全文获取类型
收费全文 | 580篇 |
免费 | 13篇 |
国内免费 | 2篇 |
专业分类
化学 | 461篇 |
晶体学 | 8篇 |
力学 | 4篇 |
数学 | 13篇 |
物理学 | 109篇 |
出版年
2022年 | 2篇 |
2021年 | 3篇 |
2020年 | 7篇 |
2019年 | 5篇 |
2018年 | 3篇 |
2017年 | 2篇 |
2016年 | 11篇 |
2015年 | 6篇 |
2014年 | 12篇 |
2013年 | 19篇 |
2012年 | 39篇 |
2011年 | 39篇 |
2010年 | 23篇 |
2009年 | 19篇 |
2008年 | 32篇 |
2007年 | 36篇 |
2006年 | 52篇 |
2005年 | 41篇 |
2004年 | 36篇 |
2003年 | 29篇 |
2002年 | 32篇 |
2001年 | 10篇 |
2000年 | 9篇 |
1999年 | 7篇 |
1998年 | 10篇 |
1997年 | 4篇 |
1996年 | 6篇 |
1995年 | 4篇 |
1994年 | 4篇 |
1993年 | 2篇 |
1992年 | 2篇 |
1991年 | 2篇 |
1990年 | 5篇 |
1989年 | 3篇 |
1988年 | 2篇 |
1986年 | 2篇 |
1985年 | 8篇 |
1984年 | 6篇 |
1983年 | 5篇 |
1982年 | 6篇 |
1981年 | 5篇 |
1980年 | 5篇 |
1979年 | 4篇 |
1978年 | 3篇 |
1977年 | 6篇 |
1976年 | 8篇 |
1975年 | 4篇 |
1974年 | 3篇 |
1973年 | 6篇 |
1966年 | 3篇 |
排序方式: 共有595条查询结果,搜索用时 38 毫秒
21.
A novel bis(beta-cyclodextrin) was synthesized, and its binding behavior with steroids was investigated to demonstrate that the cooperative co-inclusion of guest and tether by two cyclodextrin moieties is operative to afford the highest molecular selectivity of up to 3.6 for deoxycholate over taurocholate. 相似文献
22.
The relationship between the product patterns and the configurations of 1,2-cycloheptane- and 1,2-cyclooctanediols 9 in the cyclocondensations with oxalyl chloride in the presence of triethylamine at 0 degrees C has been shown analogous to that obtained for 1,2-disubstituted acyclic ethylene glycols 1: cis-1,2-cyclooctanediol (9f) produced the cyclic oxalate 14f as the major product, while trans-1,2-cycloheptanediol (9e) and trans-1,2-cyclooctanediol (9g) formed the cyclic carbonates 12e, g as the major products. On the other hand, the cyclic oxalates 14a-d were formed as the major products from 1,2-cyclopentane- and 1,2-cyclohexanediols regardless of the configuration. These results can be accounted for by assuming the boat-like transition states for cyclizations of the half esters of comparatively rigid five- and six-membered diols 9a--d. The cyclic oxalates 14a, c may be directly formed through the resulting tetrahedral intermediates from cis-diols (9a,c), and the cyclic carbonates 12a,c as the minor products after ring inversion of the tetrahedral intermediates. The tetrahedral intermediates from the trans-isomers 9b, d cannot undergo ring inversion, producing no traces of the cyclic carbonates 12b, d. 相似文献
23.
Osako T Terada S Tosha T Nagatomo S Furutachi H Fujinami S Kitagawa T Suzuki M Itoh S 《Dalton transactions (Cambridge, England : 2003)》2005,(21):3514-3521
The structure and dioxygen-reactivity of copper(I) complexes R supported by N,N-bis(6-methylpyridin-2-ylmethyl)amine tridentate ligands L2R[R (N-alkyl substituent)=-CH2Ph (Bn), -CH2CH2Ph (Phe) and -CH2CHPh2(PhePh)] have been examined and compared with those of copper(I) complex (Phe) of N,N-bis[2-(pyridin-2-yl)ethyl]amine tridentate ligand L1(Phe) and copper(I) complex (Phe) of N,N-bis(pyridin-2-ylmethyl)amine tridentate ligand L3(Phe). Copper(I) complexes (Phe) and (PhePh) exhibited a distorted trigonal pyramidal structure involving a d-pi interaction with an eta1-binding mode between the metal ion and one of the ortho-carbon atoms of the phenyl group of the N-alkyl substituent [-CH2CH2Ph (Phe) and -CH2CHPh2(PhePh)]. The strength of the d-pi interaction in (Phe) and (PhePh) was weaker than that of the d-pi interaction with an eta2-binding mode in (Phe) but stronger than that of the eta1 d-pi interaction in (Phe). Existence of a weak d-pi interaction in (Bn) in solution was also explored, but its binding mode was not clear. Redox potentials of the copper(I) complexes (E1/2) were also affected by the supporting ligand; the order of E1/2 was Phe>R>Phe. Thus, the order of electron-donor ability of the ligand is L1Phe相似文献
24.
T. Nagai K. Sakai T. Asaka A. Yamazaki Y. Matsui 《Journal of solid state chemistry》2006,179(6):1898-1903
The crystal structure of our newly discovered Sr-Co-O phase is investigated in detail through high-resolution electron microscopy (HREM) techniques. Electron diffraction (ED) measurement together with energy dispersive X-ray spectroscopy (EDS) analysis show that an ampoule-synthesized sample contains an unknown Sr-Co-O ternary phase with monoclinic symmetry and the cation ratio of Sr/Co=1. From HREM images a layered structure with a regular stacking of a CdI2-type CoO2 sheet and a rock-salt-type Sr2O2 double-layered block is observed, which confirms that the phase is the parent of the more complex “misfit-layered (ML)” cobalt oxides of [MmA2Om+2]qCoO2 with the formula of [Sr2O2]qCoO2, i.e. m=0. It is revealed that the misfit parameter q is 0.5, i.e. the two sublattices of the CoO2 sheet and the Sr2O2 block coexist to form a commensurate composite structure. We propose a structural model with monoclinic P21/m symmetry, which is supported by simulations of ED patterns and HREM images based on dynamical diffraction theory. 相似文献
25.
The ν2 (CD3 symmetrical deformation) and ν5 (CD3 degenerate deformation) fundamental bands of CD3Br were studied by 9.4- and 10.4-μm CO2 laser Stark spectroscopy. Stark resonances originating from 28 and 53 rovibrational transitions of the ν2 and ν5 bands, respectively, were assigned for each of the isotopic species, CD379Br and CD381Br. These two bands were simultaneously analyzed with explicit inclusion of the ν2-ν5 Coriolis interaction, yielding precise molecular constants in the ν2 and ν5 excited states as well as the Coriolis coupling constant. The molecular constants obtained are consistent between the two isotopic species and are in good agreement with the results of high-resolution infrared studies. The band origins and dipole moments are
CD379Br | CD381Br | |||||
991.396 82 (18) | 991.388 46 (17) | cm?1 | ||||
1055.469 00 (12) | 1055.466 32 (12) | cm?1 | ||||
1.830 42 (52) | 1.829 84 (47) | D | ||||
1.829 93 (48) | 1.829 57 (46) | D | ||||
1.832 23 (60) | 1.831 19 (56) | D |