Dynamic Kinetic Resolution of Hetero biaryl Ketones by Zinc- Catalyzed Asymmetr ic Hydrosil ylation

Adiastereo- and highly enantioselective dynamic kinetic resolution (DKR) of configurationally labile hetero- biaryl ketones is described. The DKR proceeds by zinc- catalyze dhydrosilylation of the carbonyl group ,thus leading to secondary alcohols bearing axial and central chirality .The strategy relies on the labilization of the stereogenic axis that takes place thanks to aLewis acid–base interaction between anitrogen atom in the heterocycle and the ketone carbonyl group .The synthetic utility of the methodology is demonstrated through stereospecific transformations into either N,N-ligands or appealing axially chiral, bifunctional thiourea organocata- lysts.Ministerio de Ciencia e Innovación (Grants CTQ2016-76908-C2-1-P, CTQ2016-76908-C2-2-P, contract RYC-2013-12585)European FEDER FundsJunta de Andalucía (Grant 2012/FQM 10787)European Union - Marie Skłodowska-Curie (COFUND—Grant Agreement n 8 8 291780

A Dynamic Kinetic Asymmetric Heck Reaction for the Simultaneous Generation of Central and Axial Chirality

A highly diastereo- and enantioselective, scalable Pd-catalyzed dynamic kinetic asymmetric Heck reaction of heterobiaryl sulfonates with electron-rich olefins is described. The coupling of 2,3-dihydrofuran or N-boc protected 2,3-dihydropyrrole with a variety of quinoline, quinazoline, phthalazine, and picoline derivatives takes place with simultaneous installation of central and axial chirality, reaching excellent diastereo- and enantiomeric excesses when in situ formed [Pd0/DM-BINAP] was used as the catalyst, with loadings reduced down to 2 mol % in large scale reactions. The coupling of acyclic, electron-rich alkenes can also be performed using a [Pd0/Josiphos ligand] to obtain axially chiral heterobiaryl α-substituted alkenes in high yields and enantioselectivities. Products from Boc-protected 2,3-dihydropyrrole can be easily transformed into N,N ligands or appealing axially chiral, bifunctional proline-type organocatalysts. Computational studies suggest that a β-hydride elimination is the stereocontrolling step, in agreement with the observed stereochemical outcome of the reaction.Ministerio de Ciencia e Innovación (Grants CTQ2016-76908-C2-1-P; CTQ2016-76908-C2-2-P; CTQ2016-78083-P; RYC-2013-12585)European Commission (FEDER Programme)Junta de Andalucía (Grant 2012/FQM 10787)Universidad de Sevilla (Grant No. 1800511201)European Union - Marie Skłodowska-Curie (COFUND—Grant Agreement nº 291780

Cutaneous lesions associated to multiple endocrine neoplasia syndrome type 1

Original article[Abstract] Background  Multiple endocrine neoplasia type 1 (MEN1) is a genetic disease that predisposes to endocrine tumour development. Some cutaneous lesions (angiofibromas, collagenomas, melanosis guttaca, lipomas, melanomas, ‘cafe au lait macules’) have been associated to this syndrome. We compare the prevalence of cutaneous lesion in affected patients with their non‐carrier relatives. Patients and method  We studied 9 patients with MEN1 and 20 non‐carrier, first‐degree relatives. Genetic screening was realized in all of them. Patients were examined by dermatologist, and biopsy was performed when necessary. Results  Patients with MEN1 presented hyperparathyroidism (100%), neuroendocrine tumours of pancreas (66%) and pituitary adenomas (44%); their relatives were free of endocrine features of MEN1. The studied cutaneous lesions were more prevalent in affected patients than in non‐carriers (55.5% vs. 25%; P = 0.029). Odds ratio of developing cutaneous lesions in MEN1 patients was 6.6 (95% confidence interval, 1.09–40.43). The frequency of angiofibromas was lower (22.2%) than the reported in other studies (43–88%), and we did not find any collagenoma. Conclusions  MEN1 is associated to some cutaneous lesions and could be useful for detecting MEN1 carriers in an affected family. Cutaneous lesions should be assessed in MEN1 patients.Instituto de Salud Carlos III; FIS PI051024Xunta de Galicia; PGIDT05PXIC91605P

Heterogeneous electro-Fenton treatment: preparation, characterization and performance in groundwater pesticide removal

In this work the preparation, characterization and performance of Y-zeolite as catalyst for electro-Fenton treatment of pesticides was carried out. Initially iron supported Y-zeolite (Fe-Y) was prepared and evaluated for the degradation of imidacloprid and chlorpyrifos. Kinetics studies determined that the pesticides removal followed a pseudo-first-order kinetic model. However, the reusability of this catalyst was not appropriated and to enhance its recyclability, Fe-Y catalyst was embedded in alginate (Al-Fe-Y). The new catalyst showed similar degradation efficiency; and the recyclability was improved. This study demonstrated that Al-Fe-Y could be efficiently used to remove commonly pesticides, imidacloprid and chlorpyrifos, of aqueous medium.This work has been supported by the Xunta de Galicia (EM2012/083). The authors are thankful to the Ramón y Cajal programme for Marta Pazos’ financial support and to C.A.C.T.I. from Vigo University for providing access to their Electron Microscopy Service

Geant4-GATE Simulation of a Large Plastic Scintillator for Muon Radiography

Envisaging the possibility of using large-area plastic scintillator slabs as robust detectors for high spatial resolution muon radiography, and prior to prototype development, we study expected basic performance by Monte Carlo simulation. We present preliminary results for a scalable square footprint detector unit of similar to 1 m(2), defining a representative simulation model volume of 50 cm x 50 cm, with reflective surfaces and a light readout by direct coupling of 4 small PMTs (in a square arrangement) at one face of the scintillator slab. Light detection efficiency is calculated for several light collection configurations, considering different values of surface roughness, reflectivity, optical coupling index and scintillator thickness. Values maximizing photon detection have been identified. The light response function of 2.5-3.5 cm diameter PMTs for the proposed configuration has been determined. A detector intrinsic spatial resolution of the order of 1 cm is estimated for muon interactions at the center region of the detector module, using a simple centroid positioning algorithm (Anger logic)

Cell death in hepatocellular carcinoma: Pathogenesis and therapeutic opportunities

Hepatocellular carcinoma (HCC) is the most prevalent primary liver cancer and the third leading cause of cancer death worldwide. Closely associated with liver inflammation and fibrosis, hepatocyte cell death is a common trigger for acute and chronic liver disease arising from different etiologies, including viral hepatitis, alcohol abuse, and fatty liver. In this review, we discuss the con-tribution of different types of cell death, including apoptosis, necroptosis, pyroptosis, or autophagy, to the progression of liver disease and the development of HCC. Interestingly, inflammasomes have recently emerged as pivotal innate sensors with a highly pathogenic role in various liver diseases. In this regard, an increased inflammatory response would act as a key element promoting a pro-oncogenic microenvironment that may result not only in tumor growth, but also in the formation of a premetastatic niche. Importantly, nonparenchymal hepatic cells, such as liver sinusoidal endothelial cells, hepatic stellate cells, and hepatic macrophages, play an important role in establishing the tumor microenvironment, stimulating tumorigenesis by paracrine communication through cytokines and/or angiocrine factors. Finally, we update the potential therapeutic options to inhibit tumorige-nesis, and we propose different mechanisms to consider in the tumor microenvironment field for HCC resolution. © 2021 by the authors. Licensee MDPI, Basel, Switzerland

Results of the 2004 Spanish Experimental Fishing in NAFO Subarea 1

An experimental fishing was carried out with three bottom trawlers commercial Spanish vessels from July to December of the year 2004 in the Subarea 1. The main objective of the experimental fishing was to search for cephalopods species concentrations inside the territorial waters of Greenland. During the experimental fishing a scientific observer stayed on board each vessel to collect effort data, catches and yields by haul and Division. The observers carried out length distribution samplings of the following species: Reinhardtius hippoglossoides, Pandalus borealis, Gadus morhua, Sebastes spp., Hippoglossoides platessoides and Macrourus berglax. Biological samplings of R. hippoglossoides, P. borealis, H. platessoides, G. morhua and M. berglax were also carried out. Otoliths of Greenland halibut (1 356) and Atlantic cod (739) were collected for age determination. Greenland halibut was the main species caught and the cephalopods, target species, have not been found in the experimental fishing

Recreational water skiing in people with paraplegia: A study of three cases

Objetivos: se analizaron la condición cardiorrespiratoria y la intensidad de esfuerzo durante la práctica recreativa del esquí náutico de slalom. Metodología: participaron tres esquiadores náuticos con paraplejia moderadamente activos. Realizaron un test incremental en un ergómetro de brazos para determinar su VO2pico y los umbrales ventilatorios y completaron 3 sesiones de práctica de esquí náutico, separadas por 48h, registrándose la FC cada 5 s. Resultados: obtuvieron un VO2pico de 22,3 ± 0,6 mL·kg-1·min-1 y los umbrales ventilatorios se analizaron al ~80 y ~50% del VO2pico. La FC media en las sesiones de esquí náutico fue de 111 ppm, lo que representó una intensidad de ~45% de la FC de reserva (FCR), permaneciendo por encima del 40% de la FCR ~12 min. Conclusión: la intensidad moderada de la práctica recreativa de esquí náutico de slalom podría servir para mantener o mejorar la condición cardiorrespiratoria en estas tres personas con paraplejiaObjectives: the cardiorespiratory fitness and the intensity of effort were analyzed during the recreational practice of slalom water skiing. Methodology: three moderately active water skiers with paraplegia participated. They performed an incremental test on an arm ergometer to determine their VO2peak and ventilatory thresholds and completed 3 sessions of water skiing, separated by 48h, where the HR was recorded every 5 s. Results: they obtained a VO2peak of 22.3 ± 0.6 mL·kg-1·min-1 and the ventilatory thresholds were analyzed at ~80 and ~50% of the VO2peak. The average heart rate in the water ski sessions was 111 bpm, which represented an intensity of ~45% of the heart rate reserve (HRR), remaining above 40% of the HRR ~12 min. Conclusion: the moderate intensity of recreational slalom skiing could serve to maintain or improve the cardiorespiratory fitness in these three people with paraplegi

Personalización de prácticas para el desarrollo de sistemas telemáticos avanzados

El artículo presenta la experiencia del desarrollo de un curso práctico para desarrollar Sistemas Telemáticos Avanzados, introduciendo técnicas de inteligencia artificial. El curso se ha estructurado con el fin de que los alumnos se motiven y puedan decidir el contenido y la carga de trabajo que quieren dedicarle

FinFET Versus Gate-All-Around Nanowire FET: Performance, Scaling, and Variability

Performance, scalability and resilience to variability of Si SOI FinFETs and gate-all-around (GAA) nanowires (NWs) are studied using in-house-built 3D simulation tools. Two experimentally based devices, a 25 nm gate length FinFET and a 22 nm GAA NW are modelled and then scaled down to 10.7 and 10 nm gate lengths, respectively. A TiN metal gate work-function granularity (MGG) and line edge roughness (LER) induced variability affecting OFF and ON characteristics are investigated and compared. In the OFF-region, the FinFETs have over an order of magnitude larger OFF-current that those of the equivalent GAA NWs. In the ON-region, the 25/10.7 nm gate length FinFETs deliver 20/58% larger ON-current than the 22/10 nm gate length GAA NWs. The FinFETs are more resilient to the MGG and LER variability in the sub-threshold compared to the GAA NWs. However, the MGG ON-current variability is larger for the 10.7 nm FinFET than that for the 10 nm GAA NW. The LER ON-current variability depends largely on the RMS height; whereas a 0.6 nm RMS height yields a similar variability for both FinFETs and GAA NWs. Finally, the industry preferred 110 channel orientation is more resilient to the MGG and LER variability in both architectures