全文获取类型
收费全文 | 386篇 |
免费 | 7篇 |
国内免费 | 3篇 |
专业分类
化学 | 181篇 |
晶体学 | 1篇 |
力学 | 30篇 |
数学 | 122篇 |
物理学 | 62篇 |
出版年
2022年 | 10篇 |
2021年 | 14篇 |
2020年 | 10篇 |
2019年 | 6篇 |
2018年 | 14篇 |
2017年 | 10篇 |
2016年 | 17篇 |
2015年 | 12篇 |
2014年 | 14篇 |
2013年 | 40篇 |
2012年 | 22篇 |
2011年 | 33篇 |
2010年 | 21篇 |
2009年 | 16篇 |
2008年 | 21篇 |
2007年 | 15篇 |
2006年 | 15篇 |
2005年 | 19篇 |
2004年 | 13篇 |
2003年 | 10篇 |
2002年 | 6篇 |
2001年 | 7篇 |
2000年 | 8篇 |
1999年 | 4篇 |
1998年 | 3篇 |
1997年 | 2篇 |
1996年 | 2篇 |
1995年 | 5篇 |
1994年 | 7篇 |
1993年 | 3篇 |
1992年 | 4篇 |
1991年 | 2篇 |
1990年 | 1篇 |
1989年 | 3篇 |
1985年 | 1篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1978年 | 1篇 |
1970年 | 1篇 |
1940年 | 2篇 |
排序方式: 共有396条查询结果,搜索用时 15 毫秒
41.
Hossini I Harrad MA Ait Ali M El Firdoussi L Karim A Valerga P Puerta MC 《Molecules (Basel, Switzerland)》2011,16(7):5886-5895
Friedel-Craft acylation at 100 °C of 2,5,9,9-tetramethyl-6,7,8,9-tetrahydro-5H-benzocycloheptene [ar-himachalene], a sesquiterpenic hydrocarbon obtained by catalytic dehydrogenation of α-, β- and γ-himachalenes, produces a mixture of two compounds: (3,5,5,9-tetramethyl-6,7,8,9-tetrahydro-5H-benzocyclohepten-2-yl)-ethanone (2, in 69% yield), with a conserved reactant backbone, and 3, with a different skeleton, in 21% yield. The crystal structure of 3 reveals it to be 1-(8-ethyl-8-hydroperoxy-3,5,5-trimethyl-5,6,7,8-tetrahydronaphthalen-2-yl)-ethanone. In this compound O-H…O bonds form dimers. These hydrogen-bonds, in conjunction with weaker C-H…O interactions, form a more extended supramolecular arrangement in the crystal. 相似文献
42.
Gerber I Oubenali M Bacsa R Durand J Gonçalves A Pereira MF Jolibois F Perrin L Poteau R Serp P 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(41):11467-11477
The nitric acid oxidation of multiwalled carbon nanotubes leading to surface carboxylic groups has been investigated both experimentally and theoretically. The experimental results show that such a reaction involves the initial rapid formation of carbonyl groups, which are then transformed into phenol or carboxylic groups. At room temperature, this reaction takes place on the most reactive carbon atoms. At higher temperatures a different mechanism would operate, as evidenced by the difference in activation energies. Experimental data can be partially related to first-principles calculations, showing a multistep functionalization mechanism. The theoretical aspects of the present article have led us to propose the most efficient pathway leading to carboxylic acid functional groups on the surface. Starting from mono-vacancies, it ends up with the synergistic formation of dangling -COOH groups and the enlargement of the vacancies. 相似文献
43.
Harrad MA Valerga P Puerta MC Houssini I Ali MA El Firdoussi L Karim A 《Molecules (Basel, Switzerland)》2011,16(1):367-372
A recyclable catalyst, Ni(0)-CMC-Na, composed of nickel colloids dispersed in a water soluble bioorganic polymer, sodium carboxymethylcellulose (CMC-Na), was synthesized by a simple procedure from readily available reagents. The catalyst thus obtained is stable and highly active in alkene hydrogenations. 相似文献
44.
Bourdolle A Allali M Mulatier JC Le Guennic B Zwier JM Baldeck PL Bünzli JC Andraud C Lamarque L Maury O 《Inorganic chemistry》2011,50(11):4987-4999
Two europium complexes with bis(bipyridine) azamacrocyclic ligands featuring pendant arms with or without π-conjugated donor groups are synthesized and fully characterized by theoretical calculations and NMR spectroscopy. Their photophysical properties, including two-photon absorption, are investigated in water and in various organic solvents. The nonfunctionalized ligand gives highly water-stable europium complexes featuring bright luminescence properties but poor two-photon absorption cross sections. On the other hand, the europium complex with an extended conjugated antenna ligand presents a two-photon absorption cross section of 45 GM at 720 nm but is poorly luminescent in water. A detailed solvent-dependent photophysical study indicates that this luminescence quenching is not due to the direct coordination of O-H vibrators to the metal center but to the increase of nonradiative processes in a protic solvent induced by an internal isomerization equilibrium. 相似文献
45.
Abdelmounaim Safer Mustapha Rahmouni François Carreaux Ludovic Paquin Olivier Lozach Laurent Meijer Jean Pierre Bazureau 《Chemical Papers》2011,65(3):332-337
A series of nine 5-arylidenerhodanine derivatives was prepared in good yields and purity without the use of a solvent or catalyst
under microwave-assisted condensation with some substituted isatins. All 5-arylidenerhodanines were evaluated as possible
inhibitors of the CK1α/β, CDK5/p25, and GSK-3α/β kinases. None of them showed substantive inhibitory activity against these kinases when evaluated at the concentration of
10 μM. 相似文献
46.
Heidar Raissi Effat Moshfeghi Abraham F. Jalbout Mohammad Saeid Hosseini Mustapha Fazli 《International journal of quantum chemistry》2007,107(9):1835-1845
The molecular structure and intramolecular hydrogen bond energy of 32 conformers of 4‐methylamino‐3‐penten‐2‐one were investigated at MP2 and B3LYP levels of theory using the standard 6–31G** basis set and AIM analyses. Furthermore, calculations for all the possible conformations of 4‐methylamino‐3‐penten‐2‐one in water solution were also carried out at B3LYP/6–31G** level of theory. The calculated geometrical parameters and conformational analyses in gas phase and water solution show that the ketoamine conformers of this compound are more stable than the other conformers (i.e., enolimine and ketoimine). This stability is mainly due to the formation of a strong N? H···O intramolecular hydrogen bond, which is assisted by π‐electrons resonance. Hydrogen bond energies for all conformers of 4‐methylamino‐3‐penten‐2‐one were obtained from the related rotamers method. The nature of intramolecular hydrogen bond existing within 4‐methylamino‐3‐penten‐2‐one has been investigated by means of the Bader theory of atoms in molecules, which is based on topological properties of the electron density. The results of these calculations support the results which obtained by related rotamers method. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 相似文献
47.
Khadidja Bourahla Mustapha Rahmouni Joan Fraga‐Dubreuil Jean Pierre Bazureau Jack Hamelin 《Journal of heterocyclic chemistry》2007,44(1):193-199
The synthesis of new 3‐substituted coumarins appended to imidazolium, pyridinium, 3‐dimethylamino pyridinium, 3‐chloro pyridinium and 3‐bromo pyridinium salts is reported. These salts were prepared by tandem reactions, followed by quantitative anionic metathesis. The structure of these new 3‐substituted coumarins was established by NMR (1H, 13C) and high‐resolution mass spectrometry. 相似文献
48.
A new effective approach to the synthesis of a small library of 2-amino-5-arylidene-1,3-thiazol-4(5H)-ones was reported using solvent-free reaction conditions under microwave irradiation. In the first step, rhodanines were subjected to Knoevenagel condensation with aryl aldimines according to a facile one-pot protocol. Then the (5Z)-5-arylidene rhodanine derivatives were transformed directly into the corresponding 2-amino-1,3-thiazol-4(5H)-ones by sulfur/nitrogen displacement reaction under microwaves with retention of configuration and good overall yields. 相似文献
49.
50.
El Houssine MABROUK Nadia ARROUSSE Adil KORCHI Mohammed LACHGAR Ahmad OUBAIR Abdelrhani ELACHQAR Mohamed JABHA Mohammed LACHKAR Fadoua El HAJJAJI Zakia RAIS Mustapha TALEB 《高等学校化学研究》2020,36(6):1183-1189
The α-amino acid derivatives constitute a class of compounds of particular medicinal and synthetic attention and considerable interest has been devoted to their synthesis in recent years. In the present work, we develop the computational study of the synthesis reaction of new pyrazolyl α-amino esters derivatives using the Gaussian 09 based on the DFT/B3LYP density functional theory method, with the base 6-31G(d, p) to ensure the possibility of carrying out these reactions within the laboratory of synthesis. Indeed, this research has encouraged us to establish an economical synthesis strategy of these products in overall yields of 73.5% to 87% to have access to new active biomolecule through the O-alkylation reaction between methyl α-azidoglycinate N-benzoylated and primary pyrazole alcohols[(3,5-dimethyl-1H-pyrazol-1-yl)methanol, (1H-pyrazol-1-yl)methanol and (3-ethoxy-5-methyl-1H-pyrazol-1-yl)methanol] under different operating conditions. The structure of the prepared heterocyclic systems was characterized by conventional spectroscopic techniques, like 1H NMR, 13C NMR, and MS. The results revealed that the experimental study is in good correlation with the computational one. 相似文献