全文获取类型
收费全文 | 10314篇 |
免费 | 290篇 |
国内免费 | 85篇 |
专业分类
化学 | 7337篇 |
晶体学 | 45篇 |
力学 | 235篇 |
数学 | 1570篇 |
物理学 | 1502篇 |
出版年
2022年 | 71篇 |
2021年 | 121篇 |
2020年 | 154篇 |
2019年 | 153篇 |
2018年 | 106篇 |
2017年 | 80篇 |
2016年 | 236篇 |
2015年 | 202篇 |
2014年 | 238篇 |
2013年 | 572篇 |
2012年 | 576篇 |
2011年 | 741篇 |
2010年 | 327篇 |
2009年 | 259篇 |
2008年 | 563篇 |
2007年 | 643篇 |
2006年 | 688篇 |
2005年 | 556篇 |
2004年 | 496篇 |
2003年 | 451篇 |
2002年 | 394篇 |
2001年 | 163篇 |
2000年 | 105篇 |
1999年 | 97篇 |
1998年 | 91篇 |
1997年 | 116篇 |
1996年 | 134篇 |
1995年 | 105篇 |
1994年 | 94篇 |
1993年 | 108篇 |
1992年 | 94篇 |
1991年 | 70篇 |
1990年 | 99篇 |
1989年 | 61篇 |
1988年 | 82篇 |
1987年 | 74篇 |
1986年 | 93篇 |
1985年 | 133篇 |
1984年 | 128篇 |
1983年 | 80篇 |
1982年 | 108篇 |
1981年 | 109篇 |
1980年 | 107篇 |
1979年 | 88篇 |
1978年 | 103篇 |
1977年 | 81篇 |
1976年 | 85篇 |
1975年 | 77篇 |
1974年 | 53篇 |
1973年 | 76篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
51.
Compound 1, 2-(4-phenoxyphenylsulfonylmethyl)thiirane, is a potent and selective inhibitor for human gelatinases (J. Am. Chem. Soc. 2000, 122, 6799-6800), enzymes implicated in a number of diseases, including cancer. This compound is showing excellent promise in animal trials in a number of disease models. Large quantities of this compound were necessary for these studies. A convenient four-step synthetic route for compound 1 is described herein. The synthesis is amenable to scale-up to tens of grams and gives an overall yield of 57% for this important compound. 相似文献
52.
Copolymerization of vinyl acetate with allyl carbonates that contain isopropyl groups yields highly branched poly(vinyl acetates). 相似文献
53.
Strong, low-energy two-photon absorption in extended amine-terminated cyano-substituted phenylenevinylene oligomers 总被引:8,自引:0,他引:8
Chung SJ Rumi M Alain V Barlow S Perry JW Marder SR 《Journal of the American Chemical Society》2005,127(31):10844-10845
Three quadrupolar oligophenylenevinylenes with five rings in the conjugated backbone, terminal donor groups, and various acceptors and/or donors along the backbone were synthesized and their two-photon spectroscopic properties investigated. These chromophores exhibit large two-photon absorption cross sections over a wide wavelength range and two distinct peaks, the strongest of which (deltamax > 3600 GM) is observed at 960-970 nm, a wavelength close to twice the value of the linear absorption maximum (2lambda(1)max). The findings on these chromophores are compared with those for analogous molecules with shorter conjugation length, for which the main two-photon band is at significantly shorter wavelength than 2lambda(1)max. 相似文献
54.
Stephen G. Davies Ian A. Hunter Rebecca L. Nicholson Paul.M. Roberts Edward D. Savory Andrew D. Smith 《Tetrahedron》2004,60(35):7553-7577
α-Dibenzylamino- and α-benzyloxy- derivatives of N-acetyl-(S)-4-benzyl-5,5-dimethyloxazolidin-2-one readily undergo highly stereoselective boron mediated syn-aldol reactions with a range of aromatic and aliphatic aldehydes, generating the syn-aldol products in good to excellent yields as single diastereoisomers after purification. In the α-dibenzylamino series, deprotection of the functionalised aldol fragments to the corresponding α-amino-β-hydroxy methyl ester or α-amino-β-hydroxyaldehyde proved problematic, with a range of N- and O-protecting groups giving mixtures of products arising from endocyclic and exocyclic cleavage pathways. However, in the α-benzyloxy series, O-silyl protection of the aldol products, and subsequent DIBAL reduction gives stereoselectively the corresponding N-1′-hydroxyalkyloxazolidin-2-ones, which undergo base promoted fragmentation to the desired highly functionalised and differentially protected α,β-dihydroxyaldehydes in good yields and without loss of stereochemical integrity. 相似文献
55.
Scott Charles D. Woodward Charlene A. Thompson James E. Blankinship Stephen L. 《Applied biochemistry and biotechnology》1990,24(1):799-815
Applied Biochemistry and Biotechnology - Both oxidative and reductive enzymes can be utilized to enhance coal solubilization in aqueous and organic media. Aerobic solubilization was carried out... 相似文献
56.
Merkx M Kopp DA Sazinsky MH Blazyk JL Müller J Lippard SJ 《Angewandte Chemie (International ed. in English)》2001,40(15):2725
The cover picture shows in the background the whole cell of a methanotrophic bacterium on which are superimposed components of methane monooxygenase (the structure of the hydroxylase component (top), one of the two four-helix bundles that house the catalytic diiron centers (left)) and a schematic diagram of the catalytic cycle by which the enzyme converts dioxygen and methane into methanol and water. More about this unusual enzyme system is reported by Lippard et al. on p. 2782 ff. 相似文献
57.
58.
Tamaru SI Yamamoto M Shinkai S Khasanov AB Bell TW 《Chemistry (Weinheim an der Bergstrasse, Germany)》2001,7(24):5270-5276
A dicarboxylate host (1) binds cationic monosaccharides such as D-glucosamine HCl (2), D-galactosamine-HCl (3), and D-mannosamine-HCl (4) with high affinity (K1 = 8.0 x 10(4)-2.0 x 10(5) M(-1)) in methanol. In circular dichroism (CD) spectroscopy a positive exciton-coupling band was observed near 290 nm; this indicates that the saccharides are recognized by multiple point interactions. Since the corresponding neutral monosaccharides are not significantly bound, one may conclude that complex formation is primarily due to the electrostatic interaction between NH3+ in the guest and one carboxylate in the host and secondarily due to hydrogen-bonding interactions of OH groups with the other carboxylate and/or nitrogen bases. Molar ratio plots and Job plots indicate that host 1 and cationic monosaccharide guests form CD-active, pseudo-cyclic 1:1 complexes at low guest concentration followed by the formation of CD-silent, acyclic 1:2 1-saccharide complexes at high guest concentration. The possible binding modes are discussed in detail on the basis of molecular mechanics calculations and chemical shift changes in 1H NMR spectra. The results of competition experiments with several cationic reference compounds bearing fewer OH groups than 2-4 are consistent with the proposed binding model. Thus, the present study is a rare example of saccharide recognition in a protic solvent, where in general, hydrogen-bonding interactions are rarely useful because of strong solvation energy. These are apparently the strongest saccharide complexes involving noncovalent interactions between host and guest. We believe that the findings are significant as a milestone toward development of new saccharide recognition systems ultimately useful in aqueous solution. 相似文献
59.
A detailed vibrational assignment is proposed for 1,3-dimethyl-1,3-diaza-2-boracyclopentanes: where X = Cl, Br or NMe2. The assignments are generally in accord with C2v symmetry, but there is some evidence for a slight breakdown, as some A2 modes appear in the IR. The BN2 stretches are near 1500 cm?1, (antisymmetric) and 1300 cm?1 (symmetric), consistent with a large degree of π-bonding. 相似文献
60.
The hydrogen-deuterium exchange of H-2 in 4-pyrimidone, a number of 1- and 3-alkyl-4-pyrimidones and several of their thione analogs in deuterium oxide at moderate temperatures is reported. This reaction is apparently not susceptible to acid or base catalysis. Cations of the 4-pyrimidones were found not to exchange H-2 at all in acid media. Catalytic amounts of bases do not alter the exchange rates whereas more concentrated alkali decompose the pyrimidone. However, 1,4(3,4)-dihydro-1,3-dimethyl-4-oxopyrimidinium iodide (and its 6-methyl analog) exchange H-2 quite rapidly in neutral deuterium oxide, almost instantly when triethylamine is added as a catalyst, and very slowly in dilute solutions of deuterium chloride in deuterium oxide. Mechanisms are proposed to account for these phenomena. 相似文献