Improved prediction of the optical properties in pi-conjugated polymers: the case of benzochalcogenodiazole-based copolymers with different heteroatom substitution

Donor−acceptor (D−A) approach to conjugated polymer design has become a widely used method for preparing conjugated polymers with narrow band gaps.1 One outstanding D−A polymer is poly(cyclopentadithiophene)benzothiadiazole, PCPDTBT (P1 in Figure 1), for which power conversion efficiencies in solar cells of 4.5-5.5% are reported.2 In this work, we use resonance Raman (RR) and density functional theory (DFT) calculations to investigate the tuning of the electronic and structural properties of cyclopentadithiophene-benzochalcogenodiazole D−A polymers, wherein a single atom in the benzochalcogenodiazole unit is varied from sulfur to selenium to tellurium (Fig. 1).3 Sophisticated DFT calculations have been carried out using long-range corrected functionals, considering both tuned and default range-separation parameters, aiming at predicting their optical and charge transport properties. In addition, the nature of the electronic excitation is described by analyzing the enhancement pattern in the RR spectra using Raman excitation wavelengths coincident with the various transitions in the copolymers.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tec

Quantifying the speech-gesture relation with massive multimodal datasets: informativity in time expressions

The development of large-scale corpora has led to a quantum leap in our understanding of speech in recent years. By contrast, the analysis of massive datasets has so far had a lim- ited impact on the study of gesture and other visual communicative behaviors. We utilized the UCLA-Red Hen Lab multi-billion-word repository of video recordings, all of them showing communicative behavior that was not elicited in a lab, to quantify speech-gesture co-occur- rence frequency for a subset of linguistic expressions in American English. First, we objec- tively establish a systematic relationship in the high degree of co-occurrence between gesture and speech in our subset of expressions, which consists of temporal phrases. Sec- ond, we show that there is a systematic alignment between the informativity of co-speech gestures and that of the verbal expressions with which they co-occur. By exposing deep, systematic relations between the modalities of gesture and speech, our results pave the way for the data-driven integration of multimodal behavior into our understanding of human communication

Manejo del tiempo en una organización de la rama tecnológica

Nombre del PAP: Gestión del Cambio, del Talento Humano y la Efectividad Organizacional. Propósito general del proyecto: El propósito del presente proyecto es generar, con base en una investigación y la impartición de un taller, una cultura de organización de tiempo que garantice un mayor aprovechamiento y utilización de los recursos disponibles para una organización, logrando a su vez que los trabajadores reflexionen conforme a como manejan su tiempo. El proyecto es una continuación del PAP del semestre de primavera 2022, en el que se llevó a cabo una evaluación conforme la NOM 035, misma que tuvo como producto una identificación de los riesgos psicosociales que generan mayor problema en la organización. Destacando el alcance de este proyecto se puede decir que está visualizado ante el personal de recursos humanos de una empresa de la rama tecnológica y las múltiples unidades de negocio que la conforman, de manera que la logística se llevó a cabo de manera colaborativa con el enlace que se tiene con la empresa. El resultado es un reporte ejecutivo en el que se plasma la información relevante para la organización para que a su vez aporte beneficios de gran utilidad para identificar y evitar los riesgos psicosociales.ITESO, A.C

Modelling the optical properties of Benzochalcogenodiazole-based Copolymers using Tuned Range-Separated Hybrid Functionals

Since the discovery of organic semiconductors, these systems have been deeply investigated and many strategies to module their optical and electronic properties have been established. In this sense, Donor-acceptor (D−A) approach to conjugated polymer design has become a widely used method for preparing conjugated polymers with narrow band gaps. This approach involves synthesizing a polymer with a delocalized π-electron system that comprises alternating electron-rich (donor) and electron-deficient (acceptor) repeat units. The combination of high-lying HOMO levels (residing on the donor units) and low-lying LUMO levels (residing on the acceptor units) results in an overall narrow band gap for the polymer. In this sense, poly(cyclopentadithiophene)benzothiadiazole is a D−A polymer for which power conversion efficiencies in solar cells of 5 6 % are reported. In this work, we use density functional theory (DFT) calculations to investigate the tuning of the electronic and structural properties of cyclopentadithiophene ben zochalcogenodiazole D−A polymers, wherein a single atom in the benzochalcogenodiazole unit is varied from sulfur to selenium to tellurium. Resonance Raman (RR) spectroscopy is also used to describe the nature of the electronic excitations. Improved prediction of the optical properties h as been obtained by using long range corrected functionals functionals, considering both tuned and default range separation parameters, aiming at predicting their optical and charge transport properties.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Effect of moderate prenatal ethanol exposure on the differential expression of two histamine H3 receptor isoforms in different brain regions of adult rat offspring

We have reported that prenatal alcohol exposure (PAE) elevates histamine H3 receptor (H3R) agonist-mediated inhibition of glutamatergic neurotransmission in the dentate gyrus. Here, we hypothesized that PAE alters the expression of two prominent H3R isoforms namely, the rH3A and rH3C isoforms, which have differing intrinsic activities for H3R agonists, in a manner that may contribute to heightened H3R function in PAE rats. In contrast to our predictions, we found different effects of sex and PAE in various brain regions with significant interactions between sex and PAE in dentate gyrus and entorhinal cortex for both isoforms. Subsequently, to confirm the PAE-and sex-induced differences on H3R isoform mRNA expression, we developed a polyclonal antibody selective for the rH3A inform. Western blots of rH3A mRNA-transfected HEK-293 cells identified a  ~ 48 kDa band of binding consistent with the molecular weight of rH3A, thus confirming antibody sensitivity for rH3A protein. In parallel, we also established a pan-H3R knockout mice line to confirm antibody specificity in rodent brain membranes. Both qRT-PCR and H3R agonist-stimulated [35S]-GTPγS binding confirmed the absence of mH3A mRNA and H3 receptor-effector coupling in H3R knockout (KO) mice. Subsequent western blotting studies in both rat and mouse brain membranes were unable to detect rH3A antibody binding at ~48 kDa. Rather, the H3RA antibody bound to a  ~ 55 kDa band in both rat and mouse membranes, including H3R KO mice, suggesting H3RA binding was not specific for H3Rs in rodent membranes. Subsequent LC/MS analysis of the ~55 kDa band in frontal cortical membranes identified the highly abundant beta subunit of ATPase in both WT and KO mice. Finally, LC/MS analysis of the ~48 kDa band from rH3A mRNA-transfected HEK-293 cell membranes was able to detect rH3A protein, but its presence was below the limits of quantitative reliability. We conclude that PAE alters rH3A and rH3C mRNA expression in some of the same brain regions where we have previously reported PAE-induced alterations in H3R-effector coupling. However, interpreting the functional consequences of altered H3R isoform expression was limited given the technical challenges of measuring the relatively low abundance of rH3A protein in native membrane preparations

Clinical and serological features of systemic sclerosis in a multicenter African American cohort: Analysis of the genome research in African American scleroderma patients clinical database.

Racial differences exist in the severity of systemic sclerosis (SSc). To enhance our knowledge about SSc in African Americans, we established a comprehensive clinical database from the largest multicenter cohort of African American SSc patients assembled to date (the Genome Research in African American Scleroderma Patients (GRASP) cohort).African American SSc patients were enrolled retrospectively and prospectively over a 30-year period (1987-2016), from 18 academic centers throughout the United States. The cross-sectional prevalence of sociodemographic, clinical, and serological features was evaluated. Factors associated with clinically significant manifestations of SSc were assessed using multivariate logistic regression analyses.The study population included a total of 1009 African American SSc patients, comprised of 84% women. In total, 945 (94%) patients met the 2013 American College of Rheumatology/European League Against Rheumatism (ACR/EULAR) classification criteria for SSc, with the remaining 64 (6%) meeting the 1980 ACR or CREST (calcinosis, Raynaud's phenomenon, esophageal dysmotility, sclerodactyly, telangiectasia) criteria. While 43% were actively employed, 33% required disability support. The majority (57%) had the more severe diffuse subtype and a young age at symptom onset (39.1 ± 13.7 years), in marked contrast to that reported in cohorts of predominantly European ancestry. Also, 1 in 10 patients had a severe Medsger cardiac score of 4. Pulmonary fibrosis evident on computed tomography (CT) chest was present in 43% of patients and was significantly associated with anti-topoisomerase I positivity. 38% of patients with CT evidence of pulmonary fibrosis had a severe restrictive ventilator defect, forced vital capacity (FVC) ≤50% predicted. A significant association was noted between longer disease duration and higher odds of pulmonary hypertension, telangiectasia, and calcinosis. The prevalence of potentially fatal scleroderma renal crisis was 7%, 3.5 times higher than the 2% prevalence reported in the European League Against Rheumatism Scleroderma Trials and Research (EUSTAR) cohort.Our study emphasizes the unique and severe disease burden of SSc in African Americans compared to those of European ancestry

Prenatal alcohol exposure alters mRNA expression for stress peptides, glucocorticoid receptor function and immune factors in acutely stressed neonatal brain

BackgroundThe amygdala, hippocampus and hypothalamus are critical stress regulatory areas that undergo functional maturation for stress responding initially established during gestational and early postnatal brain development. Fetal alcohol spectrum disorder (FASD), a consequence of prenatal alcohol exposure (PAE), results in cognitive, mood and behavioral disorders. Prenatal alcohol exposure negatively impacts components of the brain stress response system, including stress-associated brain neuropeptides and glucocorticoid receptors in the amygdala, hippocampus and hypothalamus. While PAE generates a unique brain cytokine expression pattern, little is known about the role of Toll-like receptor 4 (TLR4) and related proinflammatory signaling factors, as well as anti-inflammatory cytokines in PAE brain stress-responsive regions. We hypothesized that PAE sensitizes the early brain stress response system resulting in dysregulated neuroendocrine and neuroimmune activation.MethodsA single, 4-h exposure of maternal separation stress in male and female postnatal day 10 (PND10) C57Bl/6 offspring was utilized. Offspring were from either prenatal control exposure (saccharin) or a limited access (4 h) drinking-in-the-dark model of PAE. Immediately after stress on PND10, the hippocampus, amygdala and hypothalamus were collected, and mRNA expression was analyzed for stress-associated factors (CRH and AVP), glucocorticoid receptor signaling regulators (GAS5, FKBP51 and FKBP52), astrocyte and microglial activation, and factors associated with TLR4 activation including proinflammatory interleukin-1β (IL-1β), along with additional pro- and anti-inflammatory cytokines. Select protein expression analysis of CRH, FKBP and factors associated with the TLR4 signaling cascade from male and female amygdala was conducted.ResultsThe female amygdala revealed increased mRNA expression in stress-associated factors, glucocorticoid receptor signaling regulators and all of the factors critical in the TLR4 activation cascade, while the hypothalamus revealed blunted mRNA expression of all of these factors in PAE following stress. Conversely, far fewer mRNA changes were observed in males, notably in the hippocampus and hypothalamus, but not the amygdala. Statistically significant increases in CRH protein, and a strong trend in increased IL-1β were observed in male offspring with PAE independent of stressor exposure.ConclusionPrenatal alcohol exposure creates stress-related factors and TLR-4 neuroimmune pathway sensitization observed predominantly in females, that is unmasked in early postnatal life by a stress challenge

Coexistence of a fluid responsive state and venous congestion signals in critically ill patients: a multicenter observational proof-of-concept study

Background Current recommendations support guiding fluid resuscitation through the assessment of fluid responsiveness. Recently, the concept of fluid tolerance and the prevention of venous congestion (VC) have emerged as relevant aspects to be considered to avoid potentially deleterious side effects of fluid resuscitation. However, there is paucity of data on the relationship of fluid responsiveness and VC. This study aims to compare the prevalence of venous congestion in fluid responsive and fluid unresponsive critically ill patients after intensive care (ICU) admission. Methods Multicenter, prospective cross-sectional observational study conducted in three medical–surgical ICUs in Chile. Consecutive mechanically ventilated patients that required vasopressors and admitted < 24 h to ICU were included between November 2022 and June 2023. Patients were assessed simultaneously for fluid responsiveness and VC at a single timepoint. Fluid responsiveness status, VC signals such as central venous pressure, estimation of left ventricular filling pressures, lung, and abdominal ultrasound congestion indexes and relevant clinical data were collected. Results Ninety patients were included. Median age was 63 [45–71] years old, and median SOFA score was 9 [7–11]. Thirty-eight percent of the patients were fluid responsive (FR+), while 62% were fluid unresponsive (FR−). The most prevalent diagnosis was sepsis (41%) followed by respiratory failure (22%). The prevalence of at least one VC signal was not significantly different between FR+ and FR− groups (53% vs. 57%, p = 0.69), as well as the proportion of patients with 2 or 3 VC signals (15% vs. 21%, p = 0.4). We found no association between fluid balance, CRT status, or diagnostic group and the presence of VC signals. Conclusions Venous congestion signals were prevalent in both fluid responsive and unresponsive critically ill patients. The presence of venous congestion was not associated with fluid balance or diagnostic group. Further studies should assess the clinical relevance of these results and their potential impact on resuscitation and monitoring practices

Early rise in central venous pressure during a spontaneous breathing trial: A promising test to identify patients at high risk of weaning failure?

Background The spontaneous breathing trial (SBT) assesses the risk of weaning failure by evaluating some physiological responses to the massive venous return increase imposed by discontinuing positive pressure ventilation. This trial can be very demanding for some critically ill patients, inducing excessive physical and cardiovascular stress, including muscle fatigue, heart ischemia and eventually cardiac dysfunction. Extubation failure with emergency reintubation is a serious adverse consequence of a failed weaning process. Some data suggest that as many as 50% of patients that fail weaning do so because of cardiac dysfunction. Unfortunately, monitoring cardiovascular function at the time of the SBT is complex. The aim of our study was to explore if central venous pressure (CVP) changes were related to weaning failure after starting an SBT. We hypothesized that an early rise on CVP could signal a cardiac failure when handling a massive increase on venous return following a discontinuation of positive pressure ventilation. This CVP rise could identify a subset of patients at high risk for extubation failure. Methods Two-hundred and four mechanically ventilated patients in whom an SBT wa

Dark Matter and Fundamental Physics with the Cherenkov Telescope Array

The Cherenkov Telescope Array (CTA) is a project for a next-generation observatory for very high energy (GeV-TeV) ground-based gamma-ray astronomy, currently in its design phase, and foreseen to be operative a few years from now. Several tens of telescopes of 2-3 different sizes, distributed over a large area, will allow for a sensitivity about a factor 10 better than current instruments such as H.E.S.S, MAGIC and VERITAS, an energy coverage from a few tens of GeV to several tens of TeV, and a field of view of up to 10 deg. In the following study, we investigate the prospects for CTA to study several science questions that influence our current knowledge of fundamental physics. Based on conservative assumptions for the performance of the different CTA telescope configurations, we employ a Monte Carlo based approach to evaluate the prospects for detection. First, we discuss CTA prospects for cold dark matter searches, following different observational strategies: in dwarf satellite galaxies of the Milky Way, in the region close to the Galactic Centre, and in clusters of galaxies. The possible search for spatial signatures, facilitated by the larger field of view of CTA, is also discussed. Next we consider searches for axion-like particles which, besides being possible candidates for dark matter may also explain the unexpectedly low absorption by extragalactic background light of gamma rays from very distant blazars. Simulated light-curves of flaring sources are also used to determine the sensitivity to violations of Lorentz Invariance by detection of the possible delay between the arrival times of photons at different energies. Finally, we mention searches for other exotic physics with CTA.Comment: (31 pages, Accepted for publication in Astroparticle Physics