全文获取类型
收费全文 | 220651篇 |
免费 | 2967篇 |
国内免费 | 1324篇 |
专业分类
化学 | 122727篇 |
晶体学 | 3228篇 |
力学 | 8888篇 |
综合类 | 61篇 |
数学 | 24365篇 |
物理学 | 65673篇 |
出版年
2020年 | 1754篇 |
2019年 | 1896篇 |
2018年 | 2483篇 |
2017年 | 2531篇 |
2016年 | 3645篇 |
2015年 | 2424篇 |
2014年 | 3537篇 |
2013年 | 8872篇 |
2012年 | 7686篇 |
2011年 | 9395篇 |
2010年 | 6649篇 |
2009年 | 6451篇 |
2008年 | 8792篇 |
2007年 | 8900篇 |
2006年 | 8384篇 |
2005年 | 7705篇 |
2004年 | 6870篇 |
2003年 | 6053篇 |
2002年 | 5985篇 |
2001年 | 6703篇 |
2000年 | 5067篇 |
1999年 | 3669篇 |
1998年 | 3038篇 |
1997年 | 3009篇 |
1996年 | 3011篇 |
1995年 | 2618篇 |
1994年 | 2718篇 |
1993年 | 2581篇 |
1992年 | 2829篇 |
1991年 | 2894篇 |
1990年 | 2703篇 |
1989年 | 2616篇 |
1988年 | 2557篇 |
1987年 | 2497篇 |
1986年 | 2520篇 |
1985年 | 3300篇 |
1984年 | 3359篇 |
1983年 | 2804篇 |
1982年 | 3046篇 |
1981年 | 2811篇 |
1980年 | 2607篇 |
1979年 | 2790篇 |
1978年 | 2996篇 |
1977年 | 3032篇 |
1976年 | 3059篇 |
1975年 | 2793篇 |
1974年 | 2906篇 |
1973年 | 2956篇 |
1972年 | 2318篇 |
1971年 | 1845篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
1.
In a 2:2 reaction with silver(I) chloride or bromide, 1,5-bis(1-phospholano)pentane ( 1a ) afforded frame-like macrocyclic structures, with intra- ( 2 , Cl) or intermolecular ( 3 , Br) halido bridges. In contrast, 1,7-bis(1-phospholano)heptane ( 1b ) formed coordination polymers 4a (Cl) and 4b (Br) with bridging bis-phospholane and halido ligands. A unique paddle wheel-type metallacryptand structure 5 was obtained from 1a and silver(I) bromide in a 2:3 reaction (M:L). All complexes were fully characterized by NMR, IR spectroscopy, mass spectrometry, and X-ray crystallography. 相似文献
2.
Laurens Kooijman Dr. Matthias Schuster Christian Baumann Simon Jurt Dr. Frank Löhr Dr. Boris Fürtig Prof. Dr. Peter Güntert Prof. Dr. Oliver Zerbe 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(47):21151-21158
To achieve efficient proton pumping in the light-driven proton pump bacteriorhodopsin (bR), the protein must be tightly coupled to the retinal to rapidly convert retinal isomerization into protein structural rearrangements. Methyl group dynamics of bR embedded in lipid nanodiscs were determined in the dark-adapted state, and were found to be mostly well ordered at the cytosolic side. Methyl groups in the M145A mutant of bR, which displays only 10 % residual proton pumping activity, are less well ordered, suggesting a link between side-chain dynamics on the cytosolic side of the bR cavity and proton pumping activity. In addition, slow conformational exchange, attributed to low frequency motions of aromatic rings, was indirectly observed for residues on the extracellular side of the bR cavity. This may be related to reorganization of the water network. These observations provide a detailed picture of previously undescribed equilibrium dynamics on different time scales for ground-state bR. 相似文献
3.
Pengjin Qin Li-An Wang Prof. Joseph M. O'Connor Prof. Kim K. Baldridge Yifan Li Burak Tufekci Jiyue Chen Prof. Arnold L. Rheingold 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(41):18114-18121
Triene 6π electrocyclization, wherein a conjugated triene undergoes a concerted stereospecific cycloisomerization to a cyclohexadiene, is a reaction of great historical and practical significance. In order to circumvent limitations imposed by the normally harsh reaction conditions, chemists have long sought to develop catalytic variants based upon the activating power of metal–alkene coordination. Herein, we demonstrate the first successful implementation of such a strategy by utilizing [(C5H5)Ru(NCMe)3]PF6 as a precatalyst for the disrotatory 6π electrocyclization of highly substituted trienes that are resistant to thermal cyclization. Mechanistic and computational studies implicate hexahapto transition-metal coordination as responsible for lowering the energetic barrier to ring closure. This work establishes a foundation for the development of new catalysts for stereoselective electrocyclizations. 相似文献
4.
Paired single residue‐transposed Lys‐N and Lys‐C digestions for label‐free identification of N‐terminal and C‐terminal MS/MS peptide product ions: ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry and tandem mass spectrometry for peptide de novo sequencing 下载免费PDF全文
5.
Kazakova E. F. Dmitrieva N. E. Zvereva N. L. 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2020,94(2):341-344
Russian Journal of Physical Chemistry A - Rapidly quenched alloys of aluminum with cobalt and zirconium are investigated using a combination of means of physicochemical analysis to study the... 相似文献
6.
7.
8.
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
9.
Su X. F. Zhang Y. L. Maximov A. L. Zhang K. Xin Q. Feng C. Q. Bai X. F. Wu W. 《Russian Journal of Applied Chemistry》2020,93(1):127-136
Russian Journal of Applied Chemistry - Nanoscale ZSM-5 (AlZ5-D) and Ga-substituted ZSM-5 zeolites ((Al,Ga)Z5-D and GaZ5-D) were synthesized by a green dry-gel conversion strategy. For comparison,... 相似文献
10.
We consider conformal gravity as a gauge natural theory. We study its conservation laws and superpotentials. We also consider the Mannheim and Kazanas spherically symmetric vacuum solution and discuss conserved quantities associated to conformal and diffeomorphism symmetries. 相似文献