全文获取类型
收费全文 | 4001篇 |
免费 | 166篇 |
国内免费 | 4篇 |
专业分类
化学 | 2819篇 |
晶体学 | 22篇 |
力学 | 61篇 |
数学 | 536篇 |
物理学 | 733篇 |
出版年
2023年 | 30篇 |
2022年 | 25篇 |
2021年 | 59篇 |
2020年 | 65篇 |
2019年 | 42篇 |
2018年 | 78篇 |
2017年 | 65篇 |
2016年 | 142篇 |
2015年 | 133篇 |
2014年 | 145篇 |
2013年 | 263篇 |
2012年 | 281篇 |
2011年 | 330篇 |
2010年 | 151篇 |
2009年 | 151篇 |
2008年 | 247篇 |
2007年 | 242篇 |
2006年 | 218篇 |
2005年 | 213篇 |
2004年 | 191篇 |
2003年 | 147篇 |
2002年 | 140篇 |
2001年 | 102篇 |
2000年 | 104篇 |
1999年 | 63篇 |
1998年 | 33篇 |
1997年 | 35篇 |
1996年 | 68篇 |
1995年 | 27篇 |
1994年 | 25篇 |
1993年 | 31篇 |
1992年 | 32篇 |
1991年 | 27篇 |
1990年 | 22篇 |
1989年 | 18篇 |
1988年 | 13篇 |
1987年 | 9篇 |
1986年 | 22篇 |
1985年 | 21篇 |
1984年 | 20篇 |
1983年 | 15篇 |
1982年 | 23篇 |
1981年 | 8篇 |
1980年 | 13篇 |
1979年 | 15篇 |
1978年 | 14篇 |
1977年 | 10篇 |
1976年 | 11篇 |
1974年 | 7篇 |
1973年 | 6篇 |
排序方式: 共有4171条查询结果,搜索用时 15 毫秒
1.
Experimental and Theoretical Studies on the Rearrangement of 2‐Oxoazepane α,α‐Amino Acids into 2′‐Oxopiperidine β2,3,3‐Amino Acids: An Example of Intramolecular Catalysis 下载免费PDF全文
Dr. Diego Núñez‐Villanueva Dr. M. Ángeles Bonache Laura Lozano Dr. Lourdes Infantes Prof. José Elguero Prof. Ibon Alkorta Prof. M. Teresa García‐López Dr. Rosario González‐Muñiz Dr. Mercedes Martín‐Martínez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(6):2489-2500
Enantiopure β‐amino acids represent interesting scaffolds for peptidomimetics, foldamers and bioactive compounds. However, the synthesis of highly substituted analogues is still a major challenge. Herein, we describe the spontaneous rearrangement of 4‐carboxy‐2‐oxoazepane α,α‐amino acids to lead to 2′‐oxopiperidine‐containing β2,3,3‐amino acids, upon basic or acid hydrolysis of the 2‐oxoazepane α,α‐amino acid ester. Under acidic conditions, a totally stereoselective synthetic route has been developed. The reordering process involved the spontaneous breakdown of an amide bond, which typically requires strong conditions, and the formation of a new bond leading to the six‐membered heterocycle. A quantum mechanical study was carried out to obtain insight into the remarkable ease of this rearrangement, which occurs at room temperature, either in solution or upon storage of the 4‐carboxylic acid substituted 2‐oxoazepane derivatives. This theoretical study suggests that the rearrangement process occurs through a concerted mechanism, in which the energy of the transition states can be lowered by the participation of a catalytic water molecule. Interestingly, it also suggested a role for the carboxylic acid at position 4 of the 2‐oxoazepane ring, which facilitates this rearrangement, participating directly in the intramolecular catalysis. 相似文献
2.
3.
Highly Selective Copper‐Catalyzed Asymmetric [3+2] Cycloaddition of Azomethine Ylides with Acyclic 1,3‐Dienes 下载免费PDF全文
María González‐Esguevillas Ana Pascual‐Escudero Dr. Javier Adrio Prof. Dr. Juan C. Carretero 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(12):4561-4565
The first examples of the catalytic asymmetric 1,3‐dipolar cycloaddition of azomethine ylides with acyclic activated 1,3‐dienes (and 1,3‐enynes) are described. Under copper catalysis, a selective cycloaddition at the terminal γ,δ‐C?C bond is observed. In addition, depending on the ligand used, either the exo or the endo adduct can be obtained with high selectivity. Under appropriate reaction conditions, the acyclic 1,6‐addition product is detected, suggesting a stepwise mechanism. The resulting C4‐alkenyl‐substituted pyrrolidines are suitable substrates for further access to polycyclic systems, as highlighted by the preparation of hexahydrochromeno[4,3‐b]pyrrole and the tetracyclic core of the alkaloid gracilamine. 相似文献
4.
Lithium (10–150 ng ml?1) in wine is determined by atomic absorption spectrometry by direct nebulization and after digestion with mixed acids. The results of methods are similar. Thirty-four wines from various Spanish provinces are analysed. 相似文献
5.
Salvador Hernández 《Topology and its Applications》2007,154(10):2089-2098
Let C(X,G) be the group of continuous functions from a topological space X into a topological group G with pointwise multiplication as the composition law, endowed with the uniform convergence topology. To what extent does the group structure of C(X,G) determine the topology of X? More generally, when does the existence of a group homomorphism H between the groups C(X,G) and C(Y,G) implies that there is a continuous map h of Y into X such that H is canonically represented by h? We prove that, for any topological group G and compact spaces X and Y, every non-vanishing C-isomorphism (defined below) H of C(X,G) into C(Y,G) is automatically continuous and can be canonically represented by a continuous map h of Y into X. Some applications to specific groups and examples are given in the paper. 相似文献
6.
7.
O. Maksimov P. Fisher M. Skowronski P.A. Salvador M. Snyder J. Xu X. Weng 《Journal of Crystal Growth》2008,310(11):2760-2766
MgO films were grown on (0 0 1) yttria-stabilized zirconia (YSZ) substrates by molecular beam epitaxy (MBE). The crystalline structures of these films were investigated using X-ray diffraction and transmission electron microscopy. Growth temperature was varied from 350 to 550 °C, with crystalline quality being improved at higher temperatures. The MgO films had a domain structure: (1 1 1)[1 1 2¯]MgO(0 0 1)[1 0 0]YSZ with four twin variants related by a 90° in-plane rotation about the [1 1 1]MgO axis. The observed epitaxial orientation was compared to previous reports of films grown by pulsed laser deposition and sputtering and explained as resulting in the lowest interface energy. 相似文献
8.
Essam Totry Carlos González Javier LLorca 《International Journal of Solids and Structures》2008,45(6):1663-1675
The influence of the loading path on the failure locus of a composite lamina subjected to transverse compression and out-of-plane shear is analyzed through computational micromechanics. This is carried out using the finite element simulation of a representative volume element of the microstructure, which takes into account explicitly fiber and matrix spatial distribution within the lamina. In addition, the actual failure mechanisms (plastic deformation of the matrix and interface decohesion) are included in the simulations through the corresponding constitutive models. Two different interface strength values were chosen to explore the limiting cases of composites with strong or weak interfaces. It was found that failure locus was independent of the loading path for the three cases analyzed (pseudo-radial, compression followed by shear and shear followed by compression) in the composites with strong and weak interfaces. This result was attributed to the fact that the dominant failure mechanism in each material was the same in transverse compression and in shear. Failure is also controlled by the same mechanisms under a combination of both stresses and the failure locus depended mainly on the magnitude of the stresses that trigger fracture rather than in the loading path to reach the critical condition. 相似文献
9.