全文获取类型
收费全文 | 5488篇 |
免费 | 190篇 |
国内免费 | 12篇 |
专业分类
化学 | 4029篇 |
晶体学 | 51篇 |
力学 | 51篇 |
数学 | 778篇 |
物理学 | 601篇 |
无线电 | 180篇 |
出版年
2021年 | 54篇 |
2020年 | 63篇 |
2019年 | 60篇 |
2018年 | 37篇 |
2017年 | 40篇 |
2016年 | 111篇 |
2015年 | 125篇 |
2014年 | 135篇 |
2013年 | 213篇 |
2012年 | 265篇 |
2011年 | 293篇 |
2010年 | 205篇 |
2009年 | 197篇 |
2008年 | 289篇 |
2007年 | 223篇 |
2006年 | 255篇 |
2005年 | 221篇 |
2004年 | 234篇 |
2003年 | 177篇 |
2002年 | 163篇 |
2001年 | 93篇 |
2000年 | 82篇 |
1999年 | 80篇 |
1998年 | 72篇 |
1997年 | 78篇 |
1996年 | 85篇 |
1995年 | 72篇 |
1994年 | 76篇 |
1993年 | 68篇 |
1992年 | 68篇 |
1991年 | 76篇 |
1990年 | 57篇 |
1989年 | 58篇 |
1988年 | 57篇 |
1987年 | 55篇 |
1986年 | 66篇 |
1985年 | 85篇 |
1984年 | 97篇 |
1983年 | 52篇 |
1982年 | 74篇 |
1981年 | 95篇 |
1980年 | 75篇 |
1979年 | 67篇 |
1978年 | 78篇 |
1977年 | 46篇 |
1976年 | 68篇 |
1975年 | 53篇 |
1973年 | 52篇 |
1971年 | 41篇 |
1970年 | 35篇 |
排序方式: 共有5690条查询结果,搜索用时 15 毫秒
81.
New five-coordinate Pt(IV) complexes [{(o-R2-p-R'-C6H2)NC(R' ')}2CH]PtMe3 (R, R', R' ' = alkyl or H) are reported. The complex with R = Me, R' = tBu, R' ' = Me generates unsaturated Pt(II) species capable of alkane C-H bond activation and stoichiometric dehydrogenation. 相似文献
82.
Darbost U Rager MN Petit S Jabin I Reinaud O 《Journal of the American Chemical Society》2005,127(23):8517-8525
The host-guest properties of calix[6]tren 1 have been evaluated. The receptor is based on a calix[6]arene that is covalently capped at the narrow rim by a tren unit. As a result, the system presents a concave hydrophobic cavity with, at its bottom, a grid-like nitrogenous core. Despite its well-defined cavity and opening to the outside at the large rim, 1 did not behave as a good receptor for neutral molecules in chloroform. However, it exhibited efficient endo-complexation of ammonium guests. By contrast, the per-protonated host, 1.4H(+), behaved as a remarkable receptor for small organic molecules. The complexation is driven by a strong charge-dipole interaction and hydrogen bonds between the polar guest and the tetracationic cap of the calixarene. Finally, coordination of Zn(2+) to the tren core led to the asymmetrization of calixarene cavity and to the strong but selective endo-binding of neutral ligands. This study emphasizes the efficiency of a receptor presenting a concave hydrophobic cavity that is polarized at its bottom. The resulting combination of charge-dipole, hydrogen bonding, CH-pi, and van der Waals interactions highly stabilizes the supramolecular architectures. Also, importantly, the tren cap allows the tuning of the polarization, offering either a basic (1), a highly charged and acidic (1.4H(+)), or a coordination (1.Zn(2+)) site. As a result, the system proved to be highly versatile, tunable, and interconvertible in solution by simple addition of protons, bases, or metal ions. 相似文献
83.
Nina Ulrich 《Analytical and bioanalytical chemistry》1998,360(7-8):797-800
An on-line method for the analysis of Sb(III), Sb(V) and trimethylstiboxide (TMSbO) is presented. The separation is performed
using ion chromatography (IC) on a strong anion-exchange column with phthalic acid plus 2% acteone at pH 5 as mobile phase.
The chromatographic system is coupled to an ICP-MS as detector. The influence of different complexing agents on the chromatographic
behavior of the antimony species is studied. Rather stable complexes of Sb(III) seem to be formed with citrate and tartrate
under the experimental conditions. TMSbO forms a dianionic species with citrate in contrast to the otherwise monoanionic complex.
Received: 31 Juli 1997 / Revised: 8 December 1997 / Accepted: 11 December 1997 相似文献
84.
85.
The acidity functions of aqueous trifluoroacetic and trifluoromethanesulphonic acid mixtures, and aqueous hexafluoropropane-2, 2-diol solutions, have been determined by differential pulse polarography. The apparent shift of the half-wave potential for the ferrocene—ferricinium couple, as the solvent composition is changed, is used to indicate the change in potential of a glass electrode; acidity is measured as the HGF acidity function. The densities of two of these solvent systems as a function of composition are also reported. Trifluoromethanesulphonic acid—water mixtures represent the strongest aqueous acid solvent system so far studied. 相似文献
86.
A versatile process for the preparation of a number of 3-thio-substituted furans 1–4 is described. These products have very low odor thresholds and are thus potent flavor compounds. Fur-3-yl thiocyanates 10a , b as well as other S-containing analogues ( 2b , 7a , b , and 8 ) were prepared by a Michael-type addition of thiocyanic acid, thioacetic acid, alakanethiols, and sodium thiosulfate to alkynones 6 or 15 , followed by cyclization (Schemes 3 and 4). The thiocyanates 10a, b were converted to mixed disulfides 3 , symmetric disulfides 4 , thioethers 2 , and thiols 1 , using ‘hard’ or ‘soft’ nucleophiles or reducing agents, respectively (Scheme 6). 相似文献
87.
N(SCl)2⊕ [MoCl5(NSCl)]?, a Chlorothionitrene Complex of Molybdenum (VI) . The title compound is formed together with MoCl3(N3S2) by the reaction of MoCl4 or MoCl5 with (NSCl)3 in CH2Cl2. The black, crystalline compound was characterized by its i.r. spectrum and an X-ray crystal structure determination. N(SCl)2⊕[MoCl5(NSCl)]? crystallizes in the monoclinic space group P21/n with four formula units per unit cell. The lattice constants are a = 716.3, b = 1627.4, c = 1178.9 pm and β = 100.90°. The [MoCl5(NSCl)]? ion posseses an almost linear Mo = N = S grouping with bond lengths that can be interpreted as double bonds. Crystal data for AsPh4[MoCl5(NSCl)] are reported. 相似文献
88.
The mer‐octahedral complexes(2‐carbonyl)(4‐Me)(6‐tBu)phenolato[C,O]hydridotris(trimethylphosphine)cobalt(III) ( 1 ) or ‐(1‐carbonyl)(2‐oxo)(1,2‐diphenylethene)[C,O]hydridotris(trimethylphosphine)cobalt(III) ( 2 ) via formal insertion of propynoic acid ethyl ester into Co‐H functions afford pentacoordinate vinylcobalt(III) 3 and 4 , respectively, that are diamagnetic and attain a square pyramidal structure as exemplified by an X‐ray diffraction analysis of 3 . 相似文献
89.
1,3-Oxazolidin-4-ones and 1,3-oxazin-4-ones were synthesized by formal cyclocondensation of imines with α- or β-hydroxy acids. 相似文献
90.
The synthesis of the indoles 7 , 15 , 16 with a 3-methoxyphenyl group, attached via an α-side chain of 1,2,or 3 CH2 units, is reported. These compounds, after appropriate protection at C(3), were transformed into the N-[(dimethylamino)methyl]indoles 22 , 23 , and 24 , respectively. When treated with AcCl, these N-Mannich bases gave, in two cases, stable N-(chloromethyl)indoles 25 and 26 . In the presence of SnCl4, ring closure occurred via electrophilic attack of 1-methylideneindolium ions on the methoxyphenyl group. Formation of seven-membered rings (→ 27 , 28 ) and eight-membered rings (→ 29 ) was found to be a favorable process. Cyclization to six-membered rings did not occur within this series. 相似文献