Synthesis of pentabromopseudilin and other arylpyrrole derivatives via Heck arylations

Pentrabromopseudilin and other 2 and 3-arylpyrrole derivatives were synthesized through the Heck–Matsuda reaction involving endocyclic enecarbamates and N-protected 3-pyrrolines, respectively. The overall processes permitted an easy and efficient access to these structural motifs present in several bioactive compounds. Attempts to synthesize the compound isopentabromopseudilin led to a tribromo aryl maleimide. We hypothesize that this latter compound is the putative product arising from the unusual thermal instability of isopentabromopseudilin.     

Nanorings in planar confinement: the role of repulsive surfaces on the formation of lacuna smectics

ABSTRACT

We study the structure and liquid-crystalline phase behaviour of a model of confined non-convex circular soft-repulsive nanorings in a planar slit geometry using molecular-dynamics simulation. The separation distance between the structureless parallel soft-repulsive walls is made large enough to allow for the formation of a distinct bulk phase in the central region of the box which is in coexistence with the adsorbed fluid thus allowing the analysis of single-wall effects. As the density of the particles is increased, the fluid adsorbs (wets) onto the planar surfaces leading to the formation of well-defined smectic-A layers with a spacing proportional to the diameter of the rings. An analysis of the nematic order parameter at distances perpendicular to the surface reveals that the particles in each layer exhibit anti-nematic behaviour and planar (edge-on) anchoring relative to the short symmetry axis of the rings. This behaviour is in stark contrast to the behaviour observed in convex disc-like particles that have the tendency to form nematic (discotic) structures with homeotropic (face-on) anchoring. The smectic phases formed by nanorings in the bulk and under confinement are characterised by the formation of low-density layered liquid-crystalline states with large voids, referred to here as lacuna smectic phases. In contrast to what is typically found for confined liquid-crystalline systems involving convex particles, no apparent biaxiality is found for nanorings in planar confinement. We argue that formation of the low-density lacuna smectic layers with planar anchoring is a consequence of the non-convex shape of the circular rings that allow for interpenetration between the particles as observed for nanorings under bulk conditions [C. Avendaño, G. Jackson, E.A. Müller and F.A. Escobedo, Proc. Natl. Acad. Sci. U.S.A. 113, 9699 (2016); H.H. Wensink and C. Avendaño, Phys. Rev. E 94, 062704 (2016)].     

Models for the modern power grid

This article reviews different kinds of models for the electric power grid that can be used to understand the modern power system, the smart grid. From the physical network to abstract energy markets, we identify in the literature different aspects that co-determine the spatio-temporal multilayer dynamics of power system. We start our review by showing how the generation, transmission and distribution characteristics of the traditional power grids are already subject to complex behaviour appearing as a result of the the interplay between dynamics of the nodes and topology, namely synchronisation and cascade effects. When dealing with smart grids, the system complexity increases even more: on top of the physical network of power lines and controllable sources of electricity, the modernisation brings information networks, renewable intermittent generation, market liberalisation, prosumers, among other aspects. In this case, we forecast a dynamical co-evolution of the smart grid and other kind of networked systems that cannot be understood isolated. This review compiles recent results that model electric power grids as complex systems, going beyond pure technological aspects. From this perspective, we then indicate possible ways to incorporate the diverse co-evolving systems into the smart grid model using, for example, network theory and multi-agent simulation.     

Heat Release by Controlled Continuous-Time Markov Jump Processes

We derive the equations governing the protocols minimizing the heat released by a continuous-time Markov jump process on a one-dimensional countable state space during a transition between assigned initial and final probability distributions in a finite time horizon. In particular, we identify the hypotheses on the transition rates under which the optimal control strategy and the probability distribution of the Markov jump problem obey a system of differential equations of Hamilton-Jacobi-Bellman-type. As the state-space mesh tends to zero, these equations converge to those satisfied by the diffusion process minimizing the heat released in the Langevin formulation of the same problem. We also show that in full analogy with the continuum case, heat minimization is equivalent to entropy production minimization. Thus, our results may be interpreted as a refined version of the second law of thermodynamics.     

Are the New Physics Contributions from the Left-Right Symmetric Model Important for the Indirect CP Violation in the Neutral B Mesons?

No Heading Several works analyzing the new physics contributions from the Left-Right Symmetric Model to the CP violation phenomena in the neutral B mesons can be found in the literature. These works exhibit interesting and experimentally sensible deviations from the Standard Model predictions but at the expense of considering a low right scale υ_R around 1 TeV. However, when we stick to the more conservative estimates for υ_R, which say that it must be at least 10⁷ GeV, no experimentally sensible deviations from the Standard Model appear for indirect CP violation. This estimate for υ_R arises when the generation of neutrino masses is considered. In spite of the fact that this scenario is much less interesting and says nothing new about both the CP violation phenomenon and the structure of the Left-Right Symmetric Model, this possibility must be taken into account for the sake of completeness and when considering the see-saw mechanism that provides masses to the neutrino sector. ¹ Associate researcher of the Centro Internacional de Física, Ciudad Universitaria, Bogotá D.C., Colombia.     

UV filter 2‐ethylhexyl 4‐methoxycinnamate: a structure,energetic and UV–vis spectral analysis based on density functional theory

2‐Ethylhexyl 4‐methoxycinnamate (EHMC) is a very commonly used UVB filter that is known to isomerize from the (E) to the (Z) isomer in the presence of light. In this study, we have performed high level quantum chemical calculations using density functional theory (DFT) with the B3LYP density functional and extended basis sets to study the gas‐phase molecular structure of EHMC and its energetic stability. Calculations were also performed for related smaller molecules cinnamic acid and 4‐methoxycinnamic acid. Charge delocalization has been analyzed using natural charges and Wiberg bond indexes within the natural bond orbital analysis and using nucleus independent chemical shifts. Density functional theory calculations reveal that the (E) isomer of EHMC is more stable than the (Z) by about 20 kJ mol^?1 in both the gas and aqueous phases. The enthalpy of formation in the gas phase of (E)‐EHMC was derived from an isodesmic bond separation reaction. Long‐range corrected DFT calculations in implicit water were made in order to understand the excited state properties of the (E) and (Z) isomers of EHMC. Copyright © 2013 John Wiley & Sons, Ltd.