Search results for "DF"
showing 10 items of 1699 documents
Benzyl alcohol to benzaldehyde oxidation on MnOx clusters: Unraveling atomistic features
2021
Abstract The catalytic oxidation of benzyl alcohol with O 2 is a promising option for the production of benzaldehyde, from both environmental and economical viewpoints. In particular, highly dispersed MnO x systems feature good activity and selectivity in a wide range of temperatures, although deactivation phenomena by over-oxidation and/or poisoning of active sites are generally recorded. On this account, a density functional theory study was performed on cluster-sized catalyst models, namely Mn 4 O 8 and over-oxygenated Mn 4 O 9 fragments, to predict the reactivity pattern of MnO x catalysts in the selective aerobic oxidation of benzyl alcohol. Several pathways concur to determine the who…
Propan-2-ol dehydration on H-ZSM-5 and H-Y zeolite: a DFT study
2012
The catalytic dehydration of propan-2-ol over H-Y and H-ZMS-5 aluminated zeolite models, mimicking both internal cavities and external surfaces, was studied by DFT calculations to investigate the reaction mechanism. After the adsorption of propan-2-ol on the zeolite, the dehydration mechanism starts with alcohol protonation, occurring by one acidic –OH group of the zeolite fragment, followed by a concerted β-elimination to give propene. The catalytic activity is affected by the size of the zeolite cavity, which is larger in the H-Y than in the H-ZMS-5 zeolite. The adsorption energy of the reagent, as an example, decreases in the order: H-Y cavity ≃ H-ZMS-5 surface > H-ZMS-5 cavity, pointing…
Pd/C-Catalyzed Hydrosilylation of Enals and Enones with Triethylsilane: Conformer Populations Control the Stereoselectivity
2016
The palladium-on-charcoal-catalyzed chemo-, regio-, and stereoselective 1,4-hydrosilylation and transfer hydrogenation reactions of α,β-unsaturated aldehydes and ketones with triethylsilane have been investigated with a combination of experimental and theoretical methods. The reaction mechanism has been studied experimentally by monitoring the reactions by 1H NMR from aliquots withdrawn from the stirred reaction mixtures, labeling experiments, and control experiments. Our density functional theory results indicate that both aforementioned reactions are initiated with a dissociative adsorption of the triethylsilane on the palladium catalyst. In the hydrosilylation reaction, the α,β-unsaturat…
Theoretical Elucidation of β-O-4 Bond Cleavage of Lignin Model Compound Promoted by Sulfonic Acid-Functionalized Ionic Liquid
2019
While the depolymerization of lignin to chemicals catalyzed by ionic liquids has attracted significant attention, the relevant molecular mechanism, especially the cleavage of specific bonds related to efficient depolymerization, still needs to be deeply understood for the complexity of this natural aromatic polymer. This work presents a detailed understanding of the cleavage of the most abundant β-O-4 bond in the model system, guaiacylglycerol β-guaiacyl ether, by a Brønsted acidic IL (1-methyl-3-(propyl-3-sulfonate) imidazolium bisulfate ([C3SO3Hmim][HSO4]) using density functional theory calculation and molecular dynamics simulation. It has been found that [C3SO3Hmim][HSO4] generates zwit…
The relationship between motor timing, reaction time and academic achievements in primary school children.
2017
Aim: Recent studies have reported a correlation between motor skills and school performance, which is different according to the type of motor ability or academic subject examined (Fernandes et al, 2016; Bellafiore et al., 2016). The aim of this study was to analyze the relationship between motor timing, reaction time and achievements in mathematics and Italian in sedentary and active children. Methods: Seventy-eight children (8.55±1.43 years old, 28.93±5.74 kg weight, 126.54±4.74 cm height and 19.30±2.62 kg/m2 BMI) were randomly recruited by a primary school of Palermo, 68% of them practiced a sport outside the academic hours. The motor timing was measured with the finger and foot tapping …
Effects of a physical education program on the development of early literacy abilities in preschool children
2016
Introduction Several studies showed a relationship between physical activity and cognition in school-aged children (Carson et al 2015). The aim of this study was to analyse whether the amount and frequency of a physical education (PE) program affected the early reading and writing skills in preschool children. Methods This study involved 189 children (age: 4.62 ± 0.97 years; height: 107.83 ± 7.82 cm, body weight: 19.84 ± 4.95 kg) of 8 Palermo kindergartens who were randomly divided in a control group (C, n= 29), a 1-intervention group (I-1, n= 120) and a 2-intervention group (I-2, n= 40). I-1 and I-2 children performed a PE program of 16-week length for 4 and 10 hours/week, respectively (to…
Real estate crowdfunding: potential in Latvia
2017
Currently the economic environment is changing rapidly. The millennium’s development phase was followed by global financial crisis, which has changed the rules of game for all financial players and made others’ think outside the box. After the economic crisis people started losing trust in traditional financial institutions like banks, where all the processes are still very bureaucratic. Overregulated bank lending system could not satisfy the credit demand of small to medium size enterprises, thus triggering the need for a new, innovative financing model to fill the gap. At the same time, the communication afforded by Internet and information technologies opened up new opportunities. Taking…
Endothelial cells and normal breast epithelial cells enhance invasion of breast carcinoma cells by CXCR-4-dependent up-regulation of urokinase-type p…
2008
Here we show the increase of invasion of three breast cancer cell lines (8701-BC, MDA-MB-231 and SKBR3) upon long-term co-incubation with culture medium of normal microvascular endothelial cells (MVEC) and normal breast epithelial cells (HB2). The enhancement of invasion relied on the interaction of microvascular endothelial cell and normal breast epithelial cell CXCL12 (SDF1) chemokine, whose expression by breast cancer cells was very low, with the cognate CXCR4 receptor of malignant cells, which resulted in over-expression of the urokinase-type plasminogen activator receptor (uPAR) on their surfaces. uPAR over-expression, showed by RT-PCR and Western blotting, was paralleled by increased …
Ru(bpy)2Cl2: A catalyst able to shift the course of the photorearrangement in the Boulton-Katritzky reaction
2015
The Boulton-Katritzky reaction represents one of the most popular and efficient strategies used to realize azole-into-azole conversions. For example, under different experimental conditions, it allows the rearrangement of Z-arylhydrazones of 3-benzoyl-5-phenyl-1,2,4-oxadiazoles (1) into 2-aryl-4-benzoylamino-5-phenyl-2H-1,2,3-triazoles (2) in very high yields. Moreover, we have recently realized this conversion also by UV-photostimulation. Now we have enlarged the scope of the reaction irradiating with visible or UV light an acetonitrile solution of some Z-arylhydrazones (1a-e) in the presence of catalytic amounts of Ru(bpY)(2)Cl-2. We have observed the unexpected formation of the 1-aryl-5-…
Vegetation, soils, and humus forms of Sardinian holm oak forests and approximated cross-harmonization of vegetation types, WRB Soil Groups and humus …
2018
Five plant communities, related to elevation above sea level and geological substrata, are recognized in the holm oak forests of Sardinia (Italy). These forests show a considerable inhomogeneous structure due to present day and past uses. Coppice management prevails, influencing the quantity and quality of organic horizons. Most frequent mineral soils are Cambisols, Leptosols, and Regosols. Regarding the humus forms, Moder and, with less extent, Amphi, are prevailing. Furthermore, the paper presents a synoptic table giving a rough picture of the relationships between vegetation types, WRB Soil Groups and humus forms in selected Mediterranean ecosystems.