全文获取类型
收费全文 | 468篇 |
免费 | 111篇 |
国内免费 | 94篇 |
专业分类
化学 | 326篇 |
晶体学 | 4篇 |
力学 | 31篇 |
综合类 | 8篇 |
数学 | 35篇 |
物理学 | 269篇 |
出版年
2024年 | 1篇 |
2023年 | 9篇 |
2022年 | 24篇 |
2021年 | 16篇 |
2020年 | 25篇 |
2019年 | 18篇 |
2018年 | 11篇 |
2017年 | 11篇 |
2016年 | 23篇 |
2015年 | 25篇 |
2014年 | 19篇 |
2013年 | 43篇 |
2012年 | 32篇 |
2011年 | 31篇 |
2010年 | 28篇 |
2009年 | 31篇 |
2008年 | 29篇 |
2007年 | 39篇 |
2006年 | 23篇 |
2005年 | 24篇 |
2004年 | 18篇 |
2003年 | 17篇 |
2002年 | 13篇 |
2001年 | 13篇 |
2000年 | 11篇 |
1999年 | 25篇 |
1998年 | 14篇 |
1997年 | 10篇 |
1996年 | 11篇 |
1995年 | 17篇 |
1994年 | 11篇 |
1993年 | 6篇 |
1992年 | 14篇 |
1991年 | 13篇 |
1990年 | 4篇 |
1989年 | 8篇 |
1988年 | 1篇 |
1985年 | 2篇 |
1984年 | 1篇 |
1982年 | 1篇 |
1980年 | 1篇 |
排序方式: 共有673条查询结果,搜索用时 15 毫秒
31.
GOUXiao-jun ZHANGZhong-hua LIShuang KONGXiang-duo SUNYan-hong LIUWei ZHAGNJin 《高等学校化学研究》2004,20(1):55-59
Human extracellular superoxide dismutase(hEC-SOD) is a secreted tetrameric protein involved in the protection of a human body from oxygen free radicals. Its three-dimensional structure has not been confirmed, hEC-SOD couldn′t be expressed in E.coll. We constructed a hybrid enzyme, which comprises the Nterminal and C-terminal domains from hEC-SOD, fused it to human Cu, Zn-SOD. The hybrid enzyme is expressed successfully in E. coli. Further, we analyzed the expression of hEC-SOD in E. coli by mRNA differential displaying. 相似文献
32.
The covalent binding of pyrazine on Si(100) have been investigated using high-resolution electron energy loss spectroscopy (HREELS) and x-ray photoelectron spectroscopy. Experimental results clearly suggest that the attachment occurs exclusively through the bonding of the two para-nitrogen atoms with the surface without the involvement of the carbon atoms, as evidenced from the retention of the (sp2) C-H stretching mode in HREELS and a significant down shift of 1.6 eV in the binding energy of N 1s. The binding mechanism for pyrazine on Si(100) demonstrates that reaction channels for heteroatomic aromatic molecules are strongly dependent on the electronic properties of the constituent atoms. 相似文献
33.
34.
Weixing Li Luca Evangelisti Qian Gou Walther Caminati Rolf Meyer 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(3):869-875
The rotational spectra of three C‐deuterated isotopologues of the dimer of formic acid have been measured, thanks to the small dipole moment induced by asymmetric H→D substitution(s). For the DCOOH–HCOOH species, the concerted double proton transfer of the two hydroxy hydrogen atoms takes place between two equivalent minima and generates a tunneling splitting of 331.2(6) MHz. This splitting can be reproduced by a 3D model with a barrier of 2559 cm?1 (30.6 kJ mol?1) as obtained from theoretical calculations. 相似文献
35.
The last decade has witnessed multiple thermally responsive materials emerge as a significant class of stimuli‐responsive materials. These materials are elaborately designed and exert interesting properties. Herein, an overview of thermally responsive materials with respect to design strategies, fabrication procedures, and their applications is presented. Recently reported thermally responsive materials are highlighted. Then, applications of thermally responsive materials in bioimaging are summarized. 相似文献
36.
Chiral derivatives of trans-1,2-diaminocyclohexane with different N,N-dialkyl groups in well-defined orientations have been synthesized, and applied as catalysts for the asymmetric aldol reaction between a variety of aldehydes and ketones. Enantiomeric catalyst 1j catalyzed the reaction in ethanol and provided excellent diastereoselectivity and enantioselectivity. Significantly, simple replacement of organic solvents with water switched the products of the aldol reactions from anti to syn configuration. Such catalytic reactions led to the products with anti to syn diastereoselectivity up to 99:1 in ethanol, while in water gave the products with syn to anti diastereoselectivity up to 99:1. 相似文献
37.
The self‐assembly of 4 ‐ MTPP [ 4 ‐ MTPP = 2‐(methylthio)‐4‐(pyridin‐4‐yl)pyrimidine] with Cu(NO3)2 and AgNO3 was structurally investigated. For Cu(NO3)2, a discrete mononuclear CuII coordination compound, [Cu( 4 ‐ MTPP )2(NO3)2] ( 1 ), resulted that is exclusively based on Cu–N coordination. For AgNO3, a unique one‐dimensional double‐chain structure ( 2 ) was obtained with the Ag–N distances varying from 2.181(9) to 2.223(9) Å, and the average Ag–S distance being 2.98 Å. Compared to zero‐dimensional 1 , the extension to one‐dimensional 2 is considered to result from the specific affinity between Ag+ and the ligand 4 ‐ MTPP that is attributed to the strong coordinating tendency of silver for aromatic nitrogen and thioether sulfur atoms. 相似文献
38.
Jun Iwabuchi Takashi Kurokawa Zejian Gou Akira Hasegawa 《Journal of carbohydrate chemistry》2013,32(3):605-616
Abstract Benzyl 2,3-anhydro-4-azido-4-deoxy-α-L-ribopyranoside (7), an intermediate for the synthesis of Prumycin was synthesized in 72% yield in seven steps from D-arabinose. Ammonolysis of 7 followed by N-protection with the benzyloxycarbonyl group gave benzyl 4-azido-2-(benzyloxycarbonyl)amino-2,4-dideoxy-α-L-arabinopyranoside (8), which was easily converted to Prumycin. 相似文献
39.
A nondestructive desulfurization microorganism has been isolated. The metabolism product analyses show that the strain can be a kind of biocatalyst to oxidize dibenzothiophene (DBT) into 2-hydroxydiphenyl (HBP), therefore the sulfur in DBT is removed selectively. The 16SrRNA information, cell wall analysis, physical, biochemical properties and morphological properties suggest that the isolated strain is Rhodococcus erythropolis. The strain can grow in the basal salts medium (BSM) that DBT concentration is no more than 10 mmol/L, and the optimal DBT concentration for growth is 1 mmol/L, however, the optimal DBT concentration for desulfurization is 0.5 mmol/L. The further research shows that the strain can also desulfur some other or-ganosulfur-containing compounds such as thianaphthene, phenyl sulfide and 4,6-dimethyldiben-zothiophene (4,6-DMDBT). 相似文献
40.
Xingxing Gou Xiaohua Pu Zongxiao Li 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2017,91(11):2110-2116
In this paper, we selected quercetin and aromatic amino acids (tryptophan, tyrosine, phenylalanine) as the research objects to investigate the change rules in the reaction process. The thermodynamic functions (Ka, ΔG, and ΔS) of the interactions between quercetin and aromatic amino acids (tryptophan, tyrosine, phenylalanine) were measured by isothermal titration calorimetry. The values of binding constant (Ka) reached maximum at 25°C; the entropies and Gibbs free energies were both negative at different temperatures. The kinetic parameters of quercetin and amino acids in the interaction process was determined by microcalorimetry. The results inferred that the driving force of the reaction was hydrogen bond or van der Waals force. 相似文献