RESUMEN
A combined experimental and theoretical study has been carried out on 4-fluoro-threonine, the only naturally occurring fluorinated amino acid. Fluorination of the methyl group significantly increases the conformational complexity with respect to the parent amino acid threonine. The conformational landscape has been characterized in great detail, with special attention given to the inter-conversion pathways between different conformers. This led to the identification of 13 stable low-energy minima. The equilibrium population of so many conformers produces a very complicated and congested rotational spectrum that could be assigned through a strategy that combines several levels of quantum chemical calculations with the principles of machine learning. Twelve conformers out of 13 could be experimentally characterized. The results obtained from the analysis of the intra-molecular interactions can be exploited to accurately model fluorine-substitution effects in biomolecules.
RESUMEN
The 2016-2017 Central Italy earthquake sequence struck the central Apennines between August 2016 and October 2016 with Mw ∈ [5.9; 6.5], plus four earthquakes occurring in January 2017 with Mw ∈ [5.0; 5.5]. We study Global Positioning System time series including near- and far-field domains. We use a variational Bayesian independent component analysis technique to separate the post-seismic deformation from signals caused by variation of the water content in aquifers at hundreds of meters of depth and of the soil moisture. For each independent component, realistic uncertainties and a plausible physical explanation are provided. We focus on the study of afterslip on the main structures surrounding the mainshock, highlighting the role played by faults that were not activated during the co-seismic phase in accommodating the post-seismic deformation. We report aseismic deformation occurring on the Paganica fault, which hosted the Mw 6.1 2009 L'Aquila earthquake, suggesting that static stress transfer and aseismic slip influence the recurrence time of nearby (â¼50 km further south of the mainshocks) segments. A â¼2-3 km thick subhorizontal shear-zone, clearly illuminated by seismicity, which bounds at depth the west-dipping normal faults where the mainshocks nucleated, also shows aseismic slip. Since afterslip alone underestimates the displacement in the far-field domain, we consider the possibility that the shear zone marks the brittle-ductile transition, assuming the viscoelastic relaxation of the lower crust as a mechanism contributing to the post-seismic displacement. Our results suggest that multiple deformation processes are active in the first 2 years after the mainshocks.
RESUMEN
Slow earthquakes, like regular earthquakes, result from unstable frictional slip. They produce little slip and can therefore repeat frequently. We assess their predictability using the slip history of the Cascadia subduction between 2007 and 2017, during which slow earthquakes have repeatedly ruptured multiple segments. We characterize the system dynamics using embedding theory and extreme value theory. The analysis reveals a low-dimensional (<5) nonlinear chaotic system rather than a stochastic system. We calculate properties of the underlying attractor like its correlation and instantaneous dimension, instantaneous persistence, and metric entropy. We infer that the system has a predictability horizon of the order of days weeks. For the better resolved segments, the onset of large slip events can be correctly forecasted by high values of the instantaneous dimension. Longer-term deterministic prediction seems intrinsically impossible. Regular earthquakes might similarly be predictable but with a limited predictable horizon of the order of their durations.
RESUMEN
Using ascorbate as a sacrificial reductant, iodo-Bodipy dye 1b is able to promote the ATRA reaction between bromoderivatives and alkenes. This finding expands the possibility of using Bodipy dyes to promote photocatalytic reactions in efficient ways.
RESUMEN
Tuning the intermolecular interactions among suitably designed molecules forming highly ordered self-assembled monolayers is a viable approach to control their organization at the supramolecular level. Such a tuning is particularly important when applied to sophisticated molecules combining functional units which possess specific electronic properties, such as electron/energy transfer, in order to develop multifunctional systems. Here we have synthesized two tetraferrocene-porphyrin derivatives that by design can selectively self-assemble at the graphite/liquid interface into either face-on or edge-on monolayer-thick architectures. The former supramolecular arrangement consists of two-dimensional planar networks based on hydrogen bonding among adjacent molecules whereas the latter relies on columnar assembly generated through intermolecular van der Waals interactions. Scanning Tunneling Microscopy (STM) at the solid-liquid interface has been corroborated by cyclic voltammetry measurements and assessed by theoretical calculations to gain multiscale insight into the arrangement of the molecule with respect to the basal plane of the surface. The STM analysis allowed the visualization of these assemblies with a sub-nanometer resolution, and cyclic voltammetry measurements provided direct evidence of the interactions of porphyrin and ferrocene with the graphite surface and offered also insight into the dynamics within the face-on and edge-on assemblies. The experimental findings were supported by theoretical calculations to shed light on the electronic and other physical properties of both assemblies. The capability to engineer the functional nanopatterns through self-assembly of porphyrins containing ferrocene units is a key step toward the bottom-up construction of multifunctional molecular nanostructures and nanodevices.