全文获取类型
收费全文 | 9371篇 |
免费 | 414篇 |
国内免费 | 61篇 |
专业分类
化学 | 6607篇 |
晶体学 | 40篇 |
力学 | 189篇 |
数学 | 1485篇 |
物理学 | 1525篇 |
出版年
2023年 | 68篇 |
2022年 | 156篇 |
2021年 | 236篇 |
2020年 | 176篇 |
2019年 | 163篇 |
2018年 | 192篇 |
2017年 | 165篇 |
2016年 | 356篇 |
2015年 | 341篇 |
2014年 | 359篇 |
2013年 | 627篇 |
2012年 | 653篇 |
2011年 | 768篇 |
2010年 | 428篇 |
2009年 | 363篇 |
2008年 | 630篇 |
2007年 | 594篇 |
2006年 | 563篇 |
2005年 | 501篇 |
2004年 | 434篇 |
2003年 | 335篇 |
2002年 | 300篇 |
2001年 | 142篇 |
2000年 | 158篇 |
1999年 | 94篇 |
1998年 | 85篇 |
1997年 | 83篇 |
1996年 | 118篇 |
1995年 | 56篇 |
1994年 | 52篇 |
1993年 | 57篇 |
1992年 | 64篇 |
1991年 | 50篇 |
1990年 | 32篇 |
1989年 | 26篇 |
1988年 | 19篇 |
1987年 | 20篇 |
1986年 | 31篇 |
1985年 | 40篇 |
1984年 | 44篇 |
1983年 | 27篇 |
1982年 | 33篇 |
1981年 | 29篇 |
1980年 | 28篇 |
1979年 | 27篇 |
1978年 | 28篇 |
1977年 | 22篇 |
1976年 | 15篇 |
1974年 | 10篇 |
1973年 | 15篇 |
排序方式: 共有9846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.
4.
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
5.
6.
Albo Carlos Cavalheiro 《Applications of Mathematics》2006,51(6):619-628
In the paper we study the equation L
u
= f, where L is a degenerate elliptic operator, with Neumann boundary condition in a bounded open set μ. We prove existence and uniqueness
of solutions in the space H(μ) for the Neumann problem. 相似文献
7.
Complementary regioselective esterification of non-reducing oligosaccharides catalyzed by different hydrolases 总被引:1,自引:0,他引:1
The enzymatic transesterification of several tri- and tetrasaccharides with vinyl laurate is described. The lipases from Candida antarctica B (Novozym 435) and Thermomyces lanuginosus (Lipozyme TL IM) and the alkaline protease from Bacillus licheniformis (subtilisin Carlsberg) have been used with each carbohydrate to obtain different regioisomers. By using the sugars in their amorphous form, complete solubility is achieved in the reaction media (tert-butanol/pyridine mixtures for the lipases and pyridine for the protease) and high isolated yields of the corresponding monoesters are obtained. Good to excellent regioselectivity is observed for all the enzymes, showing a final complementary picture respect to the primary hydroxyls of the oligosaccharides studied. 相似文献
8.
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
9.
Marcelo Queiroz Joaquim Jú dice Carlos Humes Jr.. 《Mathematics of Computation》2004,73(248):1849-1863
In this paper the Eigenvalue Complementarity Problem (EiCP) with real symmetric matrices is addressed. It is shown that the symmetric (EiCP) is equivalent to finding an equilibrium solution of a differentiable optimization problem in a compact set. A necessary and sufficient condition for solvability is obtained which, when verified, gives a convenient starting point for any gradient-ascent local optimization method to converge to a solution of the (EiCP). It is further shown that similar results apply to the Symmetric Generalized Eigenvalue Complementarity Problem (GEiCP). Computational tests show that these reformulations improve the speed and robustness of the solution methods.
10.
Ana Luísa Daniel‐da‐Silva João Carlos Moura Bordado José Miguel Martín‐Martínez 《Journal of Polymer Science.Polymer Physics》2007,45(22):3034-3045
The degree of phase separation in several moisture‐cured poly(urethane urea)s (PUUs) was studied by FTIR spectroscopy, wide angle X‐ray diffraction (WAXD), and temperature‐modulated differential scanning calorimetry (TMDSC). This latter technique was shown to be particularly useful in analysing the degree of phase separation in PUU polymers. Both phase mixing and phase segregation coexisted in the PUUs and the degree of phase separation increased as the urea hard segment (HS) content in the PUU increased. The maximum solubility of urea HSs into the polyol soft segments (SSs) was achieved for 50 wt % urea HS content in diol‐based PUUs, whereas for triol‐based PUUs the highest solubility between HS and SS was reached for lower urea HS amount. Finally, the higher the urea HS content the higher the extent of phase separation in the PUU. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3034–3045, 2007 相似文献