全文获取类型
收费全文 | 14170篇 |
免费 | 472篇 |
国内免费 | 49篇 |
专业分类
化学 | 11323篇 |
晶体学 | 78篇 |
力学 | 223篇 |
数学 | 1821篇 |
物理学 | 1246篇 |
出版年
2023年 | 98篇 |
2022年 | 277篇 |
2021年 | 532篇 |
2020年 | 302篇 |
2019年 | 349篇 |
2018年 | 271篇 |
2017年 | 226篇 |
2016年 | 480篇 |
2015年 | 465篇 |
2014年 | 444篇 |
2013年 | 876篇 |
2012年 | 922篇 |
2011年 | 1049篇 |
2010年 | 623篇 |
2009年 | 623篇 |
2008年 | 874篇 |
2007年 | 867篇 |
2006年 | 742篇 |
2005年 | 677篇 |
2004年 | 580篇 |
2003年 | 500篇 |
2002年 | 471篇 |
2001年 | 180篇 |
2000年 | 145篇 |
1999年 | 120篇 |
1998年 | 127篇 |
1997年 | 108篇 |
1996年 | 138篇 |
1995年 | 101篇 |
1994年 | 91篇 |
1993年 | 86篇 |
1992年 | 69篇 |
1991年 | 81篇 |
1990年 | 60篇 |
1989年 | 75篇 |
1988年 | 65篇 |
1987年 | 57篇 |
1986年 | 57篇 |
1985年 | 70篇 |
1984年 | 89篇 |
1983年 | 48篇 |
1982年 | 75篇 |
1981年 | 61篇 |
1980年 | 59篇 |
1979年 | 53篇 |
1978年 | 60篇 |
1977年 | 43篇 |
1976年 | 41篇 |
1975年 | 29篇 |
1963年 | 20篇 |
排序方式: 共有10000条查询结果,搜索用时 45 毫秒
101.
Benati L Bencivenni G Leardini R Minozzi M Nanni D Scialpi R Spagnolo P Zanardi G 《The Journal of organic chemistry》2005,70(8):3046-3053
Thermal reaction of various alpha-azido esters with Bu(3)SnH in refluxing benzene results in smooth production of 3-(tributylstannyl)-1-triazene adducts affording cyclized 1,2,3-triazol-4-ones in preference to reduced amines and thence provides a new useful method for the preparation of these triazole derivatives. In the presence of AIBN the occurrence of triazene products still remains important or even exclusive and, consequently, generation of the expected stannylaminyl radicals is seriously limited. With 2-azidomalonates and alpha-azido-beta-keto esters stannyltriazenes can similarly occur in the absence of the radical initiator, but in the latter cases the ensuing triazenes undergo preferential cyclization onto the ketone moiety to give reactive hydroxytriazolines. Contrary to alpha-azido esters, in the presence of AIBN alpha-azido-beta-keto esters as well as azidomalonates give rise only to the usual stannylaminyl radicals. A possible explanation for the different behavior of the mono- and dicarbonyl azides in the presence of AIBN is put forward. 相似文献
102.
Strategically designed sample composition (SSC) is a new technique that decreases the number of analytical determinations needed in routine screening to as few as the number of original sample specimens while providing information that is specific to them. Although this new technique has been applied to environmental studies, this paper describes its first application to food safety studies. Contamination of milk samples with polychlorinated biphenyls (PCBs) was chosen as a case study to show the usefulness and potential of the SSC technique with a fast analytical procedure that involves saponification of the samples and solid-phase microextraction of the PCBs. A total of 20 sample specimens can be analyzed in 11 determinations with excellent predictions of the positive samples and the concentration levels of the contaminants. The robustness of the strategy was investigated and demonstrated. 相似文献
103.
Maria Cazacu Grigore Munteanu Angelica Vlad 《Journal of organometallic chemistry》2006,691(17):3700-3707
Two new polymeric structures containing ferrocene units along the chains, namely poly(silyl ester)s, have been synthesized and characterized: a geminal poly(silyl ester) (g-PSE) and one having a disiloxane spacer between the silyl ester groups (s-PSE). The condensation polymerization of AA/BB monomer systems in solution was used in both cases as preparation method involving a silicon-containing diol, (diphenylsilane diol or 1,3-bis(hydroxy)-tetramethyldisiloxane), and 1,1′-di(chlorocarbonyl)ferrocene. The polymers were investigated by differential pulse voltammetry in order to evaluate the redox behavior. Due to the presence of the silyl ester groups in the chain, these polymers are hydrolytically degradable. 相似文献
104.
Dimitrakakis E Haberhauer-Troyer C Abe Y Ochsenkühn-Petropoulou M Rosenberg E 《Analytical and bioanalytical chemistry》2004,379(5-6):842-848
The use of solid-phase microextraction (SPME) with gas chromatography coupled to microwave-induced plasma atomic-emission detection (GC–MIP-AED) is described for selenite [Se(IV)] speciation. Aqueous standards were derivatised with sodium tetraethyl- or tetrapropylborate and extracted by SPME. Headspace extraction of the ethyl and propyl derivatives was studied. Relevant experimental conditions were optimised, including conditions for derivatisation and extraction and those of gas chromatographic analysis. The limits of detection achieved for headspace sampling of derivatised Se(IV) were in the low ng mL–1 range for both ethylation and propylation. When the method was applied to analysis of selenite in selenised yeast reference material results were in good agreement with the indicated values. 相似文献
105.
Maria Nowakowska Mirosława Smoluch Dorota Sendor 《Journal of inclusion phenomena and macrocyclic chemistry》2001,40(3):213-219
The effect of -, - and -cyclodextrin onthe photochemical stability of 7-amino-4-methylcoumarin (C120)was studied. Using spectroscopic techniques (UV/Vis absorption spectroscopy, fluorescence, fluorescence anisotropy and circular dichroism) combined with HPLC/MS and MS analysis it was demonstrated that addition of -cyclodextrin to the aqueoussolution of C120 markedly inhibits the photodegradation of that dye. This results from theformation of an inclusion complex between C120 and -cyclodextrin. 相似文献
106.
Alves Lourdes A. Felipe Maria G. A. Silva JoÃo B. Almeida E. Silva Silvio S. Prata Arnaldo M. R. 《Applied biochemistry and biotechnology》1998,70(1):89-98
Applied Biochemistry and Biotechnology - In order to remove or reduce the concentrations of toxic substances present in the sugarcane bagasse hemicellulose hydrolysate for xyloseto-xylitol... 相似文献
107.
Determination of fluquinconazole, pyrimethanil, and clofentezine residues in fruits by liquid chromatography with ultraviolet detection 总被引:1,自引:0,他引:1
A simple method was developed for the determination of fluquinconazole, pyrimethanil, and clofentezine in whole fruit; peel; and pulp of mango, apple, and papaya. These compounds were extracted from fruit samples with a mixture of ethyl acetate-n-hexane (1 + 1, v/v). An aliquot (2 mL) of the extract was evaporated to near dryness under a stream of nitrogen, and the residue was dissolved with 2 mL methanol. The analysis was performed by means of liquid chromatography with ultraviolet detection at 254 nm using a gradient solvent system. The method was validated with fortified fruit samples at concentration levels of 0.05, 0.10, 0.20, and 0.50 mg/kg. Average recoveries (4-8 replicates) ranged from 80 to 95% with relative standard deviations between 3.5 and 12.7%. Detection limits ranged from 0.03 to 0.05 mg/kg for fruit pulp and 0.03 mg/kg for whole fruit. The quantitation limits ranged from 0.05 to 0.10 mg/kg for fruit pulp and 0.05 mg/kg for whole fruit. The analytical method was applied to fruit samples obtained from local markets. 相似文献
108.
del Mar Graciani M Rodríguez A Muñoz M Moyá ML 《Langmuir : the ACS journal of surfaces and colloids》2005,21(16):7161-7169
Micellization in water-ethylene glycol (EG) N-dodecyl, N-tetradecyl, and N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (SB3-12, SB3-14, and SB3-16, respectively) micellar solutions, with the weight percent of EG changing within the range 0-40, was studied by means of surface tension measurements. Information about the influence of the added EG on the aggregation number of the sulfobetaine micelles and on the polarity of the interfacial region of micelles was obtained through fluorescence and spectroscopic measurements. Surface tension measurements also provide information about the dependence of the surface excess concentration, the minimum area per surfactant molecule, the surface pressure at the cmc, and the standard Gibbs energy of adsorption on the added weight percent of the organic solvent. The Gordon parameter of the water-EG mixtures was also estimated by means of surface tension measurements. The thermodynamic and structural changes originated by the presence of EG control the micellar kinetic effects observed in the reaction methyl 4-nitrobenzenesulfonate + Br(-) occurring in the water-EG sulfobetaine micellar solutions. Information about the distribution of bromide ions between the bulk and micellar pseudophases was obtained through conductivity measurements. The kinetic micellar effects were quantitatively explained by using the pseudophase kinetic model. 相似文献
109.
Maria Hermínia de Paula Leite Mello 《manuscripta mathematica》1987,57(3):263-280
Let be a nonorientable m-plane bundle over a CW complex X of dimension m or less. Given a 2-plane bundle over X, we wish to know whether can be embedded as a sub-bundle of . The bundle need not be orientable. When is even-dimensional there is the added complication of twisted coefficients. In that case, we use Postnikov decomposition of certain nonsimple fibrations in order to describe the obstructions for the embedding problem. Emery Thomas [11] and [12] treated this problem for and both orientable. The results found here are applied to the tangent bundle of a closed, connected, nonorientable smooth manifold, as a special case.The writing of this paper was partially supported by CNPq grant 相似文献
110.
In this paper, we investigate {1,2,3}-semiaffine planes. All such planes of order n >51 shall be classified. It turns out that they are embeddable into projective planes of the same order n in the most natural way.Work supported by National Research Project on Strutture Geometriche Combinatoria, loro applicazioni of Italian M.P.I. and G.N.S.A.G.A. of C.N.R. 相似文献