全文获取类型
收费全文 | 5590篇 |
免费 | 147篇 |
国内免费 | 45篇 |
专业分类
化学 | 3884篇 |
晶体学 | 56篇 |
力学 | 128篇 |
综合类 | 1篇 |
数学 | 810篇 |
物理学 | 903篇 |
出版年
2022年 | 36篇 |
2021年 | 43篇 |
2020年 | 71篇 |
2019年 | 69篇 |
2018年 | 48篇 |
2017年 | 46篇 |
2016年 | 112篇 |
2015年 | 106篇 |
2014年 | 120篇 |
2013年 | 255篇 |
2012年 | 279篇 |
2011年 | 395篇 |
2010年 | 168篇 |
2009年 | 161篇 |
2008年 | 321篇 |
2007年 | 327篇 |
2006年 | 324篇 |
2005年 | 310篇 |
2004年 | 280篇 |
2003年 | 209篇 |
2002年 | 210篇 |
2001年 | 87篇 |
2000年 | 92篇 |
1999年 | 73篇 |
1998年 | 58篇 |
1997年 | 59篇 |
1996年 | 84篇 |
1995年 | 61篇 |
1994年 | 73篇 |
1993年 | 84篇 |
1992年 | 67篇 |
1991年 | 58篇 |
1990年 | 50篇 |
1989年 | 38篇 |
1988年 | 49篇 |
1987年 | 32篇 |
1986年 | 37篇 |
1985年 | 68篇 |
1984年 | 63篇 |
1983年 | 55篇 |
1982年 | 76篇 |
1981年 | 62篇 |
1980年 | 63篇 |
1979年 | 54篇 |
1978年 | 58篇 |
1977年 | 52篇 |
1976年 | 48篇 |
1975年 | 51篇 |
1974年 | 46篇 |
1973年 | 30篇 |
排序方式: 共有5782条查询结果,搜索用时 15 毫秒
71.
[structure: see text] An improved, third-generation, total synthesis of (+)-discodermolide, a potent microtubule-stabilizing anticancer agent of marine sponge origin, is achieved in 11.1% yield over 21 steps. Key steps include a Still-Gennari HWE olefination, performed using NaH as the base, between C1-C8 beta-ketophosphonate 7 and C9-C24 aldehyde 8, introducing the (8Z)-alkene with 10:1 selectivity, and K-Selectride reduction of the derived enone 16, installing the (7S)-configuration. 相似文献
72.
Jensen BP Smith CJ Bailey CJ Rodgers C Wilson ID Nicholson JK 《Rapid communications in mass spectrometry : RCM》2005,19(4):519-524
Inductively coupled plasma mass spectrometry (ICPMS) has been used to determine the rate and routes of excretion of bromine following the intraperitoneal administration (50 mg kg(-1)) of 2-, 3- and 4-bromobenzoic acids to male bile-duct-cannulated rats. Analysis of urine and bile for (79/81)Br using ICPMS showed that all three bromobenzoic acids were rapidly excreted (82-98%) within 48 h of dosing, primarily via the urine. High-performance liquid chromatography/inductively coupled plasma mass spectrometry (HPLC/ICPMS) was then used to obtain metabolite profiles for bile and urine. These profiles revealed that extensive metabolism had taken place, with the unchanged bromobenzoic acids forming a minor part of the total of compound-related material detected. Concomitant MS studies, supplemented by alkaline hydrolysis, enabled the identification of the major metabolite of all three of the bromobenzoic acids as a glycine conjugate. Ester glucuronide conjugates were also identified, but formed only a small proportion of total. 相似文献
73.
The appearance of the characteristic crystalloid core of rat liver peroxisomes is emulated by the electron microscopic (EM) appearance of highly purified urate oxidase prepared from the same tissue. The purity of the enzyme preparation was established by gel electrophoresis under various conditions and the specific enzyme activity was at least as high as any previously reported. The amino acid composition of urate oxidase was determined. As additional evidence for close association of the peroxisomal core with urate oxidase, it was demonstrated that the biphasic changes in rat liver urate oxidase activity in response to prolonged starvation were paralleled by changes in the EM appearance of peroxisomes. Under comparable conditions catalase, another peroxisomal enzyme, did not show the same changes in activity as did urate oxidase. Evidence for the possible identity of urate oxidase with the peroxisomal crystalloid of rat liver has been presented, all materials having been obtained from, and experiments performed with, the rat. 相似文献
74.
Gianluca Pozzi Marco Cavazzini Orsolya Holczknecht Silvio Quici Ian Shepperson 《Tetrahedron letters》2004,45(22):4249-4251
A fluorous-tagged TEMPO radical has been prepared and its catalytic activity in the chemoselective oxidation of alcohols to carbonyl compounds has been investigated. The new fluorous radical proved to be an efficient, selective and easily recoverable catalyst, which can be conveniently used in standard organic solvents and then isolated and recycled by fluorous liquid-liquid extraction. 相似文献
75.
Oxidation reactions of an anionic gallium(I) N-heterocyclic carbene analogue with group 16 compounds
The reactivity of an anionic gallium(I) heterocycle, [K(tmeda)][:Ga([N(Ar)C(H)]2)], Ar = C6H3Pr(i)2-2,6, towards sources of elemental chalcogens and diorgano-dichalcogenides has been investigated and comparisons drawn with the reactivity of the valence isoelectronic N-heterocyclic carbene class of ligand. The reactions of the heterocycle with N2O or (Te)PEt3 yielded the dimeric, dianionic gallium(III) complexes, [K(L)]2[(mu-E)Ga([N(Ar)C(H)]2)]2, E = O, L = tmeda; E = Te, L = THF. Treatment of [K(tmeda)][:Ga([N(Ar)C(H)]2)] with the diphenyl dichalcogenides, PhEEPh, E = Se or Te, gave the one dimensional polymer, [K[(PhSe)2Ga([N(Ar)C(H)]2)]]infinity and the monomeric complex, [K(OEt2)3][(PhTe)2Ga([N(Ar)C(H)]2)], respectively. The X-ray crystal structures of the four complexes are reported. 相似文献
76.
Hale KJ Frigerio M Manaviazar S Hummersone MG Fillingham IJ Barsukov IG Damblon CF Gescher A Roberts GC 《Organic letters》2003,5(4):499-502
[structure: see text] The synthesis of two truncated bryostatin analogues 2 and 3 is described. High-field NMR measurements on the C-ring analogue 3 in C(2)H(3)CN containing 25% (2)H(2)O have shown that it binds to the CRD2 of human PKC-alpha at virtually the same position as phorbol-13-acetate (PA) and bryostatin 1 (1). NMR titration studies have also revealed that 3 binds to the CRD2 with a potency similar in magnitude to PA but much less potently than 1. 相似文献
77.
The products of the reaction of butadiene with diethyl malonate catalysed by a palladium complex and of butadiene with acetaldehyde catalysed by a nickel(0) complex have been used in two syntheses of 3,7-dimethylpentadecan-2-ol. 相似文献
78.
[reaction: see text] An effective strategy has been developed for the rapid and efficient one-pot synthesis of 2-aryl-5-substituted-2,3-dihydrobenzofurans from readily available o-nitrotoluenes and aromatic aldehydes. This strategy allows access to a structurally diverse array of products for further manipulation. 相似文献
79.
Kiyohisa Fujimori Ian E. Craven 《Journal of polymer science. Part A, Polymer chemistry》1986,24(3):559-565
Georgiev and Shirota's simplified terminal complex model was applied to the dilatometrically measured initial rate of copolymerization of sytrene (ST) with maleic anhydride (MA) in methyl ethyl ketone (MEK) at 50°C. The rate was maximum at the feed MA mole fractions of 0.752, 0.769, and 0.806 at the total monomer concentrations of 2M, 1.5M, and 0.5M, respectively. Shirota's method gave the following ratios of propagation rate constants: βA=kAC/kAD = 8.25 and βD = kDC/kDA = 2.70. Georgiev's method gave βA = 14, βD = 2.7, and α = kAD/kDA = 22. The equilibrium constant of the donor-acceptor complexation between ST and MA in MEK was measured to be 0.045 dm3/mol at room temperature. 相似文献
80.
J. B. Wong Shing W. E. Baker K. E. Russell 《Journal of polymer science. Part A, Polymer chemistry》1995,33(4):633-642
The kinetics of grafting a basic monomer, 2-(dimethylamino)-ethyl methacrylate (DMAEMA) to hydrocarbon substrates have been investigated. These systems were chosen as models for the grafting of a homopolymerizable monomer to polyolefins such as polyethylene. The reactions with squalane and n-eicosane were initiated by an organic peroxide, 2,5-dimethyl 2,5 dit-butylperoxy)-3-hexyne; grafting yields become significant at high reaction temperatures and low monomer concentrations. In squalane, the order of reaction with respect to monomer increased from about 1.1 for 0.22?0.44M DMAEMA to almost 2 at 0.69M DMAEMA; the order with respect to initiator was 0.56. The overall activation energy in the 130?160°C temperature range was, however, surprisingly low, 42±5 kJ mol?1. When analytical data were used to separate the overall rate into those for grafting and homopolymerization, different kinetic paths were observed for the competing reactions. These results are interpreted in terms of two different mechanisms; intramolecular chain transfer plays an important role in grafting, while depropagation becomes a major factor in homopolymerization at temperatures above 150°C. © 1995 John Wiley & Sons, Inc. 相似文献