全文获取类型
收费全文 | 471篇 |
免费 | 26篇 |
国内免费 | 1篇 |
专业分类
化学 | 372篇 |
晶体学 | 2篇 |
力学 | 13篇 |
数学 | 62篇 |
物理学 | 49篇 |
出版年
2023年 | 7篇 |
2022年 | 10篇 |
2021年 | 12篇 |
2020年 | 15篇 |
2019年 | 17篇 |
2018年 | 8篇 |
2017年 | 17篇 |
2016年 | 18篇 |
2015年 | 14篇 |
2014年 | 21篇 |
2013年 | 32篇 |
2012年 | 46篇 |
2011年 | 60篇 |
2010年 | 22篇 |
2009年 | 23篇 |
2008年 | 30篇 |
2007年 | 23篇 |
2006年 | 32篇 |
2005年 | 31篇 |
2004年 | 16篇 |
2003年 | 10篇 |
2002年 | 8篇 |
2001年 | 1篇 |
2000年 | 3篇 |
1999年 | 2篇 |
1998年 | 3篇 |
1995年 | 1篇 |
1993年 | 3篇 |
1992年 | 2篇 |
1991年 | 1篇 |
1990年 | 1篇 |
1988年 | 1篇 |
1986年 | 1篇 |
1984年 | 2篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1977年 | 2篇 |
1976年 | 1篇 |
排序方式: 共有498条查询结果,搜索用时 15 毫秒
41.
Bibienne Thomas Maillaud Laurent Rousselot Steeve Taylor Lauren W. Pasquali Matteo Dollé Mickaël 《Journal of Solid State Electrochemistry》2017,21(5):1407-1416
Journal of Solid State Electrochemistry - The preparation of collector- and binder-free, high-energy density cathodes made from carbon-coated LiFePO4 (C-LFP) and single-walled carbon nanotubes... 相似文献
42.
Huffman LM Casitas A Font M Canta M Costas M Ribas X Stahl SS 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(38):10643-10650
A well-defined macrocyclic aryl–Cu(III) complex (2) reacts readily with a variety of oxygen nucleophiles, including carboxylic acids, phenols and alcohols, under mild conditions to form the corresponding aryl esters, biaryl ethers and alkyl aryl ethers. The relationship between these reactions and catalytic C-O coupling methods is demonstrated by the reaction of the macrocyclic aryl–Br species with acetic acid and p-fluorophenol in the presence of 10 mol% Cu(I). An aryl-Cu(III)-Br species 2(Br) was observed as an intermediate in the catalytic reaction. Investigation of the stoichiometric C-O bond-forming reactions revealed nucleophile-dependent changes in the mechanism. The reaction of 2 with carboxylic acids revealed a positive correlation between the log(k(obs)) and the pK(a) of the nucleophile (less-acidic nucleophiles react more rapidly), whereas a negative correlation was observed with most phenols (more-acidic phenols react more rapidly). The latter trend resembles previous observations with nitrogen nucleophiles. With carboxylic acids and acidic phenols, UV-visible spectroscopic data support the formation of a ground-state adduct between 2 and the oxygen nucleophile. Collectively, kinetic and spectroscopic data support a unified mechanism for aryl-O coupling from the Cu(III) complex, consisting of nucleophile coordination to the Cu(III) center, deprotonation of the coordinated nucleophile, and C-O (or C-N) reductive elimination from Cu(III). 相似文献
43.
Xiao D Martini LA Snoeberger RC Crabtree RH Batista VS 《Journal of the American Chemical Society》2011,133(23):9014-9022
An inverse design methodology suitable to assist the synthesis and optimization of molecular sensitizers for dye-sensitized solar cells is introduced. The method searches for molecular adsorbates with suitable photoabsorption properties through continuous optimization of "alchemical" structures in the vicinity of a reference molecular framework. The approach is illustrated as applied to the design and optimization of linker chromophores for TiO(2) sensitization, using the recently developed phenyl-acetylacetonate (i.e., phenyl-acac) anchor [McNamara et al. J. Am. Chem. Soc.2008, 130, 14329-14338] as a reference framework. A novel anchor (3-acac-pyran-2-one) is found to be a local optimum, with improved sensitization properties when compared to phenyl-acac. Its molecular structure is related to known coumarin dyes that could be used as lead chromophore anchors for practical applications in dye-sensitized solar cells. Synthesis and spectroscopic characterization confirms that the linker provides robust attachment to TiO(2), even in aqueous conditions, yielding improved sensitization to solar light and ultrafast interfacial electron injection. The findings are particularly relevant to the design of sensitizers for dye-sensitized solar cells because of the wide variety of structures that are possible but they should be equally useful for other applications such as ligand design for homogeneous catalysis. 相似文献
44.
Hapuarachchige S Montaño G Ramesh C Rodriguez D Henson LH Williams CC Kadavakkollu S Johnson DL Shuster CB Arterburn JB 《Journal of the American Chemical Society》2011,133(17):6780-6790
A new class of fluorescent triazaborolopyridinium compounds was synthesized from hydrazones of 2-hydrazinylpyridine (HPY) and evaluated as potential dyes for live-cell imaging applications. The HPY dyes are small, their absorption/emission properties are tunable through variation of pyridyl or hydrazone substituents, and they offer favorable photophysical characteristics featuring large Stokes shifts and general insensitivity to solvent or pH. The stability, neutral charge, cell membrane permeability, and favorable relative influences on the water solubility of HPY conjugates are complementary to existing fluorescent dyes and offer advantages for the development of receptor-targeted small-molecule probes. This potential was assessed through the development of a new class of cysteine-derived HPY-conjugate imaging agents for the kinesin spindle protein (KSP) that is expressed in the cytoplasm during mitosis and is a promising chemotherapeutic target. Conjugates possessing the neutral HPY or charged Alexa Fluor dyes that function as potent, selective allosteric inhibitors of the KSP motor were compared using biochemical and cell-based phenotypic assays and live-cell imaging. These results demonstrate the effectiveness of the HPY dye moiety as a component of probes for an intracellular protein target and highlight the importance of dye structure in determining the pathway of cell entry and the overall performance of small-molecule conjugates as imaging agents. 相似文献
45.
A net trans C-N reductive elimination reaction is observed from a macrocyclic aryl-Cu(III) complex, and a mechanistic study of this reaction indicates that coordinating ligands play a role in mediating this unusual transformation. 相似文献
46.
This paper studies stochastic orderings for folded beta distributions. A necessary and sufficient condition for one folded beta random variable to be larger than another in likelihood ratio order is obtained. The work is motivated by the recent results of Porzio and Ragozini on stochastic orderings for folded binomial distributions. Beta distributions are commonly used to model proportions or probabilities, particularly as conjugate distributions for binomial random variables. Stochastic orderings may arise, for instance, in considerations of fairness in coin flips. 相似文献
47.
Michele Benzi Eldad Haber Lauren Taralli 《Advances in Computational Mathematics》2011,35(2-4):149-173
We investigate the use of a preconditioning technique for solving linear systems of saddle point type arising from the application of an inexact Gauss?CNewton scheme to PDE-constrained optimization problems with a hyperbolic constraint. The preconditioner is of block triangular form and involves diagonal perturbations of the (approximate) Hessian to insure nonsingularity and an approximate Schur complement. We establish some properties of the preconditioned saddle point systems and we present the results of numerical experiments illustrating the performance of the preconditioner on a model problem motivated by image registration. 相似文献
48.
49.
Lauren K. Williams 《Advances in Mathematics》2005,190(2):216-342
Postnikov (Webs in totally positive Grassmann cells, in preparation) has given a combinatorially explicit cell decomposition of the totally nonnegative part of a Grassmannian, denoted Grk,n+, and showed that this set of cells is isomorphic as a graded poset to many other interesting graded posets. The main result of our work is an explicit generating function which enumerates the cells in Grk,n+ according to their dimension. As a corollary, we give a new proof that the Euler characteristic of Grk,n+ is 1. Additionally, we use our result to produce a new q-analog of the Eulerian numbers, which interpolates between the Eulerian numbers, the Narayana numbers, and the binomial coefficients. 相似文献
50.
Kanwarpal S Kochhar Holly J Carson Kimberly A Clouser John W Elling Lauren A Gramens Judith L Parry Helayne L Sherman Kevin Braat Harold W Pinnick 《Tetrahedron letters》1984,25(18):1871-1874
Acetoacetic ester is converted into 4-alkoxy-Δ3-pyrrolin-2-ones which can be hydrolyzed to give tetramic acids. 相似文献