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

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

Quinstant Dark Energy Predictions for Structure Formation

We explore the predictions of a class of dark energy models, quinstant dark energy, concerning the structure formation in the Universe, both in the linear and non-linear regimes. Quinstant dark energy is considered to be formed by quintessence and a negative cosmological constant. We conclude that these models give good predictions for structure formation in the linear regime, but fail to do so in the non-linear one, for redshifts larger than one.Comment: 9 pages, 14 figures, "Accepted for publication in Astrophysics & Space Science

Magnon valley Hall effect in CrI3-based vdW heterostructures

Magnonic excitations in the two-dimensional (2D) van der Waals (vdW) ferromagnet CrI3 are studied. We find that bulk magnons exhibit a non-trivial topological band structure without the need for Dzyaloshinskii-Moriya (DM) interaction. This is shown in vdW heterostructures, consisting of single-layer CrI3 on top of different 2D materials as MoTe2, HfS2 and WSe2. We find numerically that the proposed substrates modify substantially the out-of-plane magnetic anisotropy on each sublattice of the CrI3 subsystem. The induced staggered anisotropy, combined with a proper band inversion, leads to the opening of a topological gap of the magnon spectrum. Since the gap is opened non-symmetrically at the K+ and K- points of the Brillouin zone, an imbalance in the magnon population between these two valleys can be created under a driving force. This phenomenon is in close analogy to the so-called valley Hall effect (VHE), and thus termed as magnon valley Hall effect (MVHE). In linear response to a temperature gradient we quantify this effect by the evaluation of the temperature-dependence of the magnon thermal Hall effect. These findings open a different avenue by adding the valley degrees of freedom besides the spin, in the study of magnons

Coupling parameters and the form of the potential via Noether symmetry

We explore the conditions for the existence of Noether symmetries in the dynamics of FRW metric, non minimally coupled with a scalar field, in the most general situation, and with nonzero spatial curvature. When such symmetries are present we find general exact solution for the Einstein equations. We also show that non Noether symmetries can be found. Finally,we present an extension of the procedure to the Kantowski- Sachs metric which is particularly interesting in the case of degenerate Lagrangian.Comment: 13 pages, no figure

Preliminary optical design of PANIC, a wide-field infrared camera for CAHA

In this paper, we present the preliminary optical design of PANIC (PAnoramic Near Infrared camera for Calar Alto), a wide-field infrared imager for the Calar Alto 2.2 m telescope. The camera optical design is a folded single optical train that images the sky onto the focal plane with a plate scale of 0.45 arcsec per 18 micron pixel. A mosaic of four Hawaii 2RG of 2k x 2k made by Teledyne is used as detector and will give a field of view of 31.9 arcmin x 31.9 arcmin. This cryogenic instrument has been optimized for the Y, J, H and K bands. Special care has been taken in the selection of the standard IR materials used for the optics in order to maximize the instrument throughput and to include the z band. The main challenges of this design are: to produce a well defined internal pupil which allows reducing the thermal background by a cryogenic pupil stop; the correction of off-axis aberrations due to the large field available; the correction of chromatic aberration because of the wide spectral coverage; and the capability of introduction of narrow band filters (~1%) in the system minimizing the degradation in the filter passband without a collimated stage in the camera. We show the optomechanical error budget and compensation strategy that allows our as built design to met the performances from an optical point of view. Finally, we demonstrate the flexibility of the design showing the performances of PANIC at the CAHA 3.5m telescope.Comment: This paper has been presented in the SPIE of Astronomical Telescopes and Instrumentation 2008 in Marseille (France

Entomology in Ecuador : recent developments and future challenges

We review and analyze the recent development and future challenges facing entomology as a science in Ecuador, a country with limited financial and human resources and numerous environmental problems. Taxonomic studies of the Ecuadorian insect fauna have been well developed for only a few groups (e.g. Papilionoidea, Carabidae) and remains in its infancy for most insect orders. This is due to the huge diversity of species living in a great diversity of habitats and the difficulty to identify most species. There is a lack of published basic biological information and to a high rate of endemism of many groups, especially in the Andes. The development of ecological entomology as a formal discipline in Ecuador is a very recent phenomenon, and has been mostly limited to descriptive studies of the environmental factors that govern insect diversity and abundance. We outline a set of research challenges regarding the impact of global environmental changes on insect communities and habitats they live in and propose potential strategies for the development of entomology in Ecuador. Both basic and applied research will be important in this context as well as international collaboration to strengthen the role of entomological science in decision making processes in the country

Scalar-tensor theory with EGB term from Einstein Chern-Simons gravity

It is shown that the compactification a la Randall Sundrum of the so called, five dimensional Einstein Chern Simons action gravity leads to an action for a four dimensional scalar tensor gravity that includes a Gauss Bonnet term, which belongs to a particular case of the action of the Horndeski theory. The five dimensional action includes new gravitational degrees of freedom that were introduced requiring that the action be invariant under symmetries greater than the usual Poincare or (A)dS symmetries, namely the so called generalized Poincare algebras B5.Comment: To be published in Nucl. Phys.

Reservefonds gegen Naturkatastrophen auf nationaler und europäischer Ebene

Katastrophenfonds funktionieren nach dem Prinzip der Kapitalakkumulation. Sie werden teilweise auf nationaler und europäischer Ebene eingesetzt, um sich gegen die finanziellen Schäden, verursacht durch extreme Naturereignisse, zu schützen. Basierend auf Beispielen in Europa, wie dem österreichischen Katastrophenfonds sowie dem europäischen Solidaritätsfonds, werden die Vor- und Nachteile von Reservefonds aufgezeigt und mögliche Lösungsvorschläge für gegenwärtige Probleme präsentiert. Vor allem die nichtrisikobasierte Anwendung wird als Problem betrachtet. Es werden Methoden vorgestellt, wie ein wahrscheinlichkeitstheoretischer Ansatz aussehen könnte, um sowohl direkte als auch indirekte Schäden bei der Analyse mit einzubeziehen und daraus Strategien zu entwickeln, die sich langfristig als nachhaltig erweisen.Catastrophe reserve funds are used to cover the potential costs of a disaster by capital accumulation. Based on examples in Europe, especially the national disaster fund in Austria and the European Solidarity Fund, the advantages and disadvantages of such a risk management instrument are shown and possible solutions are proposed. The main criticism is the non-risk based approach of these instruments. Methodologies how one can incorporate direct as well as indirect losses within a probability based approach are presented

Transcranial magnetic stimulation in depression--lessons from the multicentre trials

Looking at novelties and advances in medicine in particular in the treatment of major depressive disorder no principally new antidepressant treatment strategy has been established in clinical routine in the last fifty years. However, regarding the considerable issue of treatment resistance in depression, new therapeutic strategies are urgently required. In this context, repetitive transcranial magnetic stimulation above the dorsolateral prefrontal cortex has been proposed as a potential new treatment option for depression; furthermore, in October 2008 a first rTMS-device (NeuroStar TMS Therapy System™) was approved by the FDA for the treatment of treatment resistant major refractory depression in adults. Yet, despite now nearly two decades of research in this field, no final answer concerning its validity for antidepressant treatment in the clinical practice is given. Numerous studies with small sample sizes and heterogeneous designs have been performed in this field yielding to different results. These were subjected to meta-analyses, assessing the antidepressant effect of rTMS, which are briefly summarized in this article. Further, multicentre-trials with larger numbers of patients were performed, which are presented and critically discussed here in more detail. This short review shall thus provide an overview of the current status of knowledge concerning rTMS in depression and it also provides some recommendations for future research in this field