全文获取类型
收费全文 | 5540篇 |
免费 | 199篇 |
国内免费 | 9篇 |
专业分类
化学 | 3645篇 |
晶体学 | 27篇 |
力学 | 156篇 |
数学 | 874篇 |
物理学 | 1046篇 |
出版年
2023年 | 52篇 |
2022年 | 61篇 |
2021年 | 116篇 |
2020年 | 90篇 |
2019年 | 87篇 |
2018年 | 105篇 |
2017年 | 98篇 |
2016年 | 184篇 |
2015年 | 172篇 |
2014年 | 177篇 |
2013年 | 350篇 |
2012年 | 391篇 |
2011年 | 408篇 |
2010年 | 220篇 |
2009年 | 224篇 |
2008年 | 316篇 |
2007年 | 335篇 |
2006年 | 307篇 |
2005年 | 292篇 |
2004年 | 257篇 |
2003年 | 194篇 |
2002年 | 169篇 |
2001年 | 113篇 |
2000年 | 115篇 |
1999年 | 74篇 |
1998年 | 47篇 |
1997年 | 52篇 |
1996年 | 87篇 |
1995年 | 42篇 |
1994年 | 36篇 |
1993年 | 41篇 |
1992年 | 41篇 |
1991年 | 28篇 |
1990年 | 28篇 |
1989年 | 26篇 |
1988年 | 15篇 |
1987年 | 17篇 |
1986年 | 27篇 |
1985年 | 37篇 |
1984年 | 38篇 |
1983年 | 23篇 |
1982年 | 36篇 |
1981年 | 26篇 |
1980年 | 30篇 |
1979年 | 23篇 |
1978年 | 21篇 |
1977年 | 21篇 |
1976年 | 20篇 |
1974年 | 15篇 |
1973年 | 17篇 |
排序方式: 共有5748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.
Probing the Catalytic Activity of Reduced Graphene Oxide Decorated with Au Nanoparticles Triggered by Visible Light 下载免费PDF全文
Dr. Jiale Wang Dr. Fabiane J. Trindade Caroline B. de Aquino Joana C. Pieretti Prof. Dr. Sergio H. Domingues Prof. Dr. Romulo A. Ando Prof. Dr. Pedro H. C. Camargo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(27):9889-9894
Hybrid materials in which reduced graphene oxide (rGO) is decorated with Au nanoparticles (rGO–Au NPs) were obtained by the in situ reduction of GO and AuCl4?(aq) by ascorbic acid. On laser excitation, rGO could be oxidized as a result of the surface plasmon resonance (SPR) excitation in the Au NPs, which generates activated O2 through the transfer of SPR‐excited hot electrons to O2 molecules adsorbed from air. The SPR‐mediated catalytic oxidation of p‐aminothiophenol (PATP) to p,p′‐dimercaptoazobenzene (DMAB) was then employed as a model reaction to probe the effect of rGO as a support for Au NPs on their SPR‐mediated catalytic activities. The increased conversion of PATP to DMAB relative to individual Au NPs indicated that charge‐transfer processes from rGO to Au took place and contributed to improved SPR‐mediated activity. Since the transfer of electrons from Au to adsorbed O2 molecules is the crucial step for PATP oxidation, in addition to the SPR‐excited hot electrons of Au NPs, the transfer of electrons from rGO to Au contributed to increasing the electron density of Au above the Fermi level and thus the Au‐to‐O2 charge‐transfer process. 相似文献
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.
A Volterra type integral equation in a Hilbert space with an additional linear operator L and a spectral parameter depending
on time is considered. If the parameter does not belong to the spectrum of L unconditional solvability of the considered problem
is proved. In the case where the initial value of the parameter coincides with some isolated point of the spectrum of the
operator L sufficient conditions for solvability are established. The obtained results are applied to the partial integral
equations associated with a contact problem of the theory of elasticity. 相似文献
7.
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
8.
9.
Lévy processes in matrix Lie groups are studied. Subordination (random time change) is used to show that quasi-invariance of the Brownian motion in a Lie group induces absolute continuity of the laws of the corresponding pure jump processes. These results are applied to several examples which are discussed in detail. 相似文献
10.
Generally, in homotopy theory a cylinder object (or, its dual, a path object) is used to define homotopy between morphisms,
and a cone object is used to build exact sequences of homotopy groups. Here, an axiomatic theory based on a cone functor is
given. Suspension objects are associated to based objects and cofibrations, obtaining homotopy groups referred to an object
and relative to a cofibration, respectively. Exact sequences of these groups are built. Algebraic and particular examples
are given. We point out that the main results of this paper were already stated in [3], and the purpose of this article is
to give full details of the foregoing. 相似文献