全文获取类型
收费全文 | 4387篇 |
免费 | 186篇 |
国内免费 | 12篇 |
专业分类
化学 | 3073篇 |
晶体学 | 34篇 |
力学 | 95篇 |
数学 | 462篇 |
物理学 | 921篇 |
出版年
2023年 | 52篇 |
2022年 | 56篇 |
2021年 | 80篇 |
2020年 | 100篇 |
2019年 | 88篇 |
2018年 | 93篇 |
2017年 | 108篇 |
2016年 | 165篇 |
2015年 | 102篇 |
2014年 | 210篇 |
2013年 | 369篇 |
2012年 | 321篇 |
2011年 | 336篇 |
2010年 | 227篇 |
2009年 | 187篇 |
2008年 | 243篇 |
2007年 | 197篇 |
2006年 | 139篇 |
2005年 | 192篇 |
2004年 | 139篇 |
2003年 | 141篇 |
2002年 | 132篇 |
2001年 | 40篇 |
2000年 | 38篇 |
1999年 | 29篇 |
1998年 | 36篇 |
1997年 | 39篇 |
1996年 | 33篇 |
1995年 | 29篇 |
1994年 | 29篇 |
1993年 | 32篇 |
1992年 | 25篇 |
1991年 | 33篇 |
1990年 | 26篇 |
1989年 | 24篇 |
1988年 | 27篇 |
1987年 | 25篇 |
1986年 | 27篇 |
1985年 | 31篇 |
1984年 | 39篇 |
1983年 | 33篇 |
1982年 | 24篇 |
1981年 | 24篇 |
1980年 | 27篇 |
1979年 | 20篇 |
1978年 | 23篇 |
1977年 | 32篇 |
1976年 | 14篇 |
1975年 | 19篇 |
1974年 | 18篇 |
排序方式: 共有4585条查询结果,搜索用时 15 毫秒
51.
[Reaction: see text] Transformation of enantiopure diastereoisomers (2R,1'S)- and (2S,1'S)-2-(1-aminoalkyl)epoxides into the corresponding 4-(1-aminoalkyl)-1,3-dioxolanes is achieved by reaction with different ketones in the presence of BF3.Et2O. The conversion takes place in very high yields, total selectivity, and without epimerization. A mechanism to explain this transformation is proposed. The obtained 1,3-dioxolanes can be deprotected, and (2R,3S)- and (2S,3S)-3-aminoalkano-1,2-diols were isolated. 相似文献
52.
Volonterio A Bellosta S Bravin F Bellucci MC Bruché L Colombo G Malpezzi L Mazzini S Meille SV Meli M Ramírez De Arellano C Zanda M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(18):4510-4522
Partially modified retro- (PMR) and retro-inverso (PMRI) psi[NHCH(CF(3))]Gly peptides, a conceptually new class of peptidomimetics, have been synthesized in wide structural diversity and variable length by aza-Michael reaction of enantiomerically pure alpha-amino esters and peptides with enantiomerically and geometrically pure N-4,4,4-trifluorocrotonoyl-oxazolidin-2-ones. The factors underlying the observed moderate to good diastereocontrol have been investigated. The conformations of model PMR-psi[NHCH(CF(3))]Gly tripeptides have been studied in solution by (1)H NMR spectroscopy supported by MD calculations, as well as in the solid-state by X-ray diffraction. Remarkable stability of turn-like conformations, comparable to that of parent malonyl-based retropeptides, was evidenced, as a likely consequence of two main factors: 1) severe torsional restrictions about sp(3) bonds in the [CO-CH(2)-CH(CF(3))-NH-CH(R)-CO] module, which is biased by the stereoelectronically demanding CF(3) group and the R side chain; 2) formation of nine-membered intramolecularly hydrogen-bonded rings, which have been clearly detected both in CHCl(3) solution and in some crystal structures. The former factor seems to be more important, as turn-like conformations were found in the solid-state even in the absence of intramolecular hydrogen bonding. The relative configuration of the -C*H(CF(3))NHC*H(R)- stereogenic centers has a major effect on the stability of the turn-like conformation, which seems to require a syn stereochemistry. X-ray diffraction and ab initio computational studies showed that the [-CH(CF(3))NH-] group can be seen as a sort of hybrid between a peptide bond mimic and a proteolytic transition state analogue, as it combines some of the properties of a peptidyl -CONH- group (low NH basicity, CH(CF(3))-NH-CH backbone angle close to 120 degrees, C-CF(3) bond substantially isopolar with the C=O) with some others of the tetrahedral intermediate [-C(OX)(O(-))NH-] involved in the protease-mediated hydrolysis reaction of a peptide bond (high electron density on the CF(3) group, tetrahedral backbone carbon). 相似文献
53.
A stereoselective synthesis of the ABCD ring framework of azaspiracid-1 and azaspiracid-3 has been achieved using a tandem bis-spiroketalization protocol in the presence of a mild proton source from 1,4-diketone precursor. A tetrahydrofuran intermediate with the correct stereochemistry for the D ring of azaspiracids-1 and 3 was then taken through a linear sequence of reactions to afford the desired diketone precursor. The D-ring of azaspiracid-1 was then constructed by employing a Sharpless asymmetric dihydroxylation followed by etherification using a homoallyl derivative. The structure of the ABCD ring framework with four contiguous rings was established by extensive NMR analysis. 相似文献
54.
55.
R. P. Rastogi Kehar Singh Ram Shabd B. M. Upadhyay 《Journal of colloid and interface science》1981,80(2):402-411
Electrical properties of cholesterol interfaces have been investigated. For this purpose electroosmotic and hydrodynamic permeation of water, sodium chloride, barium chloride, aluminum chloride, and urea solutions across a cholesterol plug have been investigated. Dependence of electroosmotic permeability on concentration of electrolytes has also been studied. Electrophoretic mobility of cholesterol particles of known size distribution and dispersed in solutions of varying concentrations of electrolytes and urea has also been studied. The data have been used to estimate ζ potentials in order to have a plausible picture of the electrical double layer at the cholesterol/ solution interfaces. 相似文献
56.
ágnes Zsigmond Ramóna Madácsi Ferenc Notheisz Erzsébet Mernyák and Ferenc Joó 《Reaction Kinetics and Catalysis Letters》2006,87(2):297-304
Summary [RuCl2(PPh3)3], [{RuCl2(TPPMS)2}2] and their heterogenized analogs were applied in the selective hydrogenation of 17-keto- and α,β-unsaturated ketosteroids.
In basic conditions these complexes selectively hydrogenated the C=O bonds, similarly to the results obtained in the case
of α,β-unsaturated aldehydes. A new method was developed for the synthesis of an expensive steroid alcohol, which can be prepared
traditionally in a more complicated way. 相似文献
57.
Ram S. Bhatt Nitya G. Kundu T. Ling Chwang Charles Heidelberger 《Journal of heterocyclic chemistry》1981,18(4):771-774
Condensation of 2,4-dimethoxy-5-iodo-6-carbomethoxypyrimidine ( 10 ) with copper (I) 3-tetrahydropyranyloxyprop-1-ynide ( 4 ) afforded 2,4-dimethoxy-5-(3′-tetrahydropyranyloxyprop-1′-yn)-6-carbomethoxypyrimidine ( 11 ), which was hydrolyzed to produce 2,4-dimethoxy-5-(3′-hydroxyprop-1′-yn)-6-carbomethoxypyrimidine ( 12 ). Oxidation of 12 with dimethyl sulfoxide-oxalyl chloride reagent gave the acetylenic aldehyde ( 13 ), which on treatment with sodium methoxide in dry tetrahydrofuran yielded 2,4-dimethoxy-5-ethynyl-6-carbomethoxypyrimidine ( 14 ). The trimethylsilyl derivative ( 15 ) was deprotected by sequential treatment with iodotrimethylsilane and aqueous sodium hydroxide, leading to the formation of 5-ethynylorotic acid ( 1 ). 相似文献
58.
L. H. C. Mattoso S. K. Manohar A. G. Macdiarmid A. J. Epstein 《Journal of polymer science. Part A, Polymer chemistry》1995,33(8):1227-1234
Syntheses of parent polyaniline and methyl, methoxy, and ethoxy ortho-substituted polyanilines were performed using the conventional chemical methodology and monitored using the new open-circuit-potential (Voc) profile technique. The intermediate pernigraniline oxidation state was identified and isolated at the Voc maximum (A) during the conventional chemical synthesis of poly(o-methoxyaniline) in the emeraldine oxidation state. The introduction of the substituent on the aniline ring leads to longer polymerization times and lower Voc values. Syntheses in the presence of two different monomers in solution were also investigated and showed preferential polymerization of the monomer with the lowest Voc potential. All polymers produced were characterized by elemental analysis, gel permeation chromatography, UV-VIS spectroscopy, and cyclic voltammetry. The influence of the substituent on the Voc profile and on the polymer characteristics are rationalized in terms of steric and electronic effects. © 1995 John Wiley & Sons, Inc. 相似文献
59.
The aim of this study was to investigate the influence of cosolvent polarity on the rheological flow properties of aqueous and hydroalcoholic gels obtained from the Carbopol Ultrez 10 base and used for topical applications. Specifically, we have examined the effect of pH (range 4.0--7.0) on the consistency and flow properties of dispersed systems in water and mixtures--15 : 85% v/v of methanol : water, ethanol : water, n-propanol : water and n-butanol : water--at a constant polymer concentration of 0.3% w/w. The gels, which had decreasing polarity values in the jellifying medium, showed qualitatively similar flow behavior, characteristic of pseudoplastic systems, and all of the flow curves were adjusted to the Ostwald model. Sigmoidal dose response functions were calculated to describe the flow and consistency indexes as a function of pH. As a result, the influence of alcohol polarity on the polymer network has been assessed meaningfully using the empirical parameters obtained: maximum consistency index value (k(max)), pH value required for 50% development of polymer network (pH(50)), and asymptotic flow index value (n(min)) for the fully structured gels. 相似文献
60.
Siya Ram William Evans Dean S. Wise Leroy B. Townsend John W. Mccall 《Journal of heterocyclic chemistry》1989,26(4):1053-1059
A series of methyl 2-substituted purine 8-carbamates was prepared and evaluated for antifilarial activity. These purines were synthesized as aza congeners of benzimidazole carbamates which have shown significant anthelmintic activity to determine the effect that this modification might have on anthelmintic activity. The compounds were tested against the filarial infection, B. pahangi, in jirds. None of the compounds prepared in this study demonstrated antifilarial activity. 相似文献