全文获取类型
收费全文 | 1675篇 |
免费 | 176篇 |
国内免费 | 331篇 |
专业分类
化学 | 2020篇 |
晶体学 | 19篇 |
力学 | 3篇 |
综合类 | 20篇 |
物理学 | 120篇 |
出版年
2024年 | 10篇 |
2023年 | 42篇 |
2022年 | 32篇 |
2021年 | 48篇 |
2020年 | 98篇 |
2019年 | 65篇 |
2018年 | 54篇 |
2017年 | 52篇 |
2016年 | 88篇 |
2015年 | 78篇 |
2014年 | 78篇 |
2013年 | 152篇 |
2012年 | 95篇 |
2011年 | 102篇 |
2010年 | 84篇 |
2009年 | 99篇 |
2008年 | 106篇 |
2007年 | 108篇 |
2006年 | 89篇 |
2005年 | 78篇 |
2004年 | 83篇 |
2003年 | 64篇 |
2002年 | 51篇 |
2001年 | 41篇 |
2000年 | 37篇 |
1999年 | 43篇 |
1998年 | 49篇 |
1997年 | 38篇 |
1996年 | 41篇 |
1995年 | 32篇 |
1994年 | 27篇 |
1993年 | 22篇 |
1992年 | 15篇 |
1991年 | 21篇 |
1990年 | 11篇 |
1989年 | 12篇 |
1988年 | 4篇 |
1987年 | 6篇 |
1986年 | 6篇 |
1985年 | 2篇 |
1984年 | 2篇 |
1983年 | 2篇 |
1981年 | 2篇 |
1979年 | 1篇 |
1978年 | 4篇 |
1977年 | 1篇 |
1975年 | 1篇 |
1974年 | 2篇 |
1973年 | 2篇 |
1968年 | 1篇 |
排序方式: 共有2182条查询结果,搜索用时 218 毫秒
81.
ESR study of free radicals formed upon UV irradiation of nitropentafluoroacetone in various solvents
B. L. Tumanskii V. I. D'yachenko Yu. I. Lyakhovetskii N. N. Bubnov S. P. Solodovnikov A. F. Kolomiets 《Russian Chemical Bulletin》1993,42(3):466-468
The formation of CF3C(O)CF2N(O.)O2CF2C(O)CF3 free radicals upon the UV irradiation of nitropentafluoroacetone (1) in toluene and mesitylene is established by ESR. The most likely cause of their formation is the one-electron oxidation of the solvents by photoexcited1 followed by decay of the radical anion formed from1 with the expulsion of an NO2 anion and attachment of the radical to a molecule of original1. The irradiation of 1 in triethylsilane results in the elimination of a fluoride ion and fixation of a CF3COCFN(O–)O' radical. UV irradiation of ketone1 in pentane results in the abstraction of a hydrogen atom from the solvent and the formation of a CF3COCF2N(OH)O ' radical.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 512–514, March, 1993. 相似文献
82.
Bis(cyclopentadienyl)methane-bridged Dinuclear Complexes, V[1]. – Heteronuclear Co/Rh-, Co/Ir-, Rh/Ir-, and Ti/Ir Complexes with the Bis(cyclopentadienyl)methane Dianion as Bridging Ligand* The lithium and sodium salts of the [C5H5CH2C5H4]- anion, 1 and 2 , react with [Co(CO)4I], [Rh(CO)2Cl]2, and [Ir(CO)3Cl]n to give predominantly the mononuclear complexes [(C5H5-CH2C5H4)M(CO)2] ( 3, 5, 7 ) together with small amounts of the dinuclear compounds [CH2(C5H4)2][M(CO)2]2 ( 4, 6, 8 ). The 1H- and 13C-NMR spectra of 3, 5 , and 7 prove that the CH2C5H5 substituent is linked to the π-bonded ring in two isomeric forms. Metalation of 5 and 7 with nBuLi affords the lithiated derivatives 9 and 10 from which on reaction with [Co(CO)4I], [Rh(CO)2Cl]2, and [C5H5TiCl3] the heteronuclear complexes [CH2(C5H4)2][M(CO)2][M′(CO)2] ( 11–13 ) and [CH2(C5H4)2]-[Ir(CO)2][C5H5TiCl2] ( 17 ) are obtained. Photolysis of 11 and 12 leads almost quantitatively to the formation of the CO-bridged compounds [CH2(C5H4)2][M(CO)(μ-CO)M′(CO)] ( 14, 15 ). According to an X-ray crystal structure analysis the Co/Rh complex 14 is isostructural to [CH2(C5H4)2][Rh2(CO)2(μ-CO)] ( 16 ). 相似文献
83.
A series of near infrared (NIR) absorbing dinuclear ruthenium dicarbonylhydrazine complexes (DCH-Ru),[{Ru(bpy)_2)_2μ-DCH]~(n ) (where bpy = 2,2'-bipyridinc and n = 2, 3 or 4), were prepared. The DCH-Ru complexes areelectrochromic in the NIR region with a high absorption coefficient at 1550-1600 nm typically over 10000 M~(-1)cm~(-1). DCH-Ru complex polymers with good NIR electrochromic properties were also obtained and processed to make a device foroptical attenuation at a wavelength of 1550 nm. The potential of these DCH-Ru polymers for use in a variable opticalattenuator has been demonstrated with an attenuating power at the 1550-nm telecommunication wavelength over 7.0 dB permicron of polymer film thickness. Other classes of NIR active materials are the pentacenediquinones and the correspondingpoly(ether pentacenediquinone)s. These polymers can be electrochemically reduced to the corresponding semiquinone(radical anion) having NIR absorption within a telecom window (e. g., 1310 nm). 相似文献
84.
The new oxonitridosilicates Ba4?xCaxSi6N10O have been synthesized by means of high‐temperature synthesis in a radio‐frequency furnace, starting from calcium, barium, silicon diimide and amorphous silicon dioxide. The maximum reaction temperature was at about 1450 °C. The solid solution series Ba4?xCaxSi6N10O with a phase width 1.81 ≤ x ≤ 2.95 was obtained. The crystal structure of Ba1.8Ca2.2Si6N10O was determined by X‐ray single‐crystal structure determination (P213, no. 198), a = 1040.2(1) pm, Z = 4, wR2 = 0.082). It can be described as a highly condensed network of corner‐sharing SiN4 and SiON3 tetrahedra, the voids of which are occupied by the alkaline earth ions. The structure is isotypic with that of BaEu(Ba0.5Eu0.5)YbSi6N11. In the 29Si solid‐state MAS‐NMR spectrum two isotropic resonances at ?50.0 and ?53.6 ppm were observed. 相似文献
85.
I. B. Sivaev V. I. Bragin V. I. Bregadze N. A. Votinova S. Sjoberg 《Russian Chemical Bulletin》2004,53(9):2092-2095
Reactions of an amino derivative of the closo-decaborate anion [1-B10H9NH3]– with aromatic aldehydes afforded Schiff bases [1-B10H9NH=CHAr]– (Ar=Ph, C6H4-2-OMe, or C6H4-4-NHCOMe). The reduction of the latter with sodium borohydride gave the corresponding benzylamino derivatives [1-B10H9NH2CH2Ar]–.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2004–2007, September, 2004. 相似文献
86.
Tamm J. Johanson U. Marandi M. Tamm T. Tamm L. 《Russian Journal of Electrochemistry》2004,40(3):344-348
Experimental and theoretical methods have been used for characterization of the properties of polypyrrole films. The AFM studies show that the morphology of polypyrrole (PPy) films on polycrystalline gold electrodes at the first stages of synthesis depends on the structure of the metal surface. It was established that mobility of anions depends remarkably on the rate of electrodeposition of the polymer film. If PPy film was deposited at relatively low current density, mobility of ClO-
4 anion was not high enough to guarantee electroneutrality during redox cycling and cations take part in this process especially when Li+ cations were replaced by more mobile + cations. Semiempirical (AM1 and PM3) quantum-chemical methods were used for theoretical studies. It was established that different size and charge of the anions together with the variation in doping levels give rise to a different optimal conformation of oligopyrrole cations which, in turn, define the resulting polymer to be either all-anti (common linear chains) or all-syn (formation of helical structures) or a combination of the two. 相似文献
87.
Fan J Gan L Kawaguchi H Sun WY Yu KB Tang WX 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(16):3965-3973
Six noninterpenetrating organic-inorganic hybridized coordination complexes, [Mn(3)(2)(H(2)O)(2)](ClO(4))(2).2 H(2)O (5), [Mn(3)(2)(H(2)O)(2)](NO(3))(2) (6), [Mn(3)(2)(N(3))(2)].2 H(2)O (7), [Cu(3)(2)(H(2)O)(2)](ClO(4))(2) (8), [Mn(4)(2)(H(2)O)(SO(4))].CH(3)OH.5 H(2)O (9) and [Mn(4)(2)](ClO(4))(2) (10) were obtained through self-assembly of novel tripodal ligands, 1,3,5-tris(1-imidazolyl)benzene (3) and 1,3-bis(1-imidazolyl)-5-(imidazol-1-ylmethyl)benzene (4) with the corresponding metal salts, respectively. Their structures were determined by X-ray crystallography. The results of structural analysis of complexes 5, 6, 7, and 8 with rigid ligand 3 indicate that their structures are mainly dependant on the nature of the organic ligand and geometric need of the metal ions, but not influenced greatly by the anions and metal ions. While in complexes 9 and 10, which contain the flexible ligand 4, the counteranion plays an important role in the formation of the frameworks. Entirely different structures of complexes 5 and 10 indicate that the organic ligands greatly affect the structures of assemblies. Furthermore, in complexes 5 and 6, the counteranions located between the cationic layers can be exchanged by other anions. Reversible anion exchanges between complexes 5 and 6 without destruction of the frameworks demonstrate that 5 and 6 can act as cationic layered materials for anion exchange, as determined by IR spectroscopy, elemental analyses, and X-ray powder diffraction. 相似文献
88.
The reaction of esterification of benzoic acid with benzyl chloride was chosen as a model reaction to study the esterification by SN2 promoted by tertiary amine as deprotonating agent. The use of ionic liquid (IL) 1,3-dimethylimidazolium methanesulfonate [MMIm][OMs] as reaction medium has proven to give quantitative yield of the ester, but interestingly the reaction does occur even in solvent-free conditions, where the acid + the amine form a liquid system (a protic IL) in situ. This last methodology was extended to several carboxylic acids in conditions of atom economy (i.e., without excess of any reagent), giving moderately good yields of esters (54–78%) recovered by weight in pure form. 相似文献
89.
90.
V. S. Kushawaha 《光谱学快报》2013,46(10):633-645
An extensive calculation was carried out using the precisely measured value of the Q-band heads and the following molecular constants for the C2π1 2 and the X2σ states, which are responsible for the Green Band System of BaF, were determined. 相似文献