全文获取类型
收费全文 | 1384篇 |
免费 | 54篇 |
国内免费 | 3篇 |
专业分类
化学 | 1158篇 |
晶体学 | 10篇 |
力学 | 18篇 |
数学 | 109篇 |
物理学 | 146篇 |
出版年
2023年 | 24篇 |
2022年 | 25篇 |
2021年 | 36篇 |
2020年 | 41篇 |
2019年 | 33篇 |
2018年 | 18篇 |
2017年 | 15篇 |
2016年 | 43篇 |
2015年 | 42篇 |
2014年 | 43篇 |
2013年 | 60篇 |
2012年 | 106篇 |
2011年 | 130篇 |
2010年 | 65篇 |
2009年 | 54篇 |
2008年 | 103篇 |
2007年 | 98篇 |
2006年 | 83篇 |
2005年 | 94篇 |
2004年 | 76篇 |
2003年 | 72篇 |
2002年 | 49篇 |
2001年 | 14篇 |
2000年 | 13篇 |
1999年 | 10篇 |
1998年 | 10篇 |
1997年 | 4篇 |
1996年 | 6篇 |
1995年 | 3篇 |
1994年 | 7篇 |
1993年 | 7篇 |
1992年 | 8篇 |
1989年 | 4篇 |
1988年 | 4篇 |
1987年 | 3篇 |
1986年 | 3篇 |
1985年 | 2篇 |
1984年 | 5篇 |
1982年 | 2篇 |
1981年 | 2篇 |
1980年 | 5篇 |
1979年 | 2篇 |
1978年 | 4篇 |
1976年 | 1篇 |
1975年 | 3篇 |
1974年 | 2篇 |
1971年 | 1篇 |
1965年 | 1篇 |
1881年 | 1篇 |
1876年 | 1篇 |
排序方式: 共有1441条查询结果,搜索用时 15 毫秒
1.
2.
Thermodynamic study of transthyretin association (wild‐type and senile forms) with heparan sulfate proteoglycan: pH effect and implication of the reactive histidine residue 下载免费PDF全文
Ambre Geneste Claire André Nadine Magy‐Bertrand Lydie Lethier Gharbi Tijani Yves Claude Guillaume 《Biomedical chromatography : BMC》2015,29(4):514-522
The tetramer destabilization of transthyretin into monomers and its fibrillation are phenomena leading to amyloid deposition. Heparan sulfate proteoglycan (HSPG) has been found in all amyloid deposits. A chromatographic approach was developed to compare binding parameters between wild‐type transthyretin (wtTTR) and an amyloidogenic transthyretin (sTTR). Results showed a greater affinity of sTTR for HSPG at pH 7.4 compared with wtTTR owing to the monomeric form of sTTR. Analysis of the thermodynamic parameters showed that van der Waals interactions were involved at the complex interface for both transthyretin forms. For sTTR, results from the plot representing the number of protons exchanged vs pH showed that the binding mechanism was pH‐dependent with a critical value at a pH 6.5. This observation was due to the protonation of a histidine residue as an imidazolium cation, which was not accessible when TTR was in its tetrameric structure. At pH >6.5, dehydration at the binding interface and several contacts between nonpolar groups of sTTR and HSPG were also coupled to binding for an optimal hydrogen‐bond network. At pH <6.5, the protonation of the His residue from sTTR monomer when pH decreased broke the hydrogen‐bond network, leading to its destabilization and thus producing slight conformational changes in the sTTR monomer structure. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
3.
Claire Moura 《Proceedings of the American Mathematical Society》2004,132(3):687-690
We determine the maximum punctual order of contact between two plane algebraic curves, of which one is reduced. We prove that, generically on the reduced curve, this quantity is always strictly bounded by the product of the degrees of the curves.
4.
The determination of the enantiomeric purity of 2 or 3-substituted cyclanones, particularly cyclohexanones, is conveniently achieved by derivatisation into cyclic aminals with commercially available (R, R)-1,2-diphenylethylenediamine. The derivatisation procedure is directly done into the NMR tube, instantaneously, and 13C NMR allows an accurate measure of the ee. 相似文献
5.
Claire Cates Haulk John Drew Charles R. Johnson J. Hunter Tart 《Linear and Multilinear Algebra》1997,43(1):35-51
For a given n-by-n matrix A, we consider the set of matrices which commute with A and all of whose principal submatrices commute with the corresponding principal submatrices of A. The properties of this set are examined, with particular attention to its dimension. 相似文献
6.
We shall prove here that any binary relation on a base E with cardinality n > 6 is reconstructible from its restrictions of cardinality 2, 3, 4 and (n - 1). This proof needs results of part I of this paper where we characterize any pair of relations R, R' which are 2-, 3- and 4-hypomorphic. As a corollary we obtain that any binary relation is (n - 4)-reconstructible (when n > 9). 相似文献
7.
Various oxazolidines were prepared from ephedrine. It was shown that their formation is not general, the reaction is not always stereoselective and can lead to isomerization of the double bond of α,β-unsaturated aldehydes. Some of these oxazolidines were used in stereoselective preparation of β-alkyl aldehydes. 相似文献
8.
Khlobystov AN Brett MT Blake AJ Champness NR Gill PM O'Neill DP Teat SJ Wilson C Schröder M 《Journal of the American Chemical Society》2003,125(22):6753-6761
A series of structurally related binuclear metallacycles [Cd(NO(3))(2)L](2), where L is an angular exo-bidentate ligand, have been synthesized. Each metallacycle contains two coordinatively unsaturated, chiral metal centers within a single molecule, and the assembly of these metallacycles into polymeric framework structures has been studied systematically for the first time. Stereoselective homochiral association of [Cd(NO(3))(2)L](2) leads to the formation of helical coordination polymers, whereas meso type association results in nonhelical chain structures. The type of stereoselective aggregation depends on the conditions of self-assembly as well as on ligand functionality. Both helical and nonhelical polymeric complexes have been isolated for the metallacycle [Cd(NO(3))(2)(2,4'-pyacph)](2) (2,4'-pyacph = 2,4'-(4-ethynylphenyl)bipyridyl). Homochiral association results in the formation of helical [Cd(NO(3))]( infinity ) chains which link the binuclear [Cd(NO(3))(2)(2,4'-pyacph)](2) metallacycles into racemic two-dimensional sheets which contain both P and M [Cd(NO(3))]( infinity ) helices. In contrast, meso-association leads to the formation of nonhelical one-dimensional chains. It is shown that the product of homochiral association is predominately formed at room temperature and that of meso-association is generated at elevated temperatures. Thus, it may be concluded that the homochiral association appears to be energetically less favorable than the meso-association, a conclusion that has been confirmed by theoretical calculations of the crystal lattice energy. Several high-yield syntheses of bipyridyl-type ligands used for metallacyclic assembly are also reported. 相似文献
9.
A concise synthesis of the complete tricyclic dibenzofuran-1,4-dione aromatic core of popolohuanone E has been demonstrated by mild base treatment of a biquinone intermediate, thus establishing a biomimetic route to this family of heterocyclic ring systems and the total synthesis of popolohuanone E. 相似文献
10.
Mangeney C Ferrage F Aujard I Marchi-Artzner V Jullien L Ouari O Rékaï el D Laschewsky A Vikholm I Sadowski JW 《Journal of the American Chemical Society》2002,124(20):5811-5821
Citrate-capped gold nanoparticles as well as planar gold surfaces can be efficiently grafted with a covalently attached polymer monolayer a few nanometers thick, by simple contact of the metal surface with dilute aqueous solutions of hydrophilic polymers that are end-capped with disulfide moieties, as shown by UV/vis absorption, dynamic light scattering, and surface plasmon resonance studies. The hydrophilic polymer-coated gold colloids can be freeze-dried and stored as powders that can be subsequently dissolved to yield stable aqueous dispersions, even at very large concentrations. They allow for applying filtrations, gel permeation chromatography, or centrifugation. They do not suffer from undesirable nonspecific adsorption of proteins while allowing the diffusion of small species within the hydrogel surface coating. In addition, specific properties of the original hydrophilic polymers are retained such as a lower critical solution temperature. The latter feature could be useful to enhance optical responses of functionalized gold surfaces toward interaction with various substrates. 相似文献