全文获取类型
收费全文 | 2384篇 |
免费 | 74篇 |
国内免费 | 16篇 |
专业分类
化学 | 1593篇 |
晶体学 | 16篇 |
力学 | 43篇 |
数学 | 466篇 |
物理学 | 356篇 |
出版年
2022年 | 23篇 |
2021年 | 28篇 |
2020年 | 26篇 |
2019年 | 36篇 |
2018年 | 23篇 |
2017年 | 25篇 |
2016年 | 37篇 |
2015年 | 31篇 |
2014年 | 42篇 |
2013年 | 107篇 |
2012年 | 83篇 |
2011年 | 131篇 |
2010年 | 79篇 |
2009年 | 64篇 |
2008年 | 115篇 |
2007年 | 92篇 |
2006年 | 110篇 |
2005年 | 106篇 |
2004年 | 118篇 |
2003年 | 102篇 |
2002年 | 87篇 |
2001年 | 20篇 |
2000年 | 33篇 |
1999年 | 23篇 |
1997年 | 20篇 |
1996年 | 52篇 |
1994年 | 29篇 |
1993年 | 21篇 |
1992年 | 25篇 |
1991年 | 22篇 |
1990年 | 28篇 |
1989年 | 21篇 |
1988年 | 20篇 |
1987年 | 18篇 |
1986年 | 21篇 |
1985年 | 43篇 |
1984年 | 34篇 |
1983年 | 28篇 |
1982年 | 32篇 |
1981年 | 32篇 |
1980年 | 31篇 |
1979年 | 27篇 |
1978年 | 35篇 |
1977年 | 32篇 |
1976年 | 22篇 |
1975年 | 29篇 |
1974年 | 34篇 |
1973年 | 30篇 |
1970年 | 20篇 |
1968年 | 19篇 |
排序方式: 共有2474条查询结果,搜索用时 218 毫秒
51.
The photochemical reaction between optically active ene carbamates and chromium alkoxycarbene complexes containing unsaturated aliphatic side chains was further developed. Although remote olefinic groups, including conjugated dienes, were tolerated, a homoallylic side chain underwent intramolecular reaction to give a strained cyclobutanone. (+)-Cerulenin was synthesized utilizing the photochemical reaction of an alkynylcarbene complex with an optically active ene carbamate and the bis(pi-crotyl)nickel halide alkylation of a vinyl bromide as key steps. 相似文献
52.
53.
54.
Atiya MS Chiang IH Frank JS Haggerty JS Ito MM Kycia TF Li KK Littenberg LS Sambamurti A Stevens A Strand RC Louis WC Akerib DS Marlow DR Meyers PD Selen MA Shoemaker FC Smith AJ Blackmore EW Bryman DA Felawka L Kitching P Konaka A Kuno Y Macdonald JA Numao T Padley P Poutissou JM Poutissou R Roy J Soluk R Turcot AS 《Physical review letters》1993,70(17):2521-2524
55.
56.
Two polyesters containing rigid biphenyl and hydroquinone bisbenzoate groups and presenting flexible thioether moieties with different lengths (14 elements in the flexible group) have been carried out using a reaction of the Michaël type. The properties of these polyesters have been compared to those of polyesters of the same type presenting shorter flexible groups (11 elements). All these polymers present thermotropic properties: the biphenyl ones are smectic and the bisbenzoate ones are nematic. The biphenyl polyesters present two types of dielectric relaxations: α and β. The bisbenzoate ones show three relaxations, α and two β (β and β′). The lengthening of the flexible group increases significantly the flexibility of the molecular chains. 相似文献
57.
Vyskocil S Meca L Tislerová I Císarová I Polásek M Harutyunyan SR Belokon YN Stead RM Farrugia L Lockhart SC Mitchell WL Kocovský P 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(20):4633-4648
The title binaphthyls 19 and 26, which are the positional isomers of 2-methoxy-2'-(diphenylphosphino)-1,1'-binaphthyl (MOP, 19) and 2-amino-2'-hydroxy-1,1'-binaphthyl (NOBIN, 26), have been synthesized by Suzuki coupling as the key step (10 + 15-->18), followed by functional group transformations, involving C-P and C-N bond formation (18-->19 and 18-->23). Racemic intermediate 22 was resolved by co-crystallization with N-benzylcinchonidinium chloride and the absolute configuration determined by X-ray crystallography. These novel binaphthyls are configurationally stable and, as such, potentially usable as chiral ligands in asymmetric reactions. Michael addition of the glycine-derived enolate 40 to methyl acrylate, carried out in the presence of (R)-(-)-27 as the chiral phase-transfer catalyst, afforded L-glutamic acid (S)-(+)-43 of 92% ee (after hydrolysis of the primary product). 相似文献
58.
59.
Application of the LCAO-MO-SCF- method to conjugated hydrocarbons leads with the effective nuclear Slater's charges, Zeff = Zeff = 3.25 to electronic transitions higher than experimental ones by about 50%.We show that in the case of all trans linear polyenes and fulvene, one may obtain satisfying results by the same method, without any reference to experience, by taking Zeff = 3.0 Zeff = 3.55. There the effective nuclear charges are near of these of the valence state of carbon V
41s2t1t2t32ptz:Zeff = 2.971 Zeff = 3.382 [10]. 相似文献
60.
Cheng Zhang Laurence Bensaid Donna McGregor Xikui Fang Robertha C. Howell Benjamin Burton-Pye Qunhui Luo Louis Todaro Lynn C. Francesconi 《Journal of Cluster Science》2006,17(2):389-425
Lanthanide complexes of polyoxometalates, including the α2-P2W17O61
10− ligand, have been pioneered by Michael T. Pope, to whom this paper is dedicated. Examination of the solid-state and solution behavior of lanthanide complexes of the α2-P2W17O61
10− ligand are reported here to identify trends that will facilitate rational synthesis of hybrid organic lanthanide polyoxometalate complexes. Therefore, combining our data with that obtained by Pope and others a number of trends come into view. It is clear that there are two structural types for the 1:1 or 2:2 [Ln(H2O)X(α2-P2W17O61)]2
14− species. The early lanthanides show a “cap to cap” structure that allows the Ln ion to be 9 coordinate and accommodates the longer bond lengths. The mid-late lanthanides show a “cap to belt” structure that allows the lanthanides to be 8 coordinate; this structural type is appropriate for the shorter bond lengths of the later lanthanides. The 1:1⇌1:2 equilibrium, that was observed by Pope for the Ce(III) analog is prevalent for the early- mid lanthanides. This equilibrium is slightly dependent on pH; however, cations have a major influence on this equilibrium. Larger, poorly hydrated cations appear to favor the 1:2 species for the early to mid lanthanides. Cations do not appear to influence the equilibrium for the later lanthanides; for all counterions, the 1:1 species was stable with no trace of the 1:2 species. Stability constants, K1 and K2, for the early to mid lanthanides were measured in this study by a competitive method and compared well with other published stability constant determinations. We suggest that the stability constants are not only dependent on the strength of interaction of the Ln with the α2-P2W17O61
10− ligand, but are also significantly influenced by the medium. The medium may bias the equilibria of the early-mid lanthanides and later lanthanides. The log K1/log K2 ratios are very close, suggesting that it is difficult to separate the 1:1 and 1:2 Ln: α2-P2W17O61
10− species.Electronic Supplementary Material Supplementary material for this article is available at and is accessible for authorized users.This paper is dedicated to Professor Michael T. Pope in honor of his substantial and sustained contributions to polyoxometalate chemistry and his inspiration to scientists working in the field. 相似文献