全文获取类型
收费全文 | 443篇 |
免费 | 13篇 |
国内免费 | 2篇 |
专业分类
化学 | 354篇 |
力学 | 8篇 |
数学 | 62篇 |
物理学 | 34篇 |
出版年
2024年 | 1篇 |
2023年 | 4篇 |
2022年 | 25篇 |
2021年 | 21篇 |
2020年 | 15篇 |
2019年 | 16篇 |
2018年 | 12篇 |
2017年 | 2篇 |
2016年 | 20篇 |
2015年 | 16篇 |
2014年 | 6篇 |
2013年 | 31篇 |
2012年 | 47篇 |
2011年 | 42篇 |
2010年 | 32篇 |
2009年 | 14篇 |
2008年 | 29篇 |
2007年 | 34篇 |
2006年 | 25篇 |
2005年 | 19篇 |
2004年 | 18篇 |
2003年 | 13篇 |
2002年 | 7篇 |
2001年 | 1篇 |
2000年 | 1篇 |
1999年 | 1篇 |
1998年 | 1篇 |
1997年 | 3篇 |
1995年 | 1篇 |
1993年 | 1篇 |
排序方式: 共有458条查询结果,搜索用时 15 毫秒
121.
Christopher Barfoot David T. Davies Ilaria Giordano Graham Jones Michael McGuire Neil Pearson Ravinder Sudini Jeffery Wood 《Tetrahedron letters》2010,51(21):2846-7488
This Letter describes the synthetic challenges in synthesising key 1,4-cis-substituted cyclohexylamide intermediate 1 for our research programme. Five different routes address the major issues of selectivity to afford the cis product in isomerically pure form and in high yield. Major purification issues were also encountered upon scaling some of the routes. The merits of the diverse routes are assessed and the reasoning given for which one was ultimately used for large-scale synthesis of 1. 相似文献
122.
This study was aimed at comparatively investigating the hydrolysis of crystalline and amorphous poly-(ethylene terephthalate) films by alkali and cutinase. Changes of surface properties were investigated by FTIR spectroscopy (ATR mode). The A1341/A1410 and I1120/I1100 absorbance ratios, and the full width at half maximum of the carbonyl stretching band (FWHM1715) were used to evaluate the polymer crystallinity and its changes upon hydrolysis. The effect of different treatments on chain orientation was evaluated by calculating R ratios of appropriate bands. The spectroscopic indexes showed that both alkali and enzyme treatments induced structural and conformational rearrangements with a consequent increase in crystallinity in both amorphous and crystalline films. The crystalline PET film was modified more strongly by alkali than by cutinase, while the opposite occurred for the amorphous one. The trend of the water contact angle (WCA) clearly indicates that alkali is more effective than cutinase in enhancing hydrophilicity of PET films and that the effect is stronger on amorphous than on crystalline films. The values of WCA correlate well with the FTIR indexes calculated from the spectra of hydrolyzed crystalline PET films. The mechanism of the surface hydrolysis of PET by alkali and cutinase is discussed. 相似文献
123.
Prestianni A Martorana A Labat F Ciofini I Adamo C 《The journal of physical chemistry. B》2006,110(25):12240-12248
With the aim of understanding the elementary steps governing the oxidation of CO catalyzed by dispersed or supported gold nanoclusters, the adsorption of molecular species, such as O2 and CO, on model neutral and positively charged clusters (Au(n)(m+) n = 1, 9, and 13; m = 0, 1, and 3) has been studied using an ab initio approach. The computed structural and thermodynamic data related to the binding process show that molecular oxygen interacts better with neutral clusters, acting as an electron acceptor, while CO more strongly binds to positively charged species, thus acting as an electron donor. 相似文献
124.
Andreotti A Bonaduce I Colombini MP Ribechini E 《Rapid communications in mass spectrometry : RCM》2004,18(11):1213-1220
Two analytical methods based on mass spectrometry were used in the characterisation of constituents of natural indigo prepared from the leaves of Indigofera tinctoria, and of shellfish purple prepared from the hypobranchial glandular secretions of Murex trunculus, following old recipes. On-line pyrolysis gas chromatography in the presence of hexamethyldisilazane followed by mass spectrometric analysis (Py-silylation/GC/MS), and direct exposure mass spectrometry (DE-MS), were used. Extensive fragmentation of indigoid dyes was obtained by Py-silylation/GC/MS. The following molecular markers were highlighted, which are useful for identification purposes: 1,2-dihydro-3H-indol-3-one for indigoid dyes, 1,3-dihydro-2H-indol-2-one for indirubine, and 6-bromo-1,2-dihydro-3H-indol-3-one for shellfish purple. Using DE-MS, 6,6'dibromoindigotine, monobromoindigotine and indigotine were identified as the main components, and the presence of tyrindoxyl, one of the dye precursors, was also assessed. 相似文献
125.
D'Acquarica I Gasparrini F Giannoli B Badaloni E Galletti B Giorgi F Tinti MO Vigevani A 《Journal of chromatography. A》2004,1061(2):167-173
We describe a new tandem-columns chiral-achiral HPLC arrangement by using a chiral column (CHIROBIOTIC TAG) connected in series with an achiral column (Spherisorb S5 SCX), based on a strong cationic exchange mechanism; this approach is very useful for the analysis of chiral molecules, containing cationic groups in their structures. We used this special combination to develop an easy and convenient procedure for the enantio- and chemo-selective dosage of propionyl L-carnitine (1) and relative impurities (2-6), which allowed for the simultaneous separation and quantitation within 30 min. Under the best chromatographic conditions (acetonitrile-10 mM sodium dihydrogen phosphate 65:35, v/v (pHa 6.80) as the mobile phase and UV detection at 205 nm], all the individual peaks were well separated. The applicability of the method, fully validated, was demonstrated by the analysis of a pharmaceutical batch of propionyl L-carnitine, where we found the following contents: 98.5% for 1 (drug substance); 0.15% for 3; 0.1% for 5 and 0.2% for 6. The enantiomeric excess (e.e.%) measured for the drug substance was 98.9%. Finally, a single mixed-bed column, packed with a binary mixture of the chiral and achiral phases, in a 1:1 ratio, gave similar chromatographic results as the tandem-columns approach, and thus, offered an easy alternative solution to the separation of the considered mixture. 相似文献
126.
Dueymes C Schönberger A Adamo I Navarro AE Meyer A Lange M Imbach JL Link F Morvan F Vasseur JJ 《Organic letters》2005,7(16):3485-3488
A new solution-phase phosphoramidite approach is reported for oligonucleotide synthesis employing recyclable solid-supported reagents. It uses polyvinyl pyridinium tosylate as the activator of a nucleoside-3'-O-phosphoramidite in the coupling step with a 5'-OH nucleoside or dinucleotide. The resulting phosphite triester was either sulfurized or oxidized using polystyrene-bound trimethylammonium tetrathionate or periodiate. This method avoids complicated purification steps, as excess reagents are easily removed by filtration. [reaction: see text] 相似文献
127.
Giorgio Lanzani Rocco Martinazzo Giuliana Materzanini Ilaria Pino Gian Franco Tantardini 《Theoretical chemistry accounts》2007,117(5-6):805-825
Recent years have witnessed an ever growing interest in theoretically studying chemical processes at surfaces. Apart from the interest in catalysis, electrochemistry, hydrogen economy, green chemistry, atmospheric and interstellar chemistry, theoretical understanding of the molecule–surface chemical bonding and of the microscopic dynamics of adsorption and reaction of adsorbates are of fundamental importance for modeling known processes, understanding new experimental data, predicting new phenomena, controlling reaction pathways. In this work, we review the efforts we have made in the last few years in this exciting field. We first consider the energetics and the structural properties of some adsorbates on metal surfaces, as deduced by converged, first-principles, plane-wave calculations within the slab-supercell approach. These studies comprise water adsorption on Ru(0001), a subject of very intense debate in the past few years, and oxygen adsorption on aluminum, the prototypical example of metal passivation. Next, we address dynamical processes at surfaces with classical and quantum methods. Here the main interest is in hydrogen dynamics on metallic and semi-metallic surfaces, because of its importance for hydrogen storage and interstellar chemistry. Hydrogen sticking is studied with classical and quasi-classical means, with particular emphasis on the relaxation of hot–atoms following dissociative chemisorption. Hot atoms dynamics on metal surfaces is investigated in the reverse, hydrogen recombination process and compared to Eley–Rideal dynamics. Finally, Eley–Rideal, collision-induced desorption, and adsorbate-induced trapping are studied quantum mechanically on a graphite surface, and unexpected quantum effects are observed. 相似文献
128.
Andrea Salvo Valentina Mangano Manuela Grimaldi Ilaria Stillitano Anna Maria D’Ursi 《Natural product research》2020,34(1):71-77
AbstractAlmonds are the tasty seeds of Prunus dulcis plants globally appreciated for the pleasant palatability and remarkable nutritional value, therefore it is very spread as snack and as basic ingredient of the confectionery products. The HR-MAS-NMR is a simple spectroscopy able to directly and quickly explore the chemical composition of powdered seed samples dispersed in D2O. 1H spectra witness the remarkable presence of triglyceride fatty esters together with sucrose; other minor water soluble metabolites are also detectable. This very rough approach is effectively providing chemical profiles featuring almond samples. In this analysis we were able to statistically distinguish the “Avola” almonds from other marketed products submitted to the same analysis. This is just a first investigation based on the main compounds but it might pave the way toward the quantitative evaluation of many other compounds in the almond therefore implementing the HR-MAS-NMR knowledge of these precious seeds. 相似文献
129.
Ilaria Paolini Maria de la Cruz Pozo-Carrero Francesca Barbetti Zbigniew J. Kaminski Anna M. Papini 《Tetrahedron letters》2007,48(16):2901-2904
Optimization of coupling reactions of glycosylamines with Fmoc-protected aspartic acid, by microwave approach, is described. Different reaction conditions, quantities of substrates and solvents were tested to develop simple and reproducible methodologies. The best results were obtained using new triazine-based coupling reagents with a monomode microwave Discover® BenchMate™ instrument (CEM). The N-glycosyl amino acids were then deprotected to achieve final products for SPPS. 相似文献
130.
Francesco Paolo Invidiata Giancarlo Furn Ilaria Lampronti Daniele Simoni 《Journal of heterocyclic chemistry》1997,34(4):1255-1258
The reaction of thiocarbohydrazide with carboxylic acids at the melting temperature allows an improved preparation of the S-substituted 4-amino-3-mercapto-1,2,4-triazole heterocycles. The crude 4-amino-5-mercapto-1,2,4-triazoles react easily with carboxylic acids or carboxylic acid chlorides to afford the 1,2,4-triazolo[3,4-fc][1,3,4]thiadiazole ring system. 相似文献