close to the magic angle with respect to the molecular long axis. 相似文献
124.
Jorge A. Vila Yelena A. Arnautova Osvaldo A. Martin Harold A. Scheraga 《Journal of computational chemistry》2014,35(4):309-312
The goal of this study is twofold. First, to investigate the relative influence of the main structural factors affecting the computation of the 13C′ shielding, namely, the conformation of the residue itself and the next nearest‐neighbor effects. Second, to determine whether calculation of the 13C′ shielding at the density functional level of theory (DFT), with an accuracy similar to that of the 13Cα shielding, is feasible with the existing computational resources. The DFT calculations, carried out for a large number of possible conformations of the tripeptide Ac‐G XY ‐NMe, with different combinations of X and Y residues, enable us to conclude that the accurate computation of the 13C′ shielding for a given residue X depends on the: (i) (?,ψ) backbone torsional angles of X ; (ii) side‐chain conformation of X ; (iii) (?,ψ) torsional angles of Y ; and (iv) identity of residue Y . Consequently, DFT‐based quantum mechanical calculations of the 13C′ shielding, with all these factors taken into account, are two orders of magnitude more CPU demanding than the computation, with similar accuracy, of the 13Cα shielding. Despite not considering the effect of the possible hydrogen bond interaction of the carbonyl oxygen, this work contributes to our general understanding of the main structural factors affecting the accurate computation of the 13C′ shielding in proteins and may spur significant progress in effort to develop new validation methods for protein structures. © 2013 Wiley Periodicals, Inc. 相似文献
125.
Using experiments and theory, we show that light scattering by inhomogeneities in the index of refraction of a fluid can drive a large-scale flow. The experiment uses a near-critical, phase-separated liquid, which experiences large fluctuations in its index of refraction. A laser beam traversing the liquid produces a interface deformation on the scale of the experimental setup and can cause a liquid jet to form. We demonstrate that the deformation is produced by a scattering-induced flow by obtaining good agreements between the measured deformations and those calculated assuming this mechanism. 相似文献
126.
Anne-Marie Caminade Jean-Pierre Majoral 《Phosphorus, sulfur, and silicon and the related elements》2014,189(7-8):1132-1143
AbstractDendrimers are hyperbranched macromolecules constituted of repetitive branched units. They are synthesized step-by-step, a method which ensures a perfectly defined structure. This mini-review reports examples of rare “multiplurifunctionalized” dendrimers that have several types of functional groups precisely located on each terminal branching point. They are obtained thanks to the specificity of the reactivity of each Cl of P(X)Cl2 (X = generally S, but also O) terminal groups on the surface of poly(phosphorhydrazone) dendrimers. 相似文献
127.
Dr. Christina I. Schroeder Dr. Lachlan D. Rash Xavier Vila‐Farrés Dr. K. Johan Rosengren Dr. Mehdi Mobli Prof. Glenn F. King Prof. Paul F. Alewood Prof. David J. Craik Dr. Thomas Durek 《Angewandte Chemie (International ed. in English)》2014,53(4):1017-1020
Mambalgins are a novel class of snake venom components that exert potent analgesic effects mediated through the inhibition of acid‐sensing ion channels (ASICs). The 57‐residue polypeptide mambalgin‐2 (Ma‐2) was synthesized by using a combination of solid‐phase peptide synthesis and native chemical ligation. The structure of the synthetic toxin, determined using homonuclear NMR, revealed an unusual three‐finger toxin fold reminiscent of functionally unrelated snake toxins. Electrophysiological analysis of Ma‐2 on wild‐type and mutant ASIC1a receptors allowed us to identify α‐helix 5, which borders on the functionally critical acidic pocket of the channel, as a major part of the Ma‐2 binding site. This region is also crucial for the interaction of ASIC1a with the spider toxin PcTx1, thus suggesting that the binding sites for these toxins substantially overlap. This work lays the foundation for structure–activity relationship (SAR) studies and further development of this promising analgesic peptide. 相似文献
128.
Palladium‐Catalysed Direct Cross‐Coupling of Organolithium Reagents with Aryl and Vinyl Triflates
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Carlos Vila Dr. Valentín Hornillos Massimo Giannerini Dr. Martín Fañanás‐Mastral Prof. Dr. Ben L. Feringa 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(41):13078-13083
A palladium‐catalysed cross‐coupling of organolithium reagents with aryl and vinyl triflates is presented. The reaction proceeds at 50 or 70 °C with short reaction times, and the corresponding products are obtained with moderate to high yields, with a variety of alkyl and (hetero)aryl lithium reagents. 相似文献
129.
130.
Control of the Electronic Ground State on an Electron‐Transfer Copper Site by Second‐Sphere Perturbations
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Marcos N. Morgada Dr. Luciano A. Abriata Ulises Zitare Dr. Damian Alvarez‐Paggi Prof. Daniel H. Murgida Prof. Alejandro J. Vila 《Angewandte Chemie (International ed. in English)》2014,53(24):6188-6192
The CuA center is a dinuclear copper site that serves as an optimized hub for long‐range electron transfer in heme–copper terminal oxidases. Its electronic structure can be described in terms of a σu* ground‐state wavefunction with an alternative, less populated ground state of πu symmetry, which is thermally accessible. It is now shown that second‐sphere mutations in the CuA containing subunit of Thermus thermophilus ba3 oxidase perturb the electronic structure, which leads to a substantial increase in the population of the πu state, as shown by different spectroscopic methods. This perturbation does not affect the redox potential of the metal site, and despite an increase in the reorganization energy, it is not detrimental to the electron‐transfer kinetics. The mutations were achieved by replacing the loops that are involved in protein–protein interactions with cytochrome c, suggesting that transient protein binding could also elicit ground‐state switching in the oxidase, which enables alternative electron‐transfer pathways. 相似文献