全文获取类型
收费全文 | 2389篇 |
免费 | 16篇 |
国内免费 | 29篇 |
专业分类
化学 | 685篇 |
晶体学 | 6篇 |
力学 | 20篇 |
综合类 | 12篇 |
数学 | 73篇 |
物理学 | 166篇 |
综合类 | 1472篇 |
出版年
2023年 | 4篇 |
2022年 | 16篇 |
2021年 | 9篇 |
2020年 | 20篇 |
2019年 | 202篇 |
2018年 | 41篇 |
2017年 | 20篇 |
2016年 | 15篇 |
2015年 | 41篇 |
2014年 | 107篇 |
2013年 | 92篇 |
2012年 | 131篇 |
2011年 | 203篇 |
2010年 | 168篇 |
2009年 | 122篇 |
2008年 | 112篇 |
2007年 | 105篇 |
2006年 | 104篇 |
2005年 | 69篇 |
2004年 | 48篇 |
2003年 | 58篇 |
2002年 | 33篇 |
2001年 | 20篇 |
2000年 | 25篇 |
1999年 | 18篇 |
1998年 | 14篇 |
1997年 | 14篇 |
1996年 | 7篇 |
1995年 | 9篇 |
1994年 | 8篇 |
1993年 | 7篇 |
1992年 | 5篇 |
1988年 | 5篇 |
1986年 | 5篇 |
1985年 | 39篇 |
1984年 | 31篇 |
1983年 | 26篇 |
1982年 | 28篇 |
1981年 | 86篇 |
1980年 | 81篇 |
1979年 | 28篇 |
1978年 | 43篇 |
1977年 | 49篇 |
1976年 | 39篇 |
1975年 | 40篇 |
1974年 | 34篇 |
1973年 | 31篇 |
1968年 | 6篇 |
1958年 | 3篇 |
1957年 | 3篇 |
排序方式: 共有2434条查询结果,搜索用时 31 毫秒
51.
Lorraine P. McDonnell Bushnell Eric R. Evitt Robert G. Bergman 《Journal of organometallic chemistry》1978,157(4):445-456
Reactions of η5-cyclopentadienylbis(triphenylphosphine)cobalt(I) (5) with several 2,n-alkadiynes (2) were investigated. Each of these reactions leads initially to a material in which one of the acetylene functional groups is π-coordinated to cobalt; this complex then undergoes conversion to a metallocycle. In cases where the two acetylene functions are connected by three- and four-carbon bridges (2b, 2c), metallocycles formed by intramolecular reaction of two acetylene functions in the same molecule may be isolated. In cases where the acetylene functions are joined by larger or smaller bridges, the reactions are more complex, and both inter- and intramolecular metallocycles are formed. Reactions of 5 with 1,8-bis(trimethylsilyl)-1,7-octadiyne (16) gives an isolable crystalline mono-acetylene complex (17), this material is stable in the solid state but undergoes conversion to metallocycle (18) in benzene solution. The relationship of these results to the mechanism of the CpCo(CO)2-catalyzed benzocycloalkene synthesis is discussed; it is suggested that intramolecular metallocycles are intermediates in reactions leading to benzocyclopentanes and -cyclohexenes, but intermolecular metallocycles are probably involved in reactions leading to benzocyclobutenes. 相似文献
52.
Ailing Zhu Yingying Guo Guangliang Liu Maoyong Song Yong Liang Yong Cai Yongguang Yin 《中国化学快报》2019,30(12):2241-2244
Dark formation of hydroxyl radical upon oxidation of reduced iron minerals plays an important role in the degradation and transformation of organic and inorganic pollutants. Herein, we compared the hydroxyl radical formation from various reduced iron minerals at different redox conditions. OH production was generally observed from the oxidation of reduced iron minerals, following the order: mackinawite (FeS) > reduced nontronite (iron-bearing smectite clay) > pyrite (FeS2) > siderite (FeCO3). Structural Fe2+ and dissolved O2 play critical roles in OH production from reduced iron minerals. OH production increases with decreasing pH, and Cl? has little effect on this process. More importantly, dissolved organic matter significantly enhances OH production, especially under O2 purging, highlighting the importance of this process in ambient environments. This sunlight-independent pathway in which OH forms during oxidation of reduced iron minerals is helpful for understanding the degradation and transformation of various inorganic and organic pollutants in the redox-fluctuation environments. 相似文献
53.
trans-Pd(NO3)H(PCy3)2 (I) when treated with Et4NCl forms the hydride trans-PdClH(PCy3)2 which in turn reacts with AgPF6 in acetonitrile to give trans-[PdH(CH3CN)(PCy3)2]PF6 (III). Both I and III react smoothly with acetylenes containing one electron-withdrawing group to give alkenyl products. The geometry of the resulting alkenyl ligand implies that cis addition has occurred and that the hydridic hydrogen adds to the acetylenic carbon containing the electron-withdrawing group.Acetylenes containing two electron-withdrawing groups give mixtures from which both alkenyl and zerovalent acetylene compounds can sometimes be isolated. In the presence of proton sponge, monosubstituted acetylenes still give alkenyl products while those substituted with two electron-withdrawing groups give the zerovalent products in good yield. The relevance of these results to an understanding of the nature of the migratory insertion reaction is discussed. 相似文献
54.
Components, of the magnetizability tensor for the B1Σ+u and a 3Σ+g states ot the hydrogen molecule have been calculated for fixed bond lengths near equilibrium. Explicitly correlated “generalised James-Coolidge” type wavefunctions were used. It is found thilt in the B 1Σ+u state the molecular magnetizability is a positive quantity. 相似文献
55.
Bromoacetyl chloride and bromoacetyl bromide are studied by gas phase electron diffraction at nozzle-tip temperatures of 70°C and 77°C, respectively. Both compounds exist as mixtures of anti and gauche conformers. The mole fraction anti, with uncertainties estimated at 2σ, was found to be 0.474(0.080) for bromoacetyl chloride and 0.615(0.069) for bromoacetyl bromide. The results for the distance (ra)and angle (∠α) parameters, with parenthesized uncertainties of 2σ including estimated uncertainty in the electron wave length and correlation effects are as follows: (1) bromoacetyl chloride, r(C-H) = 1.086(0.062) Å, r(CO) = 1.188(0.009) Å, r(C-C) = 1.519(0.018) Å, r(C-Cl) = 1.789(0.011) Å, r(C-Br) = 1.935(0.012) Å, ∠C-CO = 127.6(1.3)°, ∠C-C-Cl = 111.3(1.1)°, ∠C-C-Br = 111.0(1.5)°, ∠H-C-H = 109.5°(assumed), /o (gauche torsion angle relative to 0° for the anti form) = 110.0°(assumed); (2) bromoacetyl bromide, r(C-H) =1.110(0.088) Å, r(C=O) = 1.175(0.013) Å, r(C-C) = 1.513(0.020) Å, r(CO-Br) = 1.987(0.020) Å, r(CH2-Br) = 1.915(0.020) Å, ∠C-CO = 129.4(1.7)°, ∠CH2-CO-Br = 110.7(1.5)°, ∠CO-CH2-Br = 111.7(1.8)°, ∠H-C-H = 109.5°(assumed), ∠ø (gauche torsion angle relative to 0° for the anti form) = 105.0°(assumed). The structural results are discussed in connection with the structures of related molecules. 相似文献
56.
Y. Kuwahara H. Fukami R. Howard S. Ishii F. Matsumura W.E. Burkholder 《Tetrahedron》1978,34(12):1769-1774
Chemical an spectroscopic evidence is presented to show that 2,3-dihydro-2,3,5-trimethyl-6-(1-methyl-2-oxobutyl)-4H-pyran-4-one (10) is the sex pheromone produced by the female drugstore beetle, Stegobium paniceum L. 相似文献
57.
Assignments for oxalic acid in solution are re-examined. A detailed assignment of the IR and Raman spectra of the acid oxalate ion is presented for the first time. Raman spectroscopy is used to study the first ionization of oxalic acid. 相似文献
58.
An investigation of electronic structure in some neurotransmitter drugs has been made using the CNDO/2 semi-empirical molecular orbital method.The electronic structure has been conveniently characterized by the electronic parameters nett atomic population (NAP) and bond index (BI). A variation of these electronic parameters with respect to conformation has been studied and has been found unlikely to exceed 0.1 e in most. cases. Further, the useful extent to which the electronic parameters of some commonly occurring functional groups may be regarded as conformationally invariant has been demonstrated. Also presented are (i) a discussion on the intramolecular close-approach of functional groups — the interaction between terminal —COO? and ?NH3+ groups of α-ω anaino acids is explicitly considered; (ii) an enquiry into the extension of ‘standard’ (idealized) geometry models in the elucidation of electronic structure.The implication of the results and observations presented here are briefly discussed with reference to classical and quantum structure-activity studies of drug molecules. 相似文献
59.
The Electron impact mass spectra of (CO)3 MC6H5—X complexes (M = Cr, W; X = OCH3, OC4H9, CO2CH3, CO2C4H9) were recorded. From metastable transitions and by high-resolution measurements complete fragmentation diagrams were obtained; in some cases comparative structure determinations of fragment ions were carried out by collisional activation. The fragmentation of the tungsten complexes considerably differs from that of the chromium compounds. The differences may be attributed to the stronger-electrophilic character as well as to the more pronounced tendency of tungsten to attain higher oxidation states. 相似文献
60.
Let (F,G) be a pair of matrices defined over an arbitrary field, Fn × n, Gn × m. Consider the natural action of GLn x GLm on this pair given by (F,G) ? (gFg-1,gGh-1), where (g,h) ∈ GLn × GLm. This action is of interest in system theory as well as the representation theory of quivers. In this paper we study the stabilizer subgroup of this action stab(F,G), i.e. . 相似文献