全文获取类型
收费全文 | 2212篇 |
免费 | 41篇 |
国内免费 | 12篇 |
专业分类
化学 | 1566篇 |
晶体学 | 16篇 |
力学 | 56篇 |
数学 | 353篇 |
物理学 | 274篇 |
出版年
2020年 | 20篇 |
2019年 | 17篇 |
2018年 | 20篇 |
2017年 | 16篇 |
2016年 | 32篇 |
2015年 | 22篇 |
2014年 | 31篇 |
2013年 | 113篇 |
2012年 | 92篇 |
2011年 | 70篇 |
2010年 | 67篇 |
2009年 | 50篇 |
2008年 | 104篇 |
2007年 | 102篇 |
2006年 | 103篇 |
2005年 | 89篇 |
2004年 | 99篇 |
2003年 | 78篇 |
2002年 | 77篇 |
2001年 | 33篇 |
2000年 | 22篇 |
1999年 | 23篇 |
1998年 | 23篇 |
1997年 | 33篇 |
1996年 | 26篇 |
1995年 | 28篇 |
1994年 | 19篇 |
1993年 | 30篇 |
1992年 | 28篇 |
1990年 | 20篇 |
1989年 | 14篇 |
1988年 | 19篇 |
1987年 | 21篇 |
1986年 | 14篇 |
1985年 | 47篇 |
1984年 | 43篇 |
1983年 | 22篇 |
1982年 | 46篇 |
1981年 | 37篇 |
1980年 | 36篇 |
1979年 | 39篇 |
1978年 | 39篇 |
1977年 | 20篇 |
1976年 | 36篇 |
1975年 | 30篇 |
1974年 | 33篇 |
1973年 | 36篇 |
1972年 | 20篇 |
1970年 | 16篇 |
1968年 | 16篇 |
排序方式: 共有2265条查询结果,搜索用时 15 毫秒
61.
Direct detection of thioester intermediate mixtures bound to EpoC, a 195 kDa polyketide synthase, has been achieved using limited proteolysis and Fourier-transform mass spectrometry (FTMS). Incubation with various N-acetylcysteamine thioester (S-NAC) substrate mimics produced mass shifts on the EpoC ACP domain consistent with their condensation with an enzyme-bound carbanion produced by the decarboxylation of methylmalonyl-S-EpoC. Reconstitution of EpoA-ACP, EpoB, and EpoC gave a +165.0 Da mass shift consistent with the formation of the methylthiazolyl-methacrylyl product by incorporation of acetyl-CoA, cysteine, and methylmalonyl-CoA. Thioester-templated reaction intermediates and products are typically characterized by quantifying radioactive substrates, either enzyme bound or chemically hydrolyzed. In contrast, the MS-based methodology described here provides semiquantifiable ratios of free enzyme, intermediate, and product occupancy and reveals that certain substrates result in a >50% formation of nonproductive intermediates. 相似文献
62.
cis,cis,cis-1,2,3,4-Tetrakis(diphenylphosphinomethyl)cyclopentane/[PdCl(C3H5)]2 efficiently catalyses the Heck reaction of alk-1-en-3-ol with a variety of aryl bromides. In the presence of hex-1-en-3-ol or oct-1-en-3-ol, the β-arylated carbonyl compounds were selectively obtained. Linalool and 2-methylbut-3-en-2-ol led to the corresponding 1-arylalk-1-en-3-ol derivatives. Turnover numbers up to 69,000 can be obtained for this reaction. A minor electronic effect of the substituents of the aryl bromide was observed. Similar reaction rates were observed in the presence of activated aryl bromides such as bromoacetophenone and deactivated aryl bromides such as bromoanisole. 相似文献
63.
Leslie M. Werbel Ann Curry Edward F. Elslager Carolyn Hess 《Journal of heterocyclic chemistry》1973,10(3):363-382
A group of fifty-five 2-[(4-11[(dialkylamino)alkyI]amino11-6-methyl-2-pyrimidinyl)amino]-benzimidazoles (VII) was synthesized in 3-88% yield by the condensation of the requisite 2-[(2-benzimidazolyl)amino]-4-chloro-6-methylpyrimidine (VI) with the appropriate polyamine in ethanol-hydrochloric acid or neat with excess amine containing potassium iodide. The 2-[(2-benzimidazolyl)amino]-6-methyl-4-pyrirnidinol precursors (V), obtained in 11-51% yield by cyclization of 2-(cyanoamino)-4-hydroxy-6-methylpyrimidine with a suitably substituted o-phenylenediamine, were chlorinated with phosphorus oxychloride to give the intermediate 2-[(2-benzimidazolyl)amino]-4-chloro-6-rnethylpyrimidines (VI) (27-99%). Oxidation of 5,6-dichloro-2-[(4-11[4-(diethylamino)-l-methylbutyl] amino 11-6-methyl-2-pyrimidinyl) amino ]benzimidazole ( 29 ) with m-chloroperbenzoic acid gave the distal N4'-oxide ( 31 ) (19%). Fusion of 2,3-uiaminopyridine with 2-(cyanoamino)-4-hydroxy-6-methylpyrimidine provided 2-[(4-hydroxy-6-tnethyl-2-pyrimidinyl)amino]-lH-imitlazo[4,5-b]pyrimidine (VIII) (30%), which upon chlori-nation with phosphorus oxychloride (63%) followed by amination with i N, N-diethylethylene-diamine afforded 2-(4-11[2-(diethylamino)ethyl] amino 11-6-methyl-2-pyrimidinyl)-lH-imidazo [4,5-b]pyridine (X) (8%). Thirty-eight of the novel 2-[(4-amino-6-methyl-2-pyrimidinyl)amino]-benzimidazoles possessed “curative” activity against Plasmodium berghei at single subcutaneous doses ranging from 20.640 mg./kg. Orally, thirty-one compounds exhibited suppressive activity against P. berghei comparable with or superior to the reference drugs 1-(p-chlorophenyl)-3-(4-11[2-(diethylarnino)ethyl]amino 11-6-methyl-2-pyrimidinyl)guanidine (I) and quinine hydrochloride, while twelve of them were 5 to 28 times as potent as I and quinine hydrochloride. Eight compounds also displayed strong suppressive activity against P. gallinaceum in chicks. 5,6-Dichloro-2-[(4-112-(diethylamino)ethyl]amino11-6-methyl-2-pyrimidinyl] benzimidazole (18) showed marked activity against a cycloguanil-resistant line of P. berghei, and the most promising member of the series, namely 5,6-dichloro-2-[(4-11[4-(diethylamino)-l-methylbutyl]amino11-6-methyl-2-pyrimidinyl)amino]benzimidazole ( 29 ) (Q = 28), was designated for preclinical toxico-logical studies and clinical trial. Structure-activity relationships are discussed. 相似文献
64.
65.
The crystal structures of ice, ammonia and ammonia hydrate have been simulated with rigid molecules using the interatomic potential function EPEN/2 and the computer program WMIN. Structural parameters were adjusted to give structures with minimum energy. The hydrogen bonding in the simulated structures is compared with that in the experimental structures. 相似文献
66.
Summary Salts of the anions [SnX5]–, [SnX4Cl, [SnX3Cl2]–, [SnX3]–, [PbX3]–, [SbX4]–, [SbX3Cl]–, [SbX2Cl2]–, [BiX4]–, [AuCl2]–, [AuX2]–, [AuXCl]–, [AuX4]–, [Au2X6]2– and [PtX4]2–, where X– = C6F5S–, have been isolated and characterised. The neutral SbX3 and BiX3 species, have also been isolated and shown to be pyramidal monomers (19F.n.m.r., i.r., and Raman spectral evidence). Various physical properties of the complexes prepared, as well as their stereochemistries (where these could be ascertained), are similar to those of the known corresponding halogeno compounds of these elements. These results further demonstrate the pseudo-halide nature of the pentafluorothiophenoxide ion.Author to whom all correspondence should be directed at: Laboratoire de Chimie de Coordination, Uniyersité Louis Pasteur, 67008 Strasbourg, France. 相似文献
67.
Leslie M. Connaughton J. Peter Hershey Frank J. Millero 《Journal of solution chemistry》1986,15(12):989-1002
The densities of the major sea salts (NaCl, Na2SO4, MgCl2, and MgSO4) have been measured from 25 to 95°C and to saturation. These results have been combined with literature data and fitted to equations of the form $$\Delta d = Am{\text{ }} + {\text{ }}Bm^{3/2} {\text{ }} + {\text{ }}Cm^2 {\text{ }} + {\text{ }}Dm^{5/2} $$ where Δd=d?do (do is the density of water) and A, B, and C, etc., are polynomial functions of temperature. The standard deviations of the fits were better than ±50×10?6 g-cm?3 for all the salts from 0 to 95°C and to saturation. The apparent molal volumes V? of the salts have been fitted to the equations of Pitzer. The infinite dilution values of V? were in good agreement with literature data, provided the results were not overfit. The large deviations of V? for MgSO4 from additivity as a function of concentration were attributed to the formation of MgSO4 ion pairs. 相似文献
68.
Dai QH Tommos C Fuentes EJ Blomberg MR Dutton PL Wand AJ 《Journal of the American Chemical Society》2002,124(37):10952-10953
The use of side chains as catalytic cofactors for protein mediated redox chemistry raises significant mechanistic issues as to how these amino acids are activated toward radical chemistry in a controlled manner. De novo protein design has been used to examine the structural basis for the creation and maintenance of a tryptophanyl radical in a three-helix bundle protein maquette. Here we report the detailed structural analysis of the protein by multidimensional NMR methods. An interesting feature of the structure is an apparent pi-cation interaction involving the sole tryptophan and a lysine side chain. Hybrid density functional calculations support the notion that this interaction raises the reduction potential of the W degrees /WH redox pair and helps explain the redox characteristics of the protein. This model protein system therefore provides a powerful model for exploring the structural basis for controlled radical chemistry in protein. 相似文献
69.
Irja Piirma V. R. Kamath Maurice Morton 《Journal of polymer science. Part A, Polymer chemistry》1975,13(9):2087-2102
A study has been carried out on the kinetics of persulfate-initiated emulsion polymerization of styrene in the presence of an anionic (oleate) or mixed anionic-nonionic emulsifier. In both cases it appears that Smith-Ewart kinetics are obeyed, i.e., there is a constant-rate period up to 40–50% conversion, during which there is a concomitant constant molecular weight development. The sharp increases in molecular weight with conversion reported by Grancio and Williams appear to be an artifact resulting from the use of an impure emulsifier (Triton X-100), which acts as a chain transfer agent to reduce the molecular weight by approximately an order of magnitude. Hence there does not appear to be any kinetic justification for assuming an inhomogeneous swollen latex particle (“core-shell” morphology), and normal thermodynamic considerations should still apply to this swelling phenomemon. 相似文献
70.
cis,cis,cis-1,2,3,4-Tetrakis(diphenylphosphinomethyl)cyclopentane/[PdCl(C3H5)]2 efficiently catalyses the Heck reaction of β-substituted enol ethers with aryl bromides. Employing β-methoxystyrene, 3-ethoxyacrylonitrile or methyl 3-methoxyacrylate, the regioselective α-arylation of these enol ethers was observed in all cases, and mixtures of Z and E isomers were generally obtained, which in many cases yielded a single ketone product after acid treatment. The stereoselectivity of this reaction depends on steric and electronic factors, and better stereoselectivities in favour of Z isomers were observed with electron-rich or sterically congested aryl bromides. Better yields were obtained for this reaction with electron-rich or sterically congested aryl bromides than with electron-poor aryl bromides. This observation suggests that with these β-substituted enol ethers the rate-limiting step of the catalytic cycle is not the oxidative addition of the aryl bromide to the palladium complex. 相似文献