Ligand-controlled divergent formation of alkenyl- or allylboronates catalyzed by Pd, and synthetic applications

The use of different ligands allows the preparation of either allyl- or alkenylboronates by Pd-catalyzed borylation of allylic carbonates containing alkyne groups. Unprecedented borylative cyclisation to alkenylboronates takes place with PCy3. The difficult dissociation of NHC ligands allows borylation of carbonates in the presence of alkynes. Oxidation, regioselective Suzuki coupling, as well as Au-catalyzed cycloisomerisation of boronates illustrate the potential synthetic applications of these reactionsThis work was supported by the MICINN (CTQ2010-15927) and the CAM (Project AVANCAT). We thank the UAM for a fellowship to R. L.-D., and the CCC-UAM for computation tim

Nickel-Catalyzed cascade Cyclization-Negishi coupling of redox active esters for the synthesis of pyrrolidines

We have developed a Ni-catalyzed cascade cyclization/Negishicoupling reaction for the formation of pyrrolidines and pyrrolidinones starting from N-protected allylamines and acrylamides which contain a redox active ester group. The reaction provides two C C bonds in a single operation and takes place with both alkylzinc and arylzinc bromides as nucleophiles. Activation of RAE by low valent Ni complexes involving a radical pathway followed by a fast cyclization of intermediate carbon radicals is proposeWe thank the support by MICIU(CTQ2016-79826-R and PID2019- 109088GB I00) and for a FPI fellowship to J. C. N

Copper-catalysed cross-coupling of alkyl Grignard reagents and propargylic ammonium salts: Stereospecific synthesis of allenes

Herein we describe a robust and practical method to prepare enantiomerically enriched trisubstituted allenes using alkyl Grignard reagents and bench stable propargylic ammonium salts. Excellent yields as well as regio- and stereoselectivities are observed. Our conditions provide a solution to the allene racemization, which has been a long-standing problem when using Grignard reagents

Two-dimensional carbon-based conductive materials with dynamically controlled asymmetric Dirac cones

The design of two dimensional graphene-type materials with an anisotropic electron flow direction in the X- and Y-axes opens the door for the development of novel electronic materials with multiple functions in nanoelectronics. In the present work, we have studied the electronic transport properties of a new family of 2D graphene-graphyne hybrids presenting conformationally free phenylethylene subunits. This system ensures two different conductive pathways that are perpendicular to each other: an acene nanoribbon subunit, in the X-axis, with graphene-type conduction, and a free to rotate phenylethylene subunit, in the Y-axis, in which the magnitude of the conduction depends dynamically on the corresponding torsion angle. Our calculations have confirmed that this system presents two different conduction pathways, which are related to the presence of asymmetric Dirac-type cones. Moreover, the Dirac cones can be dynamically modified in the presence of an external gate electrode, which is unprecedented in the literatureWe thank the MICINN (project CTQ-2011.22455) and the Regional Government of Andalucía (project P09-FQM-04571) for financial support and the ‘Centro de Supercomputación de la Universidad de Granada (UGRGRID-CSIRC)’ for computation time. NF and DM thank MICINN for their research contract

Conductance and application of organic molecule pairs as nanofuses

We propose that a pair of organic molecules can mimic the behavior of a macroscopic fuse at nanoscale, one component of the pair being the on state and the other the off state. For this task wemake use of density-functional theory to calculate the physical properties of selected molecules, which have also been synthesized by our team. By this means we obtain the transmission spectra and the current of the proposed devices, which allows us to compare the behavior of the on and off states.Of particular interest is the on/off switch ratios, defined as the current ratios of the on and off structures at the corresponding bias voltage. In a first stage, we examine the best linker between the device and the electrode for high on/off switch ratios. Once this is determined, we test the influence of the electron richness of the system to provide a high on/off switch ratio. The entire analysis is also supported by the molecular projected self-consistent Hamiltonian, which provides a good way of understanding the molecular behavior. All the calculations support that interesting on/off switch ratios of two orders of magnitude could be obtained with these prototypical nanofusesWe thank the Regional Government of Andalucía for financial support (Projects No. P06-FQM-01726 and No. P09-FQM-04571), the “Centro de Supercomputación de la Universidad de Granada,” and the “Centro de Computación Científica-UAM” for computation time. The authors are also grateful to the Spanish Secretaría de Estado de Universidades e Investigación, Ministerio de Educación y Ciencia, for financial support within research projects TEC2007-66812 and TEC2010-16211. N.F. thanks the Regional Government of Andalucía for her research contract, and LAC thanks the University of Granada for his research contrac

Novel ortho-OPE metallofoldamers: binding-induced folding promoted by nucleating Ag(i)-alkyne interactions

We have developed a new family of ortho-oligophenylene ethynylene (o-OPE) metallofoldamers. The folding of these helicates is induced by nucleating carbon-metal interactions between Ag(i) cations and the alkynes of the inner core of the o-OPEs. These o-OPEs form metal-organic assemblies where at least three alkyne moieties are held in close proximity to form novel Ag(i)-complexes with the metal ion lodged into the helical cavity. NMR titration experiments and photokinetic studies have provided quantitative data about the thermodynamic and kinetic features of such binding/folding phenomena. X-ray diffraction and DFT studies have been performed to extract structural information on how the Ag(i) cation is accommodated into the cavity. The great simplicity and versatility of these new metallofoldamers open up the possibility to develop novel structures with applications in material science and/or in asymmetric catalysisThis research was funded by the Regional Government of Andalucía (project P09-FQM-4571) and the ICIQ Foundation. DM thanks Regional Government of Andalucía for her contract. AML thanks MICINN for her FPU fellowship. The authors thank the Centro de Servicios de Informática y Redes de Comunicaciones (CSIRC), Universidad de Granada, for providing the computing tim

Sex Hormone Receptor Expression in Craniopharyngiomas and Association with Tumor Aggressiveness Characteristics

Craniopharyngiomas (CPs) are rare tumors of the sellar and suprasellar regions of embryonic origin. The primary treatment for CPs is surgery but it is often unsuccessful. Although CPs are considered benign tumors, they display a relatively high recurrence rate that might compromise quality of life. Previous studies have reported that CPs express sex hormone receptors, including estrogen and progesterone receptors. Here, we systematically analyzed estrogen receptor α (ERα) and progesterone receptor (PR) expression by immunohistochemistry in a well-characterized series of patients with CP (n = 41) and analyzed their potential association with tumor aggressiveness features. A substantial proportion of CPs displayed a marked expression of PR. However, most CPs expressed low levels of ERα. No major association between PR and ERα expression and clinical aggressiveness features was observed in CPs. Additionally, in our series, β-catenin accumulation was not related to tumor recurrence. View Full-TextThis work was supported by grants from the ISCIII-Subdirección General de Evaluación y Fomento de la Investigación co-funded with Fondos FEDER (PI16/00175 to A.S-M. and D.A.C.) and the Sistema Andaluz de Salud (A-0006-2017 and A-0055-2018 to A.S-M, RC-0006-2018 to D.A.C.)

¿COVID-19 la pandemia y que sabemos de ella? Y como la afronta el Perú.

The novel coronavirus disease 2019 or COVID-19, had been reported for the first time in December 2019, in Wuhan China. To date, around 6 777 435 cases of COVID-19 were confirmed and 395 597 deaths worldwide. The COVID-19 outbreak is the largest in the past decades and is caused by a newly discovered coronavirus (SARS-CoV-2). On March 11th, 2020, the world Health Organization (WHO) has declared the COVID-19 a “Pandemic” with high rate of morbidity and mortality. This review synthesizes the scientific evidence and reports in the literature. The content of this manuscript presents the opinions of specialists and we present our interpretation and recommendations to the Peruvian government.La enfermedad del coronavirus o COVID-19, fue reportada por la primera vez en diciembre del 2019, en la ciudad de Wuhan China. A la fecha más de 6 777 435 casos de COVID-19 y 395 597muertes han sido reportadas globalmente. El brote del COVID-19 es causado por el virus SARS-CoV-2, siendo el brote más grande de las últimas décadas. Por lo cual la Organización Mundial de Salud (OMS) declaró al COVID-19 como pandemia (marzo 11, 2020), asociada con una importante morbilidad y mortalidad. Esta síntesis bibliográfica recapitula las evidencias científicas y los reportes publicados en revistas médicas. El contenido de este manuscrito recoge las opiniones y experiencias de especialistas. Y presentamos nuestra interpretación y recomendaciones a gobierno peruano

Ayotzinapa y la crisis del estado neoliberal mexicano

¿Qué pasó en Ayotzinapa? Es la pregunta que surgió el 26 de septiembre de 2014, que no encuentra una respuesta satisfactoria pese a la intervención de actores de distintas instancias, niveles y nacionalidades, y al esbozo de múltiples hipótesis sobre los enfrentamientos registrados en Iguala, Guerrero, que derivaron en la muerte de varias personas y la desaparición de 43 estudiantes de la Normal Rural “Isidro Burgos”, en una tragedia que evidenció la crisis que atraviesa el estado mexicano y que afecta a todo el país. A partir de lo acontecido en Ayotzinapa y con base en la teoría general de los campos de Pierre Bourdieu y su propuesta de análisis teórico metodológico sobre el estado, en esta obra se realiza un análisis de la práctica sistemática y generalizada de las desapariciones forzadas en México, con el fin de ofrecer otra manera de comprender el entretejido político–económico–social que hace posible este grave fenómeno, que desgarra tanto a familias como a la comunidad. La herida abierta por Ayotzinapa sangra y el objetivo último de este libro es contribuir a evitar que se cierre en tanto no se responda la interrogante de qué pasó ahí y que crímenes de lesa humanidad como este sigan aconteciendo en México.ITESO, A.C

Energy Estimation of Cosmic Rays with the Engineering Radio Array of the Pierre Auger Observatory

The Auger Engineering Radio Array (AERA) is part of the Pierre Auger Observatory and is used to detect the radio emission of cosmic-ray air showers. These observations are compared to the data of the surface detector stations of the Observatory, which provide well-calibrated information on the cosmic-ray energies and arrival directions. The response of the radio stations in the 30 to 80 MHz regime has been thoroughly calibrated to enable the reconstruction of the incoming electric field. For the latter, the energy deposit per area is determined from the radio pulses at each observer position and is interpolated using a two-dimensional function that takes into account signal asymmetries due to interference between the geomagnetic and charge-excess emission components. The spatial integral over the signal distribution gives a direct measurement of the energy transferred from the primary cosmic ray into radio emission in the AERA frequency range. We measure 15.8 MeV of radiation energy for a 1 EeV air shower arriving perpendicularly to the geomagnetic field. This radiation energy -- corrected for geometrical effects -- is used as a cosmic-ray energy estimator. Performing an absolute energy calibration against the surface-detector information, we observe that this radio-energy estimator scales quadratically with the cosmic-ray energy as expected for coherent emission. We find an energy resolution of the radio reconstruction of 22% for the data set and 17% for a high-quality subset containing only events with at least five radio stations with signal.Comment: Replaced with published version. Added journal reference and DO