Revisiting the redox transitions of Polyaniline. Semiquantitative interpretation of electrochemically induced IR bands

[EN] The redox transitions of PANI in acidic medium have been monitored by a combination of cyclic voltammetry, in situ conductance and in situ FTIR spectroscopy. The results of the semiquantitative analysis strongly suggest that the classical tetrameric model of PANI does not satisfactorily describe the actual structures of the polymer at different redox states. An octameric model is revisited, with the inclusion of essential resonant structures, to provide an appropriate prediction of the relative IR intensity changes of the aromatic Csingle bondC stretching (at around 1520 cm¿1) and the quinoid Cdouble bondC stretching (at around 1590 cm¿1) vibrations observed by FTIR, which are difficult to interpret by considering only 4 aniline rings. Particularly, it is found that the emeraldine state is better described as a resonance hybrid of the classical bipolaronic and semiquinoid (polaron lattice) structures, while most of the charge transferred at the onset of the second voltammetric peak comes from the additional oxidation of this hybrid, which becomes unstable in the electrochemical environment producing mineralization to CO2 and release of soluble quinones.This work was financed by the Spanish Ministerio de Ciencia e Innovacion (project PID2019-105923RB-I00) and by Generalitat Valenciana (Conselleria de Educacion, Investigacion, Cultura y Deporte through project PROMETEO/2018/087). The authors of this work are deeply grateful to Prof. Jose Luis Vazquez Pico (Pepe, nowadays retired) for his mentorship, which was the seed to develop this work. We appreciate the wise advice he gave us during our careers which served us to deepen the science contained in this article, as well as for the friendship with which he honored us over the years.Huerta, F.; Quijada, C.; Montilla, F.; Morallón, E. (2021). Revisiting the redox transitions of Polyaniline. Semiquantitative interpretation of electrochemically induced IR bands. Journal of Electroanalytical Chemistry. 897:1-11. https://doi.org/10.1016/j.jelechem.2021.115593S11189

Parameter-uniform numerical methods for singularly perturbed linear transport problems

Pointwise accurate numerical methods are constructed and analysed for three classes of singularly perturbed first order transport problems. The methods involve piecewise-uniform Shishkin meshes and the numerical approximations are shown to be parameter-uniformly convergent in the maximum norm. A transport problem from the modelling of fluid–particle interaction is formulated and used as a test problem for these numerical methods. Numerical results are presented to illustrate the performance of the numerical methods and to confirm the theoretical error bounds established in the paper. © 2022 The Authors. Mathematical Methods in the Applied Sciences published by John Wiley & Sons, Ltd

Una nueva asociación de matorral gipsófilo para el Sur de España (Provincia Bética)

El estudio de los matorrales gípsicos en el sur de España, revela la presencia de una comunidad diferente del resto de asociaciones descritas hasta el momento dentro de la alianza Lepidion subulati, al existir diferencias florísticas, ecológicas y biogeográficas. Por ello se propone la asociación Ononido angustifolii-Anthyllidetum cytisoidi nova, con un área subbética e hispalense, que se presenta en ambientes, secos y subhúmedos, sobre substratos gípsicos, los cuales dependiendo del ombrotipo se encuentran más o menos lavados, por lo que el matorral puede presentar más o menos gipsófitos estrictos. Asociación que se desarrolla sobre sustratos gípsicos, los cuales experimentan una pérdida de sales en ambientes seco-subhúmedos, por lo que esta nueva comunidad presenta un bajo porcentaje de gipsófilos estrictos frente a una mayor frecuencia de especies menos estrictas. Por lo que se propone la nueva alianza Resedo constrictae-Helianthemion syriacae nova de distribución ibérico-magrebíA study of the thickets growing on gypsum soils in the south of Spain reveals the presence of a community different from the other associations already described within the suballiance Lepidienion subulati as a result of the floristic, ecological and biogeographical differences. Therefore, we propose the association Ononido angustifolii-Anthyllidetum cytisoidi nova with a Subbetic and Hispalensean distribution. The association occurs in semiarid, dry and subhumid environments, on gypsum soils which, depending on the ombrotype, are more or less washed-out and, consequently, the thicket may comprise more o less strict gypsophytes. The association grows on gypsum soils which undergo salt deprivation in dry-subhumid environments. Thus, in this new community the percentage of strict gypsophilous taxa is low as compared to the number of less strict gypsophytes. To propose the new alliance Resedo constrictae-Helianthemion syriacae iberico-magrebi distribution

Clima urbano árido : Base de datos para estudios del Área Metropolitana de San Juan

Se presenta una estadística confiable de 16 años de datos meteorológicos de temperatura de bulbo seco, humedad relativa y radiación solar global, correspondientes a registros urbanos del Área Metropolitana de San Juan, relevantes para su uso como base de datos en el diseño bioclimático urbano-arquitectónico. Se calculan promedios mensuales, estacionales, anuales y del período, junto a un análisis histórico de las variables climáticas registradas. En el análisis histórico se concluye que la temperatura muestra un aumento continuado en el período (2,8 ºC más en 2010 que en 1995); la humedad relativa presenta una leve disminución (1% menos que en 1995), y la radiación solar, muestra un aumento (año 2010, 100W/m2 más que en 1995). Se manifiesta una clara tendencia a la disminución de la nubosidad desde el comienzo hasta el final del período estudiado.We present a reliable statistical weather data 16 years dry bulb temperature, relative humidity and global solar radiation corresponding to urban records Metropolitan Area San Juan, relevant for use as database in urban bioclimatic architectural design. Averages are calculated monthly, seasonal, annual and period, along with a historical analysis of the recorded climatic variables. In the historical analysis it is concluded that the temperature shows a steady increase over the period (2.8 ° C higher in 2010 than in 1995), the relative humidity has a slight decrease (1% less than in 1995), and solar radiation, shows an increase (2010, 100W/m2 more than in 1995). It shows a clear downward trend in cloudiness from the beginning to the end of the study period.Asociación Argentina de Energías Renovables y Medio Ambiente (ASADES

FIRI - a Far-Infrared Interferometer

Half of the energy ever emitted by stars and accreting objects comes to us in the FIR waveband and has yet to be properly explored. We propose a powerful Far-InfraRed Interferometer mission, FIRI, to carry out high-resolution imaging spectroscopy in the FIR. This key observational capability is essential to reveal how gas and dust evolve into stars and planets, how the first luminous objects in the Universe ignited, how galaxies formed, and when super-massive black holes grew. FIRI will disentangle the cosmic histories of star formation and accretion onto black holes and will trace the assembly and evolution of quiescent galaxies like our Milky Way. Perhaps most importantly, FIRI will observe all stages of planetary system formation and recognise Earth-like planets that may harbour life, via its ability to image the dust structures in planetary systems. It will thus address directly questions fundamental to our understanding of how the Universe has developed and evolved - the very questions posed by ESA's Cosmic Vision.Comment: Proposal developed by a large team of astronomers from Europe, USA and Canada and submitted to the European Space Agency as part of "Cosmic Vision 2015-2025

Device Therapies Among Patients Receiving Primary Prevention Implantable Cardioverter-Defibrillators in the Cardiovascular Research Network

BACKGROUND: Primary prevention implantable cardioverter-defibrillators (ICDs) reduce mortality in selected patients with left ventricular systolic dysfunction by delivering therapies (antitachycardia pacing or shocks) to terminate potentially lethal arrhythmias; inappropriate therapies also occur. We assessed device therapies among adults receiving primary prevention ICDs in 7 healthcare systems. METHODS AND RESULTS: We linked medical record data, adjudicated device therapies, and the National Cardiovascular Data Registry ICD Registry. Survival analysis evaluated therapy probability and predictors after ICD implant from 2006 to 2009, with attention to Centers for Medicare and Medicaid Services Coverage With Evidence Development subgroups: left ventricular ejection fraction, 31% to 35%; nonischemic cardiomyopathy \u3c9 \u3emonths\u27 duration; and New York Heart Association class IV heart failure with cardiac resynchronization therapy defibrillator. Among 2540 patients, 35% wereold, 26% were women, and 59% were white. During 27 (median) months, 738 (29%) received ≥1 therapy. Three-year therapy risk was 36% (appropriate, 24%; inappropriate, 12%). Appropriate therapy was more common in men (adjusted hazard ratio [HR], 1.84; 95% confidence interval [CI], 1.43-2.35). Inappropriate therapy was more common in patients with atrial fibrillation (adjusted HR, 2.20; 95% CI, 1.68-2.87), but less common among patients ≥65 years old versus younger (adjusted HR, 0.72; 95% CI, 0.54-0.95) and in recent implants (eg, in 2009 versus 2006; adjusted HR, 0.66; 95% CI, 0.46-0.95). In Centers for Medicare and Medicaid Services Coverage With Evidence Development analysis, inappropriate therapy was less common with cardiac resynchronization therapy defibrillator versus single chamber (adjusted HR, 0.55; 95% CI, 0.36-0.84); therapy risk did not otherwise differ for Centers for Medicare and Medicaid Services Coverage With Evidence Development subgroups. CONCLUSIONS: In this community cohort of primary prevention patients receiving ICD, therapy delivery varied across demographic and clinical characteristics, but did not differ meaningfully for Centers for Medicare and Medicaid Services Coverage With Evidence Development subgroups

Electrochemical synthesis of peroxomonophosphate using boron-doped diamond anodes

A new method for the synthesis of peroxomonophosphate, based on the use of boron-doped diamond electrodes, is described. The amount of oxidant electrogenerated depends on the characteristics of the supporting media (pH and solute concentration) and on the operating conditions (temperature and current density). Results show that the pH, between values of 1 and 5, does not influence either the electrosynthesis of peroxomonophosphate or the chemical stability of the oxidant generated. Conversely, low temperatures are required during the electrosynthesis process to minimize the thermal decomposition of peroxomonophosphate and to guarantee significant oxidant concentration. In addition, a marked influence of both the current density and the initial substrate is observed. This observation can be explained in terms of the contribution of hydroxyl radicals in the oxidation mechanisms that occur on diamond surfaces. In the assays carried out below the water oxidation potential, the generation of hydroxyl radicals did not take place. In these cases, peroxomonophosphate generation occurs through a direct electron transfer and, therefore, at these low current densities lower concentrations are obtained. On the other hand, at higher potentials both direct and hydroxyl radical-mediated mechanisms contribute to the oxidant generation and the process is more efficient. In the same way, the contribution of hydroxyl radicals may also help to explain the significant influence of the substrate concentration. Thus, the coexistence of both phosphate and hydroxyl radicals is required to ensure the generation of significant amounts of peroxomonophosphoric acid

Superhydrophobic Cerium-Based Coatings on Al-Mg Alloys and Aluminized Steel

Aluminum-magnesium (Al-Mg) alloy and aluminum-coated steel (aluminized steel) are typically used for the manufacturing of baking trays and molds. For these applications, these materials must be modified to develop release and hydrophobic properties. With this aim, the bare substrates are typically coated with low-surface energy materials such as fluoropolymers, elastomers, or sol-gel layers. In this work, some alternative strategies to prepare these functional surfaces are presented. We used three-step processes involving (i) micro-texturing, (ii) nano layer deposition through immersion and electrodeposition, and (iii) hydrophobization. The raw substrates were sanded or sandblasted at the micro scale, accordingly. Texturization at the nano scale was achieved with a cerium layer formed by electrodeposition or solution immersion. The cerium layers were hydrophobized with fatty acids. The wetting properties of the samples were studied with tilting-plate and bouncing drop methods. We measured the surface roughness of the samples by contact profiling and analyzed their surface morphology using a field emission scanning electron microscope (FESEM). The elemental chemical composition of the samples was analyzed by energy-dispersive X-ray spectroscopy (EDX). The wettability results indicated that the best performance for the Al-Mg substrates was reached by sandblasting and later immersion in a cerium nitrate solution. For aluminized steel substrates, the best results were obtained with both electrodeposition and immersion methods using a cerium chloride solution

Atlantic circulation change still uncertain

Deep oceanic overturning circulation in the Atlantic (Atlantic Meridional Overturning Circulation, AMOC) is projected to decrease in the future in response to anthropogenic warming. Caesar et al. 1 argue that an AMOC slowdown started in the 19 th century and intensified during the mid-20th century. Although the argument and selected evidence proposed have some merits, we find that their conclusions might be different if a more complete array of data available in the North Atlantic region had been considered. We argue that the strength of AMOC over recent centuries is still poorly constrained and the expected slowdown may not have started yet.K.H.K. acknowledges funding from NOAA grant NA20OAR4310481. D.E.A. and B.L.O.-B. acknowledge support from the National Center for Atmospheric Research, which is a major facility sponsored by the National Science Foundation under cooperative agreement no. 1852977. N.M.W. acknowledges support from a NOAA Climate and Global Change Postdoctoral Fellowship. M.F.J. acknowledges support from NSF award OCE-1846821 and C.M.L. acknowledges support from NSF award OCE-1805029. This is UMCES contribution 6062.Peer ReviewedArticle signat per 17 autors/es: University of Maryland Center for Environmental Science, Chesapeake Biological Laboratory, Solomons, MD, USA: K. Halimeda Kilbourne / Department of Geological and Atmospheric Sciences, Iowa State University, Ames, IA, USA: Alan D. Wanamaker / Geography Department, Durham University, Durham, UK: Paola Moffa-Sanchez / Centre for Geography and Environmental Sciences, University of Exeter, Penryn, UK: David J. Reynolds, Paul G. Butler & James Scourse / Climate and Global Dynamics Laboratory, National Center for Atmospheric Research, Boulder, CO, USA: Daniel E. Amrhein & Bette L. Otto-Bliesner / Woods Hole Oceanographic Institution, Falmouth, MA, USA: Geoffrey Gebbie & Nina M. Whitney / Cooperative Institute for Marine and Atmospheric Studies, University of Miami, Miami, FL, USA: Marlos Goes / Atlantic Oceanographic and Meteorological Laboratory, National Oceanic and Atmospheric Administration, Miami, FL, USA: Marlos Goes / Department of the Geophysical Sciences, The University of Chicago, Chicago, IL, USA: Malte F. Jansen / Oceanography Department, Atmospheric and Environmental Research, Inc., Texas, TX, USA: Christopher M. Little / US Geological Survey, St Petersburg Coastal and Marine Science Center, St Petersburg, FL, USA: Madelyn Mette / Barcelona Supercomputing Center, Barcelona, Spain: Eduardo Moreno-Chamarro & Pablo Ortega / Graduate School of Oceanography, University of Rhode Island, Kingston, RI, USA: Thomas Rossby / University Corporation of Atmospheric Research, Boulder, CO, USA: Nina M. WhitneyPostprint (author's final draft)Matters Arising published on 17 February 2022. The Original Article was published on 25 February 2021