MECHANISTIC STUDY OF A RUTHENIUM HYDRIDE COMPLEX OF TYPE [RuH(CO)(N-N)(PR3)2]+ AS CATALYST PRECURSOR FOR THE HYDROFORMYLATION REACTION OF 1-HEXENE

Indexación: Web of Science; Scopus; Scielo.The catalytic activity of systems of type [RuH(CO)(N-N)(PR3)(2)](+) was evaluated in the hydroformylation reaction of 1-hexene. The observed activity is explained through a reaction mechanism on the basis of the quantum theory. The mechanism included total energy calculations for each of the intermediaries of the elemental steps considered in the catalytic cycle. The deactivation of the catalyst precursors takes place via dissociation of the polypyridine ligand and the subsequent formation of thermodynamically stable species, such as RuH(CO)(3)(PPh3)(2) and RuH3(CO)(PPh3)(2), which interrupt the catalytic cycle. In addition, the theoretical study allows to explain the observed regioselectivity which is defined in two steps: (a) the hydride migration reaction with an anti-Markovnikov orientation to produce the alkyl-linear-complex (3.1a), which is more stable by 19.4 kJ/mol than the Markovnikov orientation (alkyl-branched-complex) (3.1b); (b) the carbon monoxide insertion step generates the carbonyl alkyl-linear specie (4.1a) which is more stable by 9.5 kJ/mol than the alternative species (4.1b), determining the preferred formation of heptanal in the hydroformylation of 1-hexene. Palabras clavehttp://ref.scielo.org/db4yc

Phase Diagram of a Classical Fluid in a Quenched Random Potential

We consider the phase diagram of a classical fluid in the presence of a random pinning potential of arbitrary strength. Introducing replicas for averaging over the quenched disorder, we use the hypernetted chain approximation to calculate the correlations in the replicated liquid. The freezing transition of the liquid into a nearly crystalline state is studied using a density functional approach, and the liquid-to-glass transition is studied using a phenomenological replica symmetry breaking approach introduced by Mezard and Parisi. The first-order liquid-to-crystal transition is found to change to a continuous liquid-to-glass transition as the strength of the disorder is increased above a threshold value.Comment: 7 pages, 4 figures, to appear in EuroPhysics Letter

Upper Airways Microbiota in Antibiotic-Naive Wheezing and Healthy Infants from the Tropics of Rural Ecuador

Background: Observations that the airway microbiome is disturbed in asthma may be confounded by the widespread use of antibiotics and inhaled steroids. We have therefore examined the oropharyngeal microbiome in early onset wheezinginfants from a rural area of tropical Ecuador where antibiotic usage is minimal and glucocorticoid usage is absent. Materials and Methods: We performed pyrosequencing of amplicons of the polymorphic bacterial 16S rRNA gene from oropharyngeal samples from 24 infants with non-infectious early onset wheezing and 24 healthy controls (average age 10.2 months). We analyzed microbial community structure and differences between cases and controls by QIIME software. Results: We obtained 76,627 high quality sequences classified into 182 operational taxonomic units (OTUs). Firmicutes was the most common and diverse phylum (71.22% of sequences) with Streptococcus being the most common genus (49.72%). Known pathogens were found significantly more often in cases of infantile wheeze compared to controls, exemplified by Haemophilus spp. (OR = 2.12, 95% Confidence Interval (CI) 1.82–2.47; P = 5.46610223) and Staphylococcus spp. (OR = 124.1, 95%CI 59.0–261.2; P = 1.876102241). Other OTUs were less common in cases than controls, notably Veillonella spp. (OR = 0.59, 95%CI = 0.56–0.62; P = 8.06610286). Discussion: The airway microbiota appeared to contain many more Streptococci than found in Western Europe and the USA. Comparisons between healthy and wheezing infants revealed a significant difference in several bacterial phylotypes that were not confounded by antibiotics or use of inhaled steroids. The increased prevalence of pathogens such as Haemophilus and Staphylococcus spp. in cases may contribute to wheezing illnesses in this age group

The Role of APEC in the Achievement of Regional Cooperation in Southeast Asia

The Asia Pacific Economic Cooperation (APEC) forum represents a major achievement of regional cooperation in Southeast Asia. APEC\u27s successes have resulted from its informal and amorphous nature, and reflect the fact that the forum constitutes a process for cooperation, rather than an institution. The authors trace the origins and history of APEC, follow developments through the various ministerial meetings, and assess APEC\u27s accomplishments in the areas of trade liberalization, dispute resolution, and the environment. The authors conclude, in view of the diverse interests of its members, that APEC\u27s focus on openness, voluntariness, and decentralization will continue to foster regional cooperation among its members

The Role of APEC in the Achievement of Regional Cooperation in Southeast Asia

The Asia Pacific Economic Cooperation (APEC) forum represents a major achievement of regional cooperation in Southeast Asia. APEC\u27s successes have resulted from its informal and amorphous nature, and reflect the fact that the forum constitutes a process for cooperation, rather than an institution. The authors trace the origins and history of APEC, follow developments through the various ministerial meetings, and assess APEC\u27s accomplishments in the areas of trade liberalization, dispute resolution, and the environment. The authors conclude, in view of the diverse interests of its members, that APEC\u27s focus on openness, voluntariness, and decentralization will continue to foster regional cooperation among its members

Rotating Biological Contractors as an Effective Removal System of Waste Petroleum Hydrocarbons from Untreated Wastewaters

A staged, partially submerged rotating biological disk system was assessed to determine its performance in the reduction of detectable concentrations of polynuclear aromatic hydrocarbons (PAH0 attributable to waste crankcase oils (WCCO) in wastewater effluent. Results indicate that such biological systems for the removal of WCCO aromatic hydrocarbons may be a viable alternative to secondary treatment systems commonly being employed

Control and grid integration of MW-range wind and solar energy conversion systems

Solar-based energy generation has increased by more than ten times over the same period. In total, worldwide electrical energy consumption increased by approximately 6340 TWh from 2003 to 2013. To meet the challenges created by intermittent energy generation sources, grid operators have increasingly demanded more stringent technical requirements for the connection and operation of grid-connected intermittent energy systems, for instance concerning fault ride through capability, voltage and frequency support, and inertia emulation. Ongoing developments include new or improved high-voltage converters, power converters with higher power density, control systems to provide ride-through capability, implementation of redundancy schemes to provide more reliable generation systems, and the use of high-voltage direct current (HVdc) links for the connection of large off-shore intermittent energy systems