Effect of energy disorder in interfacial kinetics of dye-sensitized solar cells with organic hole transport material

We describe the kinetic rates for dye regeneration in dye-sensitized solar cells with organic solid hole conductors, taking as a reference the experimental results of Haque et al. (ChemPhysChem 2003, 4, 89). Our model is based on Marcus rates for electron and hole transfer, emphasizing the Gaussian spread of energy levels in the molecular materials involved. We show that the energy disorder implies a broadening of the efficiency of hole transfer with respect to the thermodynamic driving force, as observed experimentally. The model also shows that tunning of the kinetic processes for high efficiency of energy conversion of the solar cell depends critically on the interplay between the reorganization energy and the broadening parameters of the energy distributions.     

The assignment of absolute configuration of cyanohydrins by NMR

Derivatization of aldehyde cyanohydrins as (R)- and (S)-MPA esters and comparison of the corresponding 1H- and 13C-NMR spectra allows the assignment of their absolute configuration.     

A cross entropy-based metaheuristic algorithm for large-scale capacitated facility location problems

In this paper, we present a metaheuristic-based algorithm for the capacitated facility location problem. The proposed scheme is made up by three phases: (i) solution construction phase, in which a cross entropy-based scheme is used to ‘intelligently’ guess which facilities should be opened; (ii) local search phase, aimed at exploring the neighbourhood of ‘elite’ solutions of the previous phase; and (iii) learning phase, aimed at fine-tuning the stochastic parameters of the algorithm. The algorithm has been thoroughly tested on large-scale random generated instances as well as on benchmark problems and computational results show the effectiveness and robustness of the algorithm.     

Magnetic Kronig-Penney-type graphene superlattices: finite energy Dirac points with anisotropic velocity renormalization

We study the energy band structure of magnetic graphene superlattices with delta-function magnetic barriers and zero average magnetic field. The dispersion relation obtained using the T-matrix approach shows the emergence of an infinite number of Dirac-like points at finite energies, while the original Dirac point is still located at the same place as that for pristine graphene. The carrier group velocity at the original Dirac point is isotropically renormalized, but at finite energy Dirac points it is generally anisotropic. An asymmetry in the width between the wells and the barriers of the periodic potential induces a shift of the original Dirac point in the zero-energy plane, keeping the velocity renormalization isotropic.     

Dynamic Axial-to-Helical Communication Mechanism in Poly[(allenylethynylenephenylene)acetylene]s under External Stimuli

Helix inversion in chiral dynamic helical polymers is usually achieved by conformational changes at the pendant groups induced through external stimuli. Herein, a different mechanism of helix inversion in poly(phenylacetylene)s (PPAs) is presented, based on the activation/deactivation of supramolecular interactions. We prepared poly[(allenylethynylenephenylene)acetylene]s (PAEPAs) in which the pendant groups are conformationally locked chiral allenes. Therefore, their substituents are placed in specific spatial orientations. As a result, the screw sense of a PAEPA is fixed by the allenyl substituent with the optimal size/distance relationship to the backbone. This helical sense command can be surpassed by supramolecular interactions between another substituent on the allene and appropriate external stimuli, such as amines. So, a helix inversion occurs through a novel axial-to-helical communication mechanism, opening a new scenario for taming the helices of chiral dynamic helical polymers.