Regio- and stereoselective synthesis of acetallic tetrahydropyrans as building blocks for natural products preparation, via a tandem [4+3]-cycloaddition/ozonolysis Process

A highly versatile synthetic pathway is presented for the preparation of polyfunctionalized acetallic tetrahydropyrans from conveniently substituted 1-methoxy-8-oxabicyclo[3.2.1]- oct-6-en-3-one derivatives, as intermediates in the total synthesis of natural and unnatural products with structural, functional and/or biological importance. This synthetic methodology involves two key steps: a [4 + 3] cycloaddition reaction between an oxyallyl cation and 2-methoxyfuran as a diene, followed by oxidative and/or reductive ozonolysis of the cycloheptenone subunit. This sequence renders polyfunctionalized 2-methoxytetrahydropyranic products capable of being easily opened under acidic conditions. The key steps, cycloaddition and subsequent ozonolysis were both fully studied under different reaction conditions and using several substrates in order to optimize yields and stereoselectivities and to study the scope of the methodology. It is noteworthy that both reactions proceed with high diastereoselectivity and, in the case of the oxidative ozonolysis, outstanding regioselectivity as well. A chemical library of 14 polyfunctionalized tetrahydrofurans, having five or seven stereocenters, has been prepared using the detailed approach

Differences in cardiorespiratory responses in winter mountaineering according to the pathway snow conditions

Locomotion during ascent requires higher energetic consumption than in flat terrain. Efficiency in locomotion decreases in snowy terrain, presumably because of the changes in the biomechanical pattern of walking. This study aims to observe differences in cardiorespiratory responses and energetic expenditure between locomotion in a snowy terrain with an already fixed footstep pathway (FP) and in fresh virgin snow (FS) that has not been previously compacted. 15 volunteers participated in the study, all of them with experience in mountain activities at a competition level, with a regular training regime up to 10 hours a week. Estimated maximal theoretical oxygen consumption showed a mild increase (2,6% CI 95%: 0.9-4.5%, t=3.2, p=0.005) when subjects progressed in FP. Time necessary to complete FS (4 min and 15 sec ± 30 sec) itinerary was longer than for FP (3 min 45 sec ± 29 sec). Uphill walking velocity improved in 0.43 ± 0.11 Km·h-1 (t=4.2 p=0,01) when progressing in CT. Respiratory rate was higher for FS (2.3 ± 2.4 b·min-1, t=4.0 p= 0.001). For a same itinerary, locomotion in snow that has not been compacted before requires more time and represents a higher energetic cost, either at maximal or submaximal intensities. This should be considered in scheduling mountain ascents as part of the safety strategies. Climbing on virgin snow impedes developing maximal aerobic power so athletes must regard the value of strength work of lower limbs to improve performance

Emergence of Zipf's Law in the Evolution of Communication

Zipf's law seems to be ubiquitous in human languages and appears to be a universal property of complex communicating systems. Following the early proposal made by Zipf concerning the presence of a tension between the efforts of speaker and hearer in a communication system, we introduce evolution by means of a variational approach to the problem based on Kullback's Minimum Discrimination of Information Principle. Therefore, using a formalism fully embedded in the framework of information theory, we demonstrate that Zipf's law is the only expected outcome of an evolving, communicative system under a rigorous definition of the communicative tension described by Zipf.Comment: 7 pages, 2 figure

Robustness of the European power grids under intentional attack

The power grid defines one of the most important technological networks of our times and sustains our complex society. It has evolved for more than a century into an extremely huge and seemingly robust and well understood system. But it becomes extremely fragile as well, when unexpected, usually minimal, failures turn into unknown dynamical behaviours leading, for example, to sudden and massive blackouts. Here we explore the fragility of the European power grid under the effect of selective node removal. A mean field analysis of fragility against attacks is presented together with the observed patterns. Deviations from the theoretical conditions for network percolation (and fragmentation) under attacks are analysed and correlated with non topological reliability measures.Comment: 7 pages, 4 figure

In-line monitoring and control of rheological properties through data-driven ultrasound soft-sensors

The use of continuous processing is replacing batch modes because of their capabilities to address issues of agility, flexibility, cost, and robustness. Continuous processes can be operated at more extreme conditions, resulting in higher speed and efficiency. The issue when using a continuous process is to maintain the satisfaction of quality indices even in the presence of perturbations. For this reason, it is important to evaluate in-line key performance indicators. Rheology is a critical parameter when dealing with the production of complex fluids obtained by mixing and filling. In this work, a tomographic ultrasonic velocity meter is applied to obtain the rheological curve of a non-Newtonian fluid. Raw ultrasound signals are processed using a data-driven approach based on principal component analysis (PCA) and feedforward neural networks (FNN). The obtained sensor has been associated with a data-driven decision support system for conducting the process

The BTB-zinc finger transcription factor abrupt acts as an epithelial oncogene in drosophila melanogaster through maintaining a progenitor-like cell state

The capacity of tumour cells to maintain continual overgrowth potential has been linked to the commandeering of normal self-renewal pathways. Using an epithelial cancer model in Drosophila melanogaster, we carried out an overexpression screen for oncogenes capable of cooperating with the loss of the epithelial apico-basal cell polarity regulator, scribbled (scrib), and identified the cell fate regulator, Abrupt, a BTB-zinc finger protein. Abrupt overexpression alone is insufficient to transform cells, but in cooperation with scrib loss of function, Abrupt promotes the formation of massive tumours in the eye/antennal disc. The steroid hormone receptor coactivator, Taiman (a homologue of SRC3/AIB1), is known to associate with Abrupt, and Taiman overexpression also drives tumour formation in cooperation with the loss of Scrib. Expression arrays and ChIP-Seq indicates that Abrupt overexpression represses a large number of genes, including steroid hormone-response genes and multiple cell fate regulators, thereby maintaining cells within an epithelial progenitor-like state. The progenitor-like state is characterised by the failure to express the conserved Eyes absent/Dachshund regulatory complex in the eye disc, and in the antennal disc by the failure to express cell fate regulators that define the temporal elaboration of the appendage along the proximo-distal axis downstream of Distalless. Loss of scrib promotes cooperation with Abrupt through impaired Hippo signalling, which is required and sufficient for cooperative overgrowth with Abrupt, and JNK (Jun kinase) signalling, which is required for tumour cell migration/invasion but not overgrowth. These results thus identify a novel cooperating oncogene, identify mammalian family members of which are also known oncogenes, and demonstrate that epithelial tumours in Drosophila can be characterised by the maintenance of a progenitor-like state

Optical properties of low background PEN structural components for the LEGEND-200 experiment

Polyethylene Naphthalate (PEN) plastic scintillator has been identified as potential self-vetoing structural material in low-background physics experiments. Scintillating components have been produced radio-pure from PEN using injection compression molding technology. These low-background PEN components will be used as active holders to mount the Germanium detectors in the \legend-$200$ neutrinoless double beta decay experiment. In this paper we present the measurement of the optical properties of these PEN components. Thus, the emission spectrum, time constant, attenuation and bulk absorption length as well as light output and light yield are reported. In addition, the surface of these PEN components has been characterized and an estimation of the surface roughness is presented. Moreover, the light output of the final \legend-$200$ detector holders has been measured and is reported. These measurements were used to estimate the self-vetoing efficiency of these holders

Sobredosis de Colchicina: Reporte de un Caso. Discusión de la dosis tóxica

La intoxicación por colchicina es una entidad poco común, pero que constituye una emergencia toxicológica extremadamente grave que pone en riesgo la vida del paciente. La intoxicación puede ocurrir por ingestión de tabletas de drogas que contienen colchicina o por ingesta de Colchicum autumnale, que florece en otoño en el Pirineo y es erróneamente colectado en lugar de Allium ursinum. La sobredosis debe ser reconocida tempranamente ya que el abordaje terapéutico debe ser llevado a cabo lo más rápido posible, para lograr un efecto beneficioso para el paciente. En este trabajo se presenta un caso de intoxicación con 50mg de colchicina como tentativa suicida, queevoluciona con falla multiorgánica y posterior buena evolución clínica que genera su alta a los diez días del ingreso al hospital. La falta de relación entre la alta dosis ingerida y la buena evolución de la paciente podrían explicarse por la existencia de polimorfismos en las enzimas involucradas en elmetabolismo de esta droga

Persistent Scatterer Interferometry (PSI) technique for landslide characterization and monitoring

: The measurement of landslide superficial displacement often represents the most effective method for defining its behavior, allowing one to observe the relationship with triggering factors and to assess the effectiveness of the mitigation measures. Persistent Scatterer Interferometry (PSI) represents a powerful tool to measure landslide displacement, as it offers a synoptic view that can be repeated at different time intervals and at various scales. In many cases, PSI data are integrated with in situ monitoring instrumentation, since the joint use of satellite and ground-based data facilitates the geological interpretation of a landslide and allows a better understanding of landslide geometry and kinematics. In this work, PSI interferometry and conventional ground-based monitoring techniques have been used to characterize and to monitor the Santo Stefano d’Aveto landslide located in the Northern Apennines, Italy. This landslide can be defined as an earth rotational slide. PSI analysis has contributed to a more in-depth investigation of the phenomenon. In particular, PSI measurements have allowed better redefining of the boundaries of the landslide and the state of activity, while the time series analysis has permitted better understanding of the deformation pattern and its relation with the causes of the landslide itself. The integration of ground-based monitoring data and PSI data have provided sound results for landslide characterization. The punctual information deriving from inclinometers can help in defining the actual location of the sliding surface and the involved volumes, while the measuring of pore water pressure conditions or water table level can suggest a correlation between the deformation patterns and the triggering factors