全文获取类型
收费全文 | 355篇 |
免费 | 10篇 |
国内免费 | 3篇 |
专业分类
化学 | 260篇 |
力学 | 5篇 |
数学 | 77篇 |
物理学 | 26篇 |
出版年
2023年 | 3篇 |
2022年 | 4篇 |
2021年 | 15篇 |
2020年 | 14篇 |
2019年 | 5篇 |
2018年 | 4篇 |
2017年 | 2篇 |
2016年 | 8篇 |
2015年 | 6篇 |
2014年 | 14篇 |
2013年 | 10篇 |
2012年 | 13篇 |
2011年 | 29篇 |
2010年 | 13篇 |
2009年 | 10篇 |
2008年 | 25篇 |
2007年 | 37篇 |
2006年 | 20篇 |
2005年 | 17篇 |
2004年 | 17篇 |
2003年 | 19篇 |
2002年 | 18篇 |
2001年 | 3篇 |
2000年 | 8篇 |
1999年 | 2篇 |
1997年 | 2篇 |
1996年 | 2篇 |
1995年 | 2篇 |
1994年 | 3篇 |
1993年 | 2篇 |
1992年 | 2篇 |
1991年 | 3篇 |
1989年 | 3篇 |
1987年 | 3篇 |
1985年 | 3篇 |
1984年 | 2篇 |
1983年 | 2篇 |
1981年 | 3篇 |
1978年 | 2篇 |
1977年 | 3篇 |
1973年 | 1篇 |
1971年 | 1篇 |
1970年 | 1篇 |
1969年 | 1篇 |
1967年 | 1篇 |
1966年 | 1篇 |
1965年 | 1篇 |
1963年 | 1篇 |
1906年 | 1篇 |
1904年 | 1篇 |
排序方式: 共有368条查询结果,搜索用时 312 毫秒
51.
Maria Grazia Concilio 《Magnetic resonance in chemistry : MRC》2020,58(8):691-717
Computational modeling is becoming an essential tool in magnetic resonance to design and optimize experiments, test the performance of theoretical models, and interpret experimental data. Recent theoretical research and software development made possible simulations of large spin systems, for example, proteins with thousands of spins, in reasonable time. In the last few years, the Fokker–Planck formalism also re-emerged due to its ability to handle spatial dynamics. The purpose of this tutorial is to describe advantages and disadvantages of the most common formalisms, the latest developments and strategies to improve the computational efficiency, and to guide users in the setting up of a simulation using the Spinach software. 相似文献
52.
Silvia Rita Amato Aviva Burnstock Maureen Cross Koen Janssens Francesca Rosi Laura Cartechini Raffaella Fontana Alice Dal Fovo Marco Paolantoni Chiara Grazia Aldo Romani Anne Michelin Christine Andraud Aurélie Tournié Joris Dik 《X射线光谱测定》2019,48(4):282-292
The paintings by Édouard Manet in The Courtauld Gallery Déjeuner sur l'herbe (1863–68), Marguerite de Conflans en Toilette de Bal (1870–1880), Banks of the Seine at Argenteuil (1874), and A Bar at the Folies–Bergère (1882) were investigated for the first time using a range of non-invasive in situ analyses. The aims of the study were to investigate the painting techniques and materials used for this group of works and to critically evaluate the technical evidence derived from the integrated use of imaging techniques and portable spectroscopic methods in this context. The paintings were investigated by means of macro X-ray fluorescence (MA-XRF), reflection spectral imaging, portable UV–Vis–NIR spectroscopy, portable Raman spectroscopy, and reflection FTIR. MA-XRF and reflection spectral imaging allowed visualising elements in the compositions that were not visible using traditional methods of technical study. For example, MA-XRF analysis of Déjeuner sur l'herbe revealed elements of the development of the composition that provided new evidence to consider its relationship to other versions of the composition. The study also highlighted questions about the interpretation of elemental distribution maps and spectral images that did not correspond to the reworking visible in X-radiographs. For example, in A Bar at the Folies–Bergère Manet made numerous changes during painting, which were not clearly visualised with any of the techniques used. The research has wider implications for the study of Impressionist paintings, as the results will support technical studies of works by other artists of the period who used similar materials and painting methods. 相似文献
53.
54.
Giovanni Neri Giuseppe Rizzo Lidia De Luca Andrea Donato Maria Grazia Musolino Rosario Pietropaolo 《Reaction Kinetics and Catalysis Letters》2008,93(2):193-202
Selective catalytic reduction of campholenic aldehyde to naturanol was investigated over Sn-and Fe-doped SiO2, and Fe2O3-supported Pd catalysts. On Pd/SiO2 and Pd-Sn/SiO2 only saturated campholenic aldehyde is formed. Addition of Fe increases the C=O hydrogenation rate producing the corresponding
unsaturated alcohol with a good selectivity. Also Fe2O3-supported catalysts were found to be more selective towards carbonyl hydrogenation. Addition of tin to Pd/Fe2O3 contributes to a further selectivity enhancement towards naturanol. 相似文献
55.
ATP-Independent and Cell-Free Biosynthesis of β-Hydroxy Acids Using Vinyl Esters as Smart Substrates
Dr. Alejandro H. Orrego Dr. Maria Grazia Rubanu Idania L. López Daniel Andrés-Sanz Dr. Guillermo García-Marquina Dr. German E. Pieslinger Prof. Luca Salassa Prof. Fernando López-Gallego 《Angewandte Chemie (International ed. in English)》2023,62(13):e202218312
In vitro biosynthetic pathways that condense and reduce molecules through coenzyme A (CoASH) activation demand energy and redox power in the form of ATP and NAD(P)H, respectively. These coenzymes must be orthogonally recycled by ancillary reactions that consume chemicals, electricity, or light, impacting the atom economy and/or the energy consumption of the biosystem. In this work, we have exploited vinyl esters as dual acyl and electron donor substrates to synthesize β-hydroxy acids through a non-decarboxylating Claisen condensation, reduction and hydrolysis stepwise cascade, including a NADH recycling step, catalyzed by a total of 4 enzymes. Herein, the chemical energy to activate the acyl group with CoASH and the redox power for the reduction are embedded into the vinyl esters. Upon optimization, this self-sustaining cascade reached a titer of (S)-3-hydroxy butyrate of 24 mM without requiring ATP and simultaneously recycling CoASH and NADH. This work illustrates the potential of in vitro biocatalysis to transform simple molecules into multi-functional ones. 相似文献
56.
We have re-examined the problem of the interaction of melanins with metal ions. Metal ions are normal constituents of the
pigment, but in some cases they can be related to pathologies, mainly at the level of the skin (Cu2+ and Fe3+) and of the central nervous system (Fe2+ and Mn2+). Our approach has been based on the mechanisms of adsorption on the particle surface, by the use of theoretical adsorption
isotherms and kinetic models. Although this analysis doesn’t give detailed information on the specific sites involved, it
is useful to better characterize the surface behaviour of the colloidal melanin. The results obtained demonstrate that the
affinity of melanin for metal ions is very high, comparable to the most efficient materials employed in decontamination and
recovery techniques. Moreover, our results demonstrate that three-parameters models, such as Langmuir-Freundlich, Redlich-Peterson
and Tóth equations, fit the experimental data with great accuracy and that the adsorption follows pseudo-second-order kinetics. 相似文献
57.
Grazia Cafeo Dr. Franz H. Kohnke Prof. Luca Valenti Andrew J. P. White Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(36):11593-11600
10α,20α‐Bis(4‐nitrophenyl)calix[4]pyrrole ( 1 ) forms 1:1 complexes with anions of selected aromatic hydroxy acids in which the host orientation within the guest is controlled by a change in the pH value. Some bis‐anionic guests, including those obtained from 4‐hydroxybenzoic acid, 1,4‐ and 1,3‐benzenedicarboxylic acids, induce the self‐assembly of molecular capsules involving two molecules of the receptor. 1H NMR data and solid‐state structures of the 1:1 complex of 1 with p‐C6H4(COOH)(COO?)+NMe4 and the 2:1 capsule [( 1 )2m‐C6H4(COO?)2(+NMe4)2] provide structural details in solution and in the solid state. 相似文献
58.
59.
The self-assembly of a thymine nucleotide-calixarene hybrid (1) in CDCl3 as a solvent was investigated. FT-IR, ESI-MS, 1H and DOSY-NMR spectra evidenced that compound 1 (ammonium or sodium salt) self-assembles in a triangular trimeric supramolecule by thymine-thymine hydrogen bonding. The saline form is crucial for the arrangement in the cyclic trimer as the protonation of the nucleotide phosphate groups leads the assembly toward a dimeric species. 相似文献
60.
The electronic properties of a single layer (SL) of pentacene molecules are investigated by high-resolution UV photoemission and near-edge X-ray absorption spectroscopy in different configurations of the SL, either standing up on an aromatic self-assembled monolayer or planar on a bare Cu(001) substrate. The weakly interacting pentacene molecules in the standing-up SL present a semiconducting character, and the empty states distribution reflects that of gas-phase pentacene, while the planar pentacene-Cu system shows a metallic interface with redistribution of the empty molecular states. The highest-occupied molecular orbital lineshape in the weakly interacting SL shows a double structure, attributed to two nonequivalent molecules in the ordered configuration. 相似文献