Electrostatic considerations affecting the calculated HOMO-LUMO gap in protein molecules.

A detailed study of energy differences between the highest occupied and lowest unoccupied molecular orbitals (HOMO-LUMO gaps) in protein systems and water clusters is presented. Recent work questioning the applicability of Kohn-Sham density-functional theory to proteins and large water clusters (E. Rudberg, J. Phys.: Condens. Mat. 2012, 24, 072202) has demonstrated vanishing HOMO-LUMO gaps for these systems, which is generally attributed to the treatment of exchange in the functional used. The present work shows that the vanishing gap is, in fact, an electrostatic artefact of the method used to prepare the system. Practical solutions for ensuring the gap is maintained when the system size is increased are demonstrated. This work has important implications for the use of large-scale density-functional theory in biomolecular systems, particularly in the simulation of photoemission, optical absorption and electronic transport, all of which depend critically on differences between energies of molecular orbitals.Comment: 13 pages, 4 figure

Single polymer composite sheets from polypropylene nonwoven fabric and films. Influence of processing conditions on final properties

Single polypropylene (PP) composites from a film/nonwoven fabric/film was obtained by hot calendering in order to develop recyclable, flexible, and low-cost sheets. Processing temperature (Tp) influence on morphology and mechanical properties of developed single composites was analyzed. Two different values of roll temperature (140 and 150°C) were studied, keeping constant rotation speed and rolls distance. Results revealed notable differences in materials microstructure induced by a difference of only 10°C in Tp. Sheets obtained at 140°C presented a well-defined film/nonwoven fabric/film structure, meanwhile the highest Tp led to a greater melting extent of external films which penetrate into the fabric, creating a more compact structure. Moreover, results confirmed that changes in Tp can induce a differential mechanical performance showing higher strength, and ductility in sheets processed at 150°C. Homogeneous sheets with good mechanical behavior, proper nonwoven fabric/films adhesion, and uniform thickness were obtained.Fil: Vazquez, Yamila Victoria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; Argentina. Universidad Nacional del Sur. Departamento de Ingeniería Química; ArgentinaFil: Castillo, Luciana Andrea. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; Argentina. Universidad Nacional del Sur. Departamento de Ingeniería Química; ArgentinaFil: Barbosa, Silvia Elena. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; Argentina. Universidad Nacional del Sur. Departamento de Ingeniería Química; Argentin

Dipole Antenna Printed on Paper Substrate for WLAN Applications

International audienceThe design of a dipole antenna printed on a paper substrate is presented in this paper. The antenna which integrates a compact balun is devoted for dual-band 2.4/5 GHz WLAN applications. The antenna is based on a double-side printed multilayer paper substrate and is fed with a coaxial cable for the testing. The simulated results of the whole structure are also presented in detail and compared with the measured performances

VLA Observations of a New Population of Blazars

We present the first deep VLA radio images of flat-spectrum radio quasars (FSRQ) with multiwavelength emission properties similar to those of BL Lacs with synchrotron X-rays. Our observations of twenty-five of these sources show that their radio morphologies are similar to those of other radio quasars. However, their range of extended powers is more similar to that of BL Lacertae objects (BL Lacs) and extends down to the low values typical of FR I radio galaxies. Five out of our nine lobe-dominated sources have extended radio powers in the range typical of both FR I and FR II radio galaxies, but their extended radio structure is clearly FR II-like. Therefore, we have not yet found a large population of radio quasars hosted by FR Is. Two thirds of our sources have a core-dominated radio morpholgy and thus X-rays likely dominated by the jet. We find that their ratios of radio core to total X-ray luminosity are low and in the regime indicative of synchrotron X-rays. This result shows that also blazars with strong emission lines can produce jets of high-energy synchrotron emission and undermines at least in part the ``blazar sequence'' scenario which advocates that particle Compton cooling by an external radiation field governs the frequency of the synchrotron emission peak.Comment: 26 pages, 33 figures. Accepted for publication in Ap

Modular peptide binders - development of a predictive technology as alternative for reagent antibodies

Current biomedical research and diagnostics critically depend on detection agents for specific recognition and quantification of protein molecules. Monoclonal antibodies have been used for this purpose over decades and facilitated numerous biological and biomedical investigations. Recently, however, it has become apparent that many commercial reagent antibodies lack specificity or do not recognize their target at all. Thus, synthetic alternatives are needed whose complex designs are facilitated by multidisciplinary approaches incorporating experimental protein engineering with computational modeling. Here, we review the status of such an engineering endeavor based on the modular armadillo repeat protein scaffold and discuss challenges in its implementation. Keywords: affinity reagent; armadillo repeat proteins; computational design; directed evolution; library generation; protein-peptide interfac

Linear-scaling time-dependent density-functional theory beyond the Tamm-Dancoff approximation: Obtaining efficiency and accuracy with in situ optimised local orbitals.

We present a solution of the full time-dependent density-functional theory (TDDFT) eigenvalue equation in the linear response formalism exhibiting a linear-scaling computational complexity with system size, without relying on the simplifying Tamm-Dancoff approximation (TDA). The implementation relies on representing the occupied and unoccupied subspaces with two different sets of in situ optimised localised functions, yielding a very compact and efficient representation of the transition density matrix of the excitation with the accuracy associated with a systematic basis set. The TDDFT eigenvalue equation is solved using a preconditioned conjugate gradient algorithm that is very memory-efficient. The algorithm is validated on a small test molecule and a good agreement with results obtained from standard quantum chemistry packages is found, with the preconditioner yielding a significant improvement in convergence rates. The method developed in this work is then used to reproduce experimental results of the absorption spectrum of bacteriochlorophyll in an organic solvent, where it is demonstrated that the TDA fails to reproduce the main features of the low energy spectrum, while the full TDDFT equation yields results in good qualitative agreement with experimental data. Furthermore, the need for explicitly including parts of the solvent into the TDDFT calculations is highlighted, making the treatment of large system sizes necessary that are well within reach of the capabilities of the algorithm introduced here. Finally, the linear-scaling properties of the algorithm are demonstrated by computing the lowest excitation energy of bacteriochlorophyll in solution. The largest systems considered in this work are of the same order of magnitude as a variety of widely studied pigment-protein complexes, opening up the possibility of studying their properties without having to resort to any semiclassical approximations to parts of the protein environment.T.J.Z. acknowledges the support of EPSRC under Grant No. EP/J017639/1 and the ARCHER eCSE programme. M.C.P. and P.D.H. acknowledge the support of EPSRC under Grant No. EP/J015059/1. The underlying data of this publication can be accessed via the following persistent URI: https://www.repository.cam.ac.uk/handle/1810/251293This is the author accepted manuscript. The final version is available from AIP via http://dx.doi.org/10.1063/1.493628

Predicting solvatochromic shifts and colours of a solvated organic dye: the example of nile red

The solvatochromic shift, as well as the change in colour of the simple organic dye nile red, is studied in two polar and two non-polar solvents in the context of large-scale time-dependent density-functional theory (TDDFT) calculations treating large parts of the solvent environment from first principles. We show that an explicit solvent representation is vital to resolve absorption peak shifts between nile red in n-hexane and toluene, as well as acetone and ethanol. The origin of the failure of implicit solvent models for these solvents is identified as being due to the strong solute-solvent interactions in form of π-stacking and hydrogen bonding in the case of toluene and ethanol. We furthermore demonstrate that the failures of the computationally inexpensive Perdew-Burke-Ernzerhof (PBE) functional in describing some features of the excited state potential energy surface of the S1 state of nile red can be corrected for in a straightforward fashion, relying only on a small number of calculations making use of more sophisticated range-separated hybrid functionals. The resulting solvatochromic shifts and predicted colours are in excellent agreement with experiment, showing the computational approach outlined in this work to yield very robust predictions of optical properties of dyes in solution

The Wilderness Expedition: An effective life course intervention to improve young peoples well-being and connectedness to nature

It is well understood that wilderness expeditions improve well-being; however, there is little supporting quantitative data. The aim of this study was to measure the impact of wilderness expeditions on self-esteem (SE) and connectedness to nature (CN) and assess whether benefits varied according to participant and expedition characteristics. SE and CN were assessed pre– and post–wilderness expeditions in 130 adolescents using Rosenberg’s SE scale and the state CN scale. Two-way ANOVA revealed significant increases in SE and CN (p < .001) as a result of single expeditions. There was also an interaction effect of expedition and gender on SE (p < .05). Males had a higher SE at the start but female SE increased most. Linear regression revealed that living environment, gender, and the length and location of the expedition did not contribute to changes in SE and CN. Regular contact with natural environments will improve adolescent well-being, with the largest improvements in females

“It’s like my life but more, and better!” - Playing with the Cathaby Shark Girls: MMORPGs, young people and fantasy-based social play

This article is available open access through the publisher’s website at the link below. Copyright @ 2011 A B Academic Publishers.Digital technology has opened up a range of new on-line leisure spaces for young people. Despite their popularity, on-line games and Massive Multiplayer Online Role Playing Games in particular are still a comparatively under-researched area in the fields of both Education and more broadly Youth Studies. Drawing on a Five year ethnographic study, this paper considers the ways that young people use the virtual spaces offered by MMORPGs. This paper suggests that MMORPGs represent significant arenas within which young people act out a range of social narratives through gaming. It argues that MMORPG have become important fantasy spaces which offer young people possibilities to engage in what were formally material practices. Although this form of play is grounded in the everyday it also extends material practices and offers new and unique forms of symbolic experimentation, thus I argue that game-play narratives cannot be divorced from the everyday lives of their participants