Asymmetric Hydrogenation vs Transfer Hydrogenation in the Reduction of Cyclic Imines

A comparison between the two most common reduction approaches for obtaining chiral amines, asymmetric hydrogenation (AH) versus asymmetric transfer hydrogenation (ATH), was accomplished by using iridium complexes based on atropoisomeric diphosphines and cyclic diamines as ligands respectively. Seven substrates, different in electronic and steric properties, were screened applying both reduction methods. For AH the best results in terms of enantioselectivity (e.e. up to 64%) were obtained by using [Ir(COD)(TetraMe-BITIOP)]Cl in the presence of DCDMH as additive. ATH was carried out with [IrCp*(CAMPY)Cl]Cl as catalyst, allowing the obtainment of the products with appreciable e.e. (up to 76%)

Next generation sequencing for gut microbiome characterization in rainbow trout (Oncorhynchus mykiss) fed animal by-product meals as an alternative to fishmeal protein sources

Animal by-product meals from the rendering industry could provide a sustainable and commercially viable alternative to fishmeal (FM) in aquaculture, as they are rich in most essential amino acids and contain important amounts of water-soluble proteins that improve feed digestibility and palatability. Among them, poultry by-product meal (PBM) have given encouraging results in rainbow trout (Oncorhynchus mykiss). However, the introduction of new ingredients in the diet needs to be carefully evaluated since diet is one of the main factors affecting the gut microbiota, which is a complex community that contributes to host metabolism, nutrition, growth, and disease resistance. Accordingly, we investigated the effects of partial replacement of dietary FM with a mix of animal by-product meals and plant proteins on intestinal microbiota composition of rainbow trout in relation to growth and feeding efficiency parameters. We used 1540 trout with an initial mean body weight of 94.6 +/- 14.2 g. Fish were fed for 12 weeks with 7 different feed formulations. The growth data showed that trout fed on diets rich in animal by-product meals grew as well as fish fed on control diet, which was rich in FM (37.3%) and PBM-free. High-throughput 16S rRNA gene amplicon sequencing (MiSeq platform, Illumina) was utilised to study the gut microbial community profile. After discarding Cyanobacteria (class Chloroplast) and mitochondria reads a total of 2,701,274 of reads taxonomically classified, corresponding to a mean of 96,474 +/- 68,056 reads per sample, were obtained. Five thousand three hundred ninety-nine operational taxonomic units (OTUs) were identified, which predominantly mapped to the phyla of Firmicutes, Proteobacteria, Bacteroidetes and Actinobacteria. The ratio between vegetable and animal proteins proved to play a central role in determining microbiome profiles and Firmicutes and Proteobacteria phyla were particularly discriminatory for diet type in trout. Plant ingredients favoured a higher Firmicutes: Proteobacteria ratio than animal proteins. Acceptable abundance of Firmicutes was guaranteed by including at least 25% of vegetable proteins in the diet regardless of animal protein source and percentage. In summary animal by-product meals, as replacements to FM, gave good results in terms of growth performances and did not induce significant changes in gut microbial richness, thus proving to be a suitable protein source for use in rainbow trout aqua feed

Control of spatiotemporal rogue waves by harmonic pump modulation in a semiconductor laser with a saturable absorber

Through numerical simulations, statistical and dynamical properties of extreme events in a broad-area semiconductor laser with intracavity saturable absorber are investigated. By inclusion of a diffusion coefficient for the field, formation of rogue waves in a state of extended turbulence is studied and shown to be affected by harmonic perturbations. In particular, we propose a control technique based on periodic modulation of the pump parameter which can either drive the state of the system closer to or away from the chaotic attractors respectively enhancing or suppressing the generation of rogue waves. By statistical and dynamical analysis of the events in terms of intensity and optical gain, we show that when the system is under resonant modulation with frequency close to that of the dominant oscillations in the turbulent state (which is equal to the relaxation oscillation frequency typical of semiconductor lasers), more rogue waves are triggered with larger intensities and shorter lifetimes. On the other hand, off-resonant modulations restrain the formation of rogue waves where they appear in lower intensities and longer lifetimes. An example of special cases where the proposed scheme can completely forbid or allow the emission of rogue waves is also presented

Efficient methodology to produce a duloxetine precursor using whole cells of Rhodotorula rubra

Different types of yeasts were employed as biocatalysts in the reduction of \u3b2-ketonitriles. The red microorganism, Rhodotorula rubra, was selected as the best performing catalyst in the reduction of different substituted ketonitriles giving total stereoselectivity in most cases (90-99% ee). In particular, its use as fresh and lyophilised cells was expanded to a semi-preparative scale for the production of the duloxetine precursor 1a. R. rubra was screened in the reduction of alkylation products in comparison with Pichia henricii for assignment of configuration of products 2a and 11a after derivatisation with S-MPA

Vancomycin-Iridium (III) Interaction: An Unexplored Route for Enantioselective Imine Reduction

The chiral structure of antibiotic vancomycin (Van) was exploited as an innovative coordination sphere for the preparation of an IrCp* based hybrid catalysts. We found that Van is able to coordinate iridium (Ir(III)) and the complexation was demonstrated by several analytical techniques such as MALDI-TOF, UV, Circular dichroism (CD), Raman IR, and NMR. The hybrid system so obtained was employed in the Asymmetric Transfer Hydrogenation (ATH) of cyclic imines allowing to obtain a valuable 61% e.e. (R) in the asymmetric reduction of quinaldine 2. The catalytic system exhibited a saturation kinetics with a calculated eciency of Kcat/KM = 0.688 h1mM

Vascular dysfunction in children conceived by assisted reproductive technologies: underlying mechanisms and future implications.

Epidemiological studies in humans have demonstrated a relationship between pathological events during fetal development and increased cardiovascular risk later in life and have led to the so called "Fetal programming of cardiovascular disease hypothesis". The recent observation of generalised vascular dysfunction in young apparently healthy children conceived by assisted reproductive technologies (ART) provides a novel and potentially very important example of this hypothesis. This review summarises recent data in ART children demonstrating premature subclinical atherosclerosis in the systemic circulation and pulmonary vascular dysfunction predisposing to exaggerated hypoxia-induced pulmonary hypertension. These problems appear to be related to the ART procedure per se. Studies in ART mice demonstrating premature vascular aging and arterial hypertension further demonstrate the potential of ART to increase cardiovascular risk and have allowed to unravel epigenetic alterations of the eNOS gene as an underpinning mechanism. The roughly 25% shortening of the life span in ART mice challenged with a western style high-fat-diet demonstrates the potential importance of these alterations for the long-term outcome. Given the young age of the ART population, data on cardiovascular endpoints will not be available before 20 to 30 years from now. However, already now cohort studies of the ART population are needed to early detect cardiovascular alterations with the aim to prevent or at least optimally treat cardiovascular complications. Finally, a debate needs to be engaged on the future of ART and the consequences of its exponential growth for public health

Fast shower simulation in the ATLAS calorimeter

The time to simulate pp collisions in the ATLAS detector is largely dominated by the showering of electromagnetic particles in the heavy parts of the detector, especially the electromagnetic barrel and endcap calorimeters. Two procedures have been developed to accelerate the processing time of electromagnetic particles in these regions: (1) a fast shower parameterisation and (2) a frozen shower library. Both work by generating the response of the calorimeter to electrons and positrons with Geant 4, and then reintroduce the response into the simulation at runtime. In the fast shower parameterisation technique, a parameterisation is tuned to single electrons and used later by simulation. In the frozen shower technique, actual showers from low-energy particles are used in the simulation. Full Geant 4 simulation is used to develop showers down to ~1 GeV, at which point the shower is terminated by substituting a frozen shower. Judicious use of both techniques over the entire electromagnetic portion of the ATLAS calorimeter produces an important improvement of CPU time. We discuss the algorithms and their performance in this paper

Presencia de Hydrochoerus hydrochaeris (Hydrochoeridae, Rodentia, Mammalia) en la cuenca del río Carcarañá, Santa Fe, Argentina: Comentarios acerca de su conservación y biogeografía en Argentina

Capybara (Hydrochoerus hydrochaeris) is the world largest rodent and a typical mammal of the phytogeographical provinces of Pampa and Espinal, inhabiting the eastern sector of the same. These regions have been categorized by the World Wildlife Foundation (WWF) as "critical/ endangered threatened" and are assigned the highest priority level of conservation as a result of habitat destruction, overexploitation, pollution and introduction of exotic species. The capybara has a marked preference for environments with permanent water where the marsh vegetation provides food and shelter. Thus, both water bodies as associated vegetation is critical to the prevalence of populations of capybaras in a given environment. In Santa Fe province, records are not very abundant, registering until now about 33 points based on collected and observed specimens, most located in the center and north of the province. The aim of this contribution is to present new records of capybara in Carcarañá river basin (south of Santa Fe province), and its association with some climatic-environmental variables, and evaluate the distribution of this species. Finally, we discussed the possible expansion or migration of this species to the west of Santa Fe and Buenos Aires provinces.El carpincho (Hydrochoerus hydrochaeris) es el roedor actual más grande del mundo y uno de los mamíferos típico de las Provincias Fitogeográficas Pampeana y del Espinal, habitando todo el sector Este de las mismas. Estas regiones han sido categorizadas por la World Wildlife Foundation (WWF) como áreas "en peligro crítico/ amenazada", y se les asigna el nivel de máxima prioridad de conservación como consecuencia de la destrucción de hábitat, la sobreexplotación, la contaminación y la introducción de especies exóticas. El carpincho presenta una preferencia marcada por los ambientes con abundancia de cuerpos de agua donde la vegetación palustre le proporciona alimento y refugio. De esta forma, tanto los cuerpos de agua como la vegetación asociada es determinante para la prevalescencia de poblaciones de carpinchos en un ambiente determinado. Para la provincia de Santa Fe los registros no son muy abundantes, registrándose hasta la actualidad unos 33 puntos de colecta/observación, la gran mayoría ubicados en el centro y norte de la provincia. El objetivo de la presente contribución es presentar nuevos registros de presencia de Hydrochoerus hydrochaeris en la cuenca del río Carcarañá (sur de la provincia de Santa Fe), y su asociación con algunas variables climático-ambientales y evaluar la distribución de esta especie. Finalmente, se discute la posible expansión o migración de este especie hacia el oeste de esta provincia y de la provincia de Buenos Aires

Presencia de Hydrochoerus hydrochaeris (Hydrochoeridae, Rodentia, Mammalia) en la cuenca del río Carcarañá, Santa Fe, Argentina: Comentarios acerca de su conservación y biogeografía en Argentina

El carpincho (Hydrochoerus hydrochaeris) es el roedor actual más grande del mundo y uno de los mamíferos típico de las Provincias Fitogeográficas Pampeana y del Espinal, habitando todo el sector Este de las mismas. Estas regiones han sido categorizadas por la World Wildlife Foundation (WWF) como áreas "en peligro crítico/ amenazada", y se les asigna el nivel de máxima prioridad de conservación como consecuencia de la destrucción de hábitat, la sobreexplotación, la contaminación y la introducción de especies exóticas. El carpincho presenta una preferencia marcada por los ambientes con abundancia de cuerpos de agua donde la vegetación palustre le proporciona alimento y refugio. De esta forma, tanto los cuerpos de agua como la vegetación asociada es determinante para la prevalescencia de poblaciones de carpinchos en un ambiente determinado. Para la provincia de Santa Fe los registros no son muy abundantes, registrándose hasta la actualidad unos 33 puntos de colecta/observación, la gran mayoría ubicados en el centro y norte de la provincia. El objetivo de la presente contribución es presentar nuevos registros de presencia de Hydrochoerus hydrochaeris en la cuenca del río Carcarañá (sur de la provincia de Santa Fe), y su asociación con algunas variables climático-ambientales y evaluar la distribución de esta especie. Finalmente, se discute la posible expansión o migración de este especie hacia el oeste de esta provincia y de la provincia de Buenos Aires