全文获取类型
收费全文 | 779篇 |
免费 | 31篇 |
国内免费 | 3篇 |
专业分类
化学 | 674篇 |
晶体学 | 3篇 |
力学 | 8篇 |
数学 | 42篇 |
物理学 | 86篇 |
出版年
2024年 | 1篇 |
2023年 | 5篇 |
2022年 | 3篇 |
2021年 | 10篇 |
2020年 | 14篇 |
2019年 | 7篇 |
2018年 | 7篇 |
2017年 | 8篇 |
2016年 | 24篇 |
2015年 | 27篇 |
2014年 | 20篇 |
2013年 | 37篇 |
2012年 | 60篇 |
2011年 | 86篇 |
2010年 | 34篇 |
2009年 | 21篇 |
2008年 | 48篇 |
2007年 | 84篇 |
2006年 | 69篇 |
2005年 | 71篇 |
2004年 | 44篇 |
2003年 | 35篇 |
2002年 | 28篇 |
2001年 | 9篇 |
2000年 | 3篇 |
1999年 | 4篇 |
1998年 | 7篇 |
1997年 | 3篇 |
1996年 | 5篇 |
1995年 | 1篇 |
1994年 | 3篇 |
1993年 | 3篇 |
1992年 | 1篇 |
1991年 | 2篇 |
1990年 | 2篇 |
1987年 | 1篇 |
1985年 | 4篇 |
1984年 | 4篇 |
1982年 | 2篇 |
1981年 | 3篇 |
1980年 | 1篇 |
1977年 | 2篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1973年 | 2篇 |
1971年 | 1篇 |
1963年 | 1篇 |
1923年 | 1篇 |
1918年 | 2篇 |
排序方式: 共有813条查询结果,搜索用时 15 毫秒
61.
Plieger PG Downard AJ Moubaraki B Murray KS Brooker S 《Dalton transactions (Cambridge, England : 2003)》2004,(14):2157-2165
A bis(pyridine-armed) acyclic Schiff base ligand L1 has been synthesised from 3,6-diformylpyridazine and two equivalents of 2-(2-aminoethyl)pyridine. Reduction of this ligand using NaBH(4) resulted in the formation of the amine analogue L2. Complexes of the form [M(2)L1(mu-X)]Y(2)ClO(4)[where: M = Cu(II), X = OH(-) and Y = ClO(4)(-) 1, Cl(-) 2, Br(-) 3 or I(-) 4; M = Co(II), X = OH(-) and Y = ClO(4)(-) 5; M = Ni(II), X = SCN(-) 6 or X = N(3)(-) 7 and Y = ClO(4)(-)], and [Cu(2)L2(mu-OH)](ClO(4))(3) 8 were prepared and characterised. The complexes 1 and 5-7 have been characterised by single-crystal X-ray diffraction. The acyclic L1 ligand provides three nitrogen donor atoms per metal centre, including a pyridazine bridge between the metal centres, and the anion X also bridges the two metal centres. As required, coordinating solvent molecules or additional anions make up the remainder of the coordination sphere. The two copper centres of 1 are very strongly antiferromagnetically coupled (2J=-1146 cm(-1))via the pyridazine and hydroxide ion bridges, whereas the competing antiferromagnetic pyridazine bridging pathway and ferromagnetic 1,1-bridging azide pathway resulted in the observation of weak antiferromagnetic exchange in the dinickel(II) complex 7 (2J=-14 cm(-1)). Electrochemical examination of L1, L2 and complexes 1 and 5-8 revealed multiple redox processes. These have been tentatively assigned to a mixture of metal centred and ligand centred redox processes on the basis of cyclic voltammetry and coulometry results and comparisons with literature examples. 相似文献
62.
An evaluation of alpha-aryl-alpha-diazodiones in tandem carbonyl ylide formation-enantioselective [3 + 2]-cycloaddition reactions is described. Such substrates were designed to allow investigation of the electronic characteristics of the dipole upon asymmetric induction. Intramolecular cycloadditions (with a tethered alkene dipolarophile) were found to occur in good to quantitative yields, with a difference in ee exhibited by the two electronically different diazodiones 8 and 9. Intermolecular cycloadditions using diazodiones 12 and 13 with DMAD and arylacetylenes 16-18 again demonstrated that electronics play a key role in determining the outcome of the cycloaddition reactions. Enantioselectivities of up to 76% were observed. 相似文献
63.
Ashcroft AE 《Natural product reports》2003,20(2):202-215
Proteomics encompasses several disciplines in the quest to unravel the science of life. Mass spectrometry plays a key r?le in proteomics-associated analyses and this review describes that function in terms of the instrumentation used, the results generated, data interpretation and the advances in analytical techniques being made to deal with the production of highly specific, high throughput data. The review has 151 references. 相似文献
64.
Hervé G Hahn DU Hervé AC Goodworth KJ Hill AM Hailes HC 《Organic & biomolecular chemistry》2003,1(2):427-435
Methodologies to access water soluble large ringed calixarenes in good yield using efficient synthetic procedures have been investigated. Symmetrical partial functionalisations at the lower rim are described using activated [n]ethylene glycol chains and the addition behaviour contrasted with that of bromoalkanenitriles which proceeds with no observed regioselectivity. Full functionalisations of the calixarenes bearing hydrophilic groups are then investigated and a two-step procedure established which appears to be generally applicable for the addition of different [n]ethylene glycol chains. Furthermore, difunctionalisation under different reaction conditions are described. Throughout, strategies for the characterisation of these high mass compounds are outlined. 相似文献
65.
66.
Determining the amino acid content of a protein involves the hydrolysis of that protein, usually in acid, until the protein-bound amino acids are released and made available for detection. Both the variability in the ease of peptide bond cleavage and differences in the acid stability of certain amino acids can significantly affect determination of a protein's amino acid content. By using multiple hydrolysis intervals, a greater degree of accuracy can be obtained in amino acid analysis. Correction factors derived by linear extrapolation of serial hydrolysis data are currently used. Compartmental modeling of the simultaneous hydrolysis (yield) and degradation (decay) of amino acids by nonlinear multiple regression of serial hydrolysis data has also been validated and applied to determine the amino acid composition of various biological samples, including egg-white lysozyme, human milk protein, and hair. Implicit in the routine application of serial hydrolysis in amino acid analysis, however, is an understanding that correction factors, derived either linearly or through the more accurate nonlinear multiple regression approach, need to be determined for individual proteins rather than be applied uniformly across all protein types. 相似文献
67.
Determination of capsaicinoids in salsa by liquid chromatography and enzyme immunoassay 总被引:2,自引:0,他引:2
Perkins B Bushway R Guthrie K Fan T Stewart B Prince A Williams M 《Journal of AOAC International》2002,85(1):82-85
Two simple and rapid methods were developed to monitor pungency of salsa in production. Capsaicin (C) and dihydrocapsaicin (DHC) were quantitated in 17 commercially available tomato-based salsas by enzyme immunoassay (EIA) and liquid chromatography (LC) with fluorescent detection. Samples were extracted with methanol and the extracts were subjected to solid-phase extraction (SPE) using polystyrene-divinylbenzene columns. Analysis of SPE eluates showed good correlation (r2 = 0.953) between LC and EIA, with a slightly high bias for EIA. Salsa fortified with C and DHC from 0.118 to 103.2 microg/g resulted in recoveries of 90-112% (C) and 76-97% (DHC). Limits of detection by LC were 0.1 microg/g for each capsaicinoid and 0.1 microg/g by EIA for total capsaicinoids. The LC on-column response was linear from 0.2 to 100 ng for both C and DHC, whereas the working range for EIA was 0.1-2.0 ppm. Pungency varied between different salsa brands labeled mild, medium, and hot. 相似文献
68.
Two approaches have been developed for the enantioselective Reformatsky reaction of ethyl iododifluoroacetate with ketones to form a quaternary carbon centre using (1R,2S)-1-phenyl-2-(1-pyrrolidinyl)-1-propanol as the chiral ligand. Good yields and high enantioselectivities (80-91% ee) were achieved with a range of alkyl aryl ketones in a convenient one-pot protocol using ethyl iododifluoroacetate and diethylzinc to form the difluorinated Reformatsky reagent homogeneously. In the traditional two-step Reformatsky reaction using the preformed Reformatsky reagent generated from ethyl iododifluoroacetate and zinc dust, good yields and good enantioselectivities (75-84% ee) were also obtained. 相似文献
69.
Yuli Xie Yidong Liu Alison Rinderspacher Donald W. Landry 《Tetrahedron letters》2008,49(14):2320-2323
An efficient synthesis of a series of N-8-quinolinyl benzenesultams as novel NF-κB inhibitors was described via diazotization-induced cyclization of easily accessible N-8-quinolinyl-2-aminobenzenesulfonamides. 相似文献
70.
Corey L. Jones Colan E. Hughes Hamish H.-M. Yeung Alison Paul Kenneth. D. M. Harris Timothy L. Easun 《Chemical science》2021,12(4):1486
The formation processes of metal–organic frameworks are becoming more widely researched using in situ techniques, although there remains a scarcity of NMR studies in this field. In this work, the synthesis of framework MFM-500(Ni) has been investigated using an in situ NMR strategy that provides information on the time-evolution of the reaction and crystallization process. In our in situ NMR study of MFM-500(Ni) formation, liquid-phase 1H NMR data recorded as a function of time at fixed temperatures (between 60 and 100 °C) afford qualitative information on the solution-phase processes and quantitative information on the kinetics of crystallization, allowing the activation energies for nucleation (61.4 ± 9.7 kJ mol−1) and growth (72.9 ± 8.6 kJ mol−1) to be determined. Ex situ small-angle X-ray scattering studies (at 80 °C) provide complementary nanoscale information on the rapid self-assembly prior to MOF crystallization and in situ powder X-ray diffraction confirms that the only crystalline phase present during the reaction (at 90 °C) is phase-pure MFM-500(Ni). This work demonstrates that in situ NMR experiments can shed new light on MOF synthesis, opening up the technique to provide better understanding of how MOFs are formed.A new in situ NMR methodology for studying the formation processes of MOFs is reported, supported by SAXS and PXRD experiments. Synthesis of a phosphonate-based MOF is described, from molecular aggregation through to nucleation and crystallisation. 相似文献