全文获取类型
收费全文 | 4084篇 |
免费 | 53篇 |
国内免费 | 8篇 |
专业分类
化学 | 2769篇 |
晶体学 | 26篇 |
力学 | 56篇 |
数学 | 577篇 |
物理学 | 717篇 |
出版年
2018年 | 28篇 |
2017年 | 29篇 |
2016年 | 41篇 |
2015年 | 42篇 |
2014年 | 44篇 |
2013年 | 102篇 |
2012年 | 106篇 |
2011年 | 148篇 |
2010年 | 97篇 |
2009年 | 100篇 |
2008年 | 124篇 |
2007年 | 146篇 |
2006年 | 140篇 |
2005年 | 154篇 |
2004年 | 133篇 |
2003年 | 115篇 |
2002年 | 112篇 |
2001年 | 89篇 |
2000年 | 108篇 |
1999年 | 81篇 |
1998年 | 65篇 |
1997年 | 78篇 |
1996年 | 82篇 |
1995年 | 86篇 |
1994年 | 63篇 |
1993年 | 87篇 |
1992年 | 73篇 |
1991年 | 52篇 |
1990年 | 44篇 |
1989年 | 41篇 |
1988年 | 55篇 |
1987年 | 51篇 |
1986年 | 55篇 |
1985年 | 67篇 |
1984年 | 50篇 |
1983年 | 41篇 |
1982年 | 53篇 |
1981年 | 64篇 |
1980年 | 55篇 |
1979年 | 66篇 |
1978年 | 51篇 |
1977年 | 59篇 |
1976年 | 52篇 |
1975年 | 41篇 |
1974年 | 50篇 |
1973年 | 34篇 |
1972年 | 27篇 |
1971年 | 31篇 |
1970年 | 29篇 |
1930年 | 21篇 |
排序方式: 共有4145条查询结果,搜索用时 0 毫秒
51.
A new synthetic route for the preparation of the betain-like compound (CH3N)6P4F8 from (CH3NPF3)2,N-methyl-hexamethyldisilazane andN,N-dimethyl-urea has been found. The steps of this multi-stage reaction could be rationalized to a far extent.
10. Mitteilung:Kubjacek M., Utvary K., Mh. Chem.112, 305 (1981). 相似文献
52.
53.
54.
The synthesis of endo- and exo-13-oxo-4b, 5, 12, 12a-tetrahydro-5, 12-ethanoindeno[2,3-b]anthracene ( 23 ; Schemes 1 and 2), exo- and endo-11-oxo-4b, 5, 10, 10a-tetrahydro-5, 10-ethano-indeno[2,3-b]naphthalene ( 31 ; Scheme 3), 1,2,3,4,4a,9a-hexahydro?1,4-(peri-naphthaleno)-fluoren-9-one (36; Scheme 4), and the corresponding hydrocarbons of the stereoisomeric ketone pairs 23 and 36 , is described. 相似文献
55.
Synthesis, IR Spectrum, and Crystal Structure of N,N'-Bis(trimethylsilyl)benzamidinium Tetrachloroferrate(III) The title compound [C6H5? C(NHSiMe3)2][FeCl4] is obtained by the reaction of FeCl3 with N,N,N'-tris(trimethylsilyl)benzamidine in the presence of tetrahydrofurane, forming yellow, moisture sensitive crystals. The compound is characterized by its IR spectrum as well as by an X-ray structure determination. Space group P21/n, Z = 8, 5974 independent observed reflexions, R = 0.066. The lattice dimensions are at ?70°C: a = 2110.7, b = 1109.5, c = 2120.4 pm; β = 111.17º. The compound forms ion pairs, in which the H atoms of the amidinium cation are coordinated with one chlorine ligand of the FeCl4? ion in a chelating manner. 相似文献
56.
Coexistence Relations, Preparation and Properties of Ternary Compounds in the System Cu/Mo/O The phase diagram of the ternary system Cu/Mo/O is presented at 773 K. The compounds CuMoO4, Cu3Mo2O9, Cu4Mo5O17, Cu6Mo5O18, Cu4–xMo3O12, and CuxMoO3 are found to be thermodynamical stable. The homogeneity range of Cu4–xMo3O12 runs to x = 0.1–0.2. Single crystals of CuMoO4 and Cu3Mo2O9 were grown by chemical transport reactions with TeCl4, Cl2, HCl, and Br2 as transport agent. The results were compared with thermochemical calculations. The decomposition of CuMoO4 and Cu3Mo2O9 was investigated with thermal analysis and decompositon pressure measurements. 相似文献
57.
Enantioselective Reactions on Porphine Type Nickel Complexes The thermodynamically controlled addition of alcohols to (+)-(1R)-[1-methyl-8H-HDP]nickelperchlorate ( 1 ; e.e. 92%) yields exclusively the corresponding cis-1,11-disubstituted porphinoids. Chemical transformation of functional groups in the alkoxy side-chain of the chiral addition product followed by acid catalyzed elimination yields the derived alcohols and 1 . By this procedure, the following enantioselective transformations were studied: methylation of meso-2,3-butandiol ( 5 ) to (+)-(2R,3S)-3-methoxy-2-butanol ( 8a ; e.e. 87%), diimide reduction of 2-ethylallyl alcohol ( 9 ) to (+)-(2R)-2-methyl-1-butanol ( 12a ; e.e. 15%), and hydride reduction of 4-hydroxy-2-butanone ( 13 ) to (+)-(3S)-1,3-butandiol ( 16a ; e.e. 20%). Addition of 2,2-dimethyl-1,3-propandiol ( 17 ) to 4 , followed by esterification of the free hydroxy group with trifluoromethanesulfonic anhydride and solvolysis of the sulfonate 19 yielded a bridged complex with unrearranged alkyl chain for which structure 20 is proposed. 相似文献
58.
Cayuela E Jalón FA Manzano BR Espino G Weissensteiner W Mereiter K 《Journal of the American Chemical Society》2004,126(22):7049-7062
Diastereomerically pure complexes of formula CpRuCl(PP) and CpRuH(PP) with chiral ferrocenyl diphosphines were prepared and the selectivity of proton-transfer processes over the monohydride compounds with different acids was studied. With 1 equiv of HBF(4) the cis-dihydrogen and trans-dihydride complexes were formed while with 3 equiv of CF(3)CO(2)H the trans-dihydride derivative was the only product. However, the use of 1 equiv of CF(3)CO(2)H led to a dihydrogen bonded complex with an extremely short RuH...HO(2)CF(3) interaction that exhibits proton-hydride exchange. Using the labeled acid CF(3)CO(2)D, a stereoselective transference of the deuteron was demonstrated that implies the previous epimerization of the monohydride and the subsequent attack of the acid in the position previously occupied by the hydride. 相似文献
59.
60.
Mei Y Wu T Xu C Langenbach KJ Elliott JT Vogt BD Beers KL Amis EJ Washburn NR 《Langmuir : the ACS journal of surfaces and colloids》2005,21(26):12309-12314
A simple yet versatile method was developed to prepare a low-density polymerization initiator gradient, which was combined with surface-initiated atom transfer radical polymerization (ATRP) to produce a well-defined poly(2-hydroxyethyl methacrylate) (HEMA) gradient substrate. A smooth variation in film thickness was measured across the gradient, ranging from 20 A to over 80 A, but we observed a nonmonotonic variation in water contact angle. Fits of X-ray reflectivity profiles suggested that at the low graft density end, the polymer chain structure was in a "mushroom" regime, while the polymer chains at high graft density were in a "brush" regime. It was found that the "mushroom" region of the gradient could be made adhesive to cells by adsorbing adhesion proteins, and cell adhesion could be tuned by controlling the density of the polymer grafts. Fibroblasts were seeded on gradients precoated with fibronectin to test cellular responses to this novel substrate, but it was found that cell adhesion did not follow the expected trend; instead, saturated cell adhesion and spreading was found at the low grafting density region. 相似文献