Chemical physics insight of PPy-based modified ion exchange membranes: a fundamental approach

Four commercially available, cost-effective ion exchange membranes (two cationic and two anionic exchange membranes, CEMs and AEMs, respectively) were modified to mitigate crossover phenomena of the redox active species typically observed in Aqueous Organic Redox Flow Batteries (AORFB) systems. The modification strategy was carried out using a pyrrole(Py)-based polymer which successfully reduced the permeation of two redox active organic molecules, a viologen derivative (named BP7 throughout this study) and TEMPOL, by an order of magnitude. Additionally, modified membranes showed not significant changes in ion conductivity, with negligible effect on the electrical conductivity of the membranes at a given conditions. The morphology, physicochemical, mechanical, and electrochemical properties of the membranes were determined to evaluate the impact of these modifications. AEMs modified in this manner were found to have optimal properties, showing an increase in ion exchange capacity while maintaining excellent mechanical stability and unaltered permselectivity. Additionally, the diffusion boundary layer of these AEMs was slightly extended, which suggests a greater double layer stability for ion exchange processes than in the case of CEMs. Our work shows that these modified membranes could be an appealing approach for AORFB applicationsThis work has been funded by the European Union under the HIGREEW project, Affordable High-performance Green Redox Flow batteries (Grant agreement no. 875613). H2020: LC-BAT-4-2019875613

Holocene summer temperature reconstruction based on a chironomid record from Sierra Nevada, southern Spain

This study was supported by projects CGL2013-47038-R, CGL2017-85415-R and PID2021-125619OB-C21/C22, funded by the Ministerio de Ciencia e Innovación of Spain, the Agencia Estatal de Investigación and the Fondo Europeo de Desarrollo Regional FEDER MCIN/AEI/10.13039/501100011033/FEDER, UE”; Junta de Andalucía I + D + i Junta de Andalucía 2020 Retos P-20-00059, UGR-FEDER B-RNM-144-UGR18, UGR-FEDER A-RNM-336-UGR20, Project cofinanced by FEDER and LifeWatch-Eric LifeWatch-2019-10-UGR-01 and the research group RNM-190 (Junta de Andalucía). RSA acknowledges several travel grants from Northern Arizona University to support this work. JC thanks the Ministerio de Ciencia e Innovación of Spain for the Juan de la Cierva Formación postdoctoral fellowship. ALA acknowledges the predoctoral fellowship BES-2018-084293 provided by the MCIN/AEI/10.13039/501100011033/. CLB acknowledges the European Union for her Marie Sklodowska-Curie grant agreement number 892487 under Horizon 2020 funds. LJ acknowledges the Ministry of Universities of Spain for her Margarita Salas grant (MS2021-204) financed by the European Union -Next Generation EU funds.Obtaining accurate temperature reconstructions from the past is crucial in understanding the consequences of changes in external climate forcings, such as orbital-scale insolation or multidecadal to centennial-scale variability on the climate system and the environment. In addition, these reconstructions help in comprehending the amplitude of natural temperature changes in the past, which can assist in evaluating the amplitude and rate of recent anthropogenic global warming. Here we present the first detailed Holocene mean July air temperature reconstruction based on chironomid assemblages from sediments retrieved from Laguna de Río Seco, an alpine lake in Sierra Nevada, southern Spain. Coldest climate conditions are recorded during the last glacial maximum and the last deglaciation. Warming occurred in the Early Holocene and warmest summer temperature conditions and the Holocene thermal maximum (HTM) occurred in the interval roughly between 9000 and 7200 cal yr BP, concurrent with summer insolation maxima. Rapid cooling of ∼1.5 °C occurred after the warmest maximum and between ∼7200 and 6500 cal yr BP, and temperatures stabilized between ∼6500 and 3000 cal yr BP. A further cooling began ∼3000 cal yr BP and culminated with coldest summer conditions during the Dark Ages (DA) and Little Ice Age (LIA) at ∼1550 cal yr BP (∼400 CE) and ∼200 cal yr BP (∼1750 CE), respectively. This cooling temperature trend was interrupted by warmer conditions during the Iberian-Roman Humid Period (IRHP) ∼2000 cal yr BP and during the Medieval Climate Anomaly (MCA) at ∼1000 cal yr BP. Our reconstruction shows a greater than two-degree cooling during the Middle and Late Holocene, agreeing with global mean surface temperature (GMST) reconstructions. Modern climate warming (MCW) during summer exceeds the two-degree Celsius forecasted for the future due to anthropogenic greenhouse gases, suggesting that recent warming is amplified at high elevations. Alpine environments and the biodiversity contained there are thus in danger if the observed temperature trend continues in the next decades.Ministerio de Ciencia e Innovación of Spain CGL2013-47038-R, CGL2017-85415-R, PID2021-125619OB-C21/C22Agencia Estatal de InvestigaciónFondo Europeo de Desarrollo Regional FEDER MCIN/AEI/10.13039/501100011033/FEDER, UEJunta de Andalucía P-20-00059, UGR-FEDER B-RNM-144-UGR18, UGR-FEDER A-RNM-336-UGR20FEDERLifeWatch-Eric LifeWatch-2019-10-UGR-01Research group RNM-190 (Junta de Andalucía)Northern Arizona UniversityMinisterio de Ciencia e Innovación of SpainMCIN/AEI/10.13039/501100011033/ BES-2018-084293Horizon 2020 European Union Marie Sklodowska-Curie 892487European Union -Next Generation EU funds MS2021-20

Paleoenvironmental evolution of Laguna Seca lake (Sierra Nevada, southern Iberia) since the Late Glacial

Comunicación oral en XXI INQUA Congress. Rome (Italy). 14-20th july 2023Laguna Seca lake at 2259 masl has provided the longest alpine sedimentary record in southern Iberia, registering the last ~18 kyr in a ~14-meter-long sediment core. The oldest part of the sedimentary record represents a phase of subaerial debris flows and a small glacier/nivation hollow. The sediment characteristics abruptly changed at ~15.7 cal kyr BP, when a lake environment was established. A multi-proxy approach (magnetic susceptibility, organic geochemical analyses in bulk sediment, XRF core scanner data, and algae identification) has allowed the characterization of three different environmental phases in this lake. Deep lake conditions are identified from ~15.7 to ~10.6 cal kyr BP, agreeing with overall increasing precipitation in southern Iberia coinciding with augmenting summer insolation. This part of the record is characterized by grey lutites with high total organic carbon (TOC) content, high algae productivity, high vascular plant inputs (high C/N ratio) from the catchment and low Fe/S ratio, suggesting low oxygen conditions in the water-sediment interphase. Between ~10.6 and 8.2-8.0 cal kyr BP higher TOC and low Fe/S ratio are also recorded as well as higher algae content and low C/N ratio suggesting high aquatic production and more algae contribution to the local organic matter pool. This period registered the highest lake levels agreeing with summer insolation maximum and highest precipitation in southern Iberia. An abrupt lowering of the lake level is recorded after 8.0 cal kyr BP in the area. This is deduced by the decrease in TOC and algae in the sediments and more siliciclastic contribution from the catchment basin, evidenced by a high increase in siliciclastic elements (Si, Al, K, Ti, among others), with increased oxic conditions in the water-sediment interphase pointed out by the high increase in Fe/S ratio. Additionally, a potential increase in north African aeolian inputs (rich in Fe cations and Fe compounds) can be interpreted for the Middle and Late Holocene, evidenced by high Fe/Al values. This environmental change agrees with an aridification trend previously observed in the southern Iberian Peninsula

Brood parasitism, provisioning rates and breeding phenology of male and female magpie hosts

Parental care is a costly behaviour that raises the prospects of offspring survival. In species with biparental care these costs are shared by both parents, although there may be a conflict regarding the relative investment of each sex. Avian brood parasites leave all the costs of rearing offspring to their hosts. The magnitude of these costs and their consequences on the relative role of both sexes in parental care and future reproduction remain mostly unknown. Here, we investigate whether provisioning rate of nestlings by magpie hosts Pica pica differs between broods parasitized by the great spotted cuckoo Clamator glandarius and non-parasitized broods, and whether the relative contribution of each sex to provisioning is affected by parasitism. Furthermore, we explore the effect of parasitism on magpie’s future reproduction. We found that provisioning rate was similar in parasitized and non-parasitized broods, and that the relative contribution of males and females was also similar, irrespectively of the parasitism status. However, rearing parasitic offspring seems to have a negative long-term effect on magpie’s breeding phenology in the following breeding season. Our results suggest that, although brood parasitism by great spotted cuckoos does not seem to influence the relative contribution of both sexes to parental care, it may entail long-term extra costs in terms of breeding delay for magpies.Junta de Andalucía (Proyecto P06-RNM-01862)Ministerio de Ciencia (proyecto CGL2014-55362-P)Programa Juan de la Cierva –Incorporación (IJC2018-036411-I)German Research Foundation (SFB TRR 212 (NC3) – Projectos n. 316099922 y 396782608

Caffeine as a tool for investigating the integration of Cdc25 phosphorylation, activity and ubiquitin-dependent degradation in Schizosaccharomyces pombe

The evolutionarily conserved Cdc25 phosphatase is an essential protein that removes inhibitory phosphorylation moieties on the mitotic regulator Cdc2. Together with the Wee1 kinase, a negative regulator of Cdc2 activity, Cdc25 is thus a central regulator of cell cycle progression in Schizosaccharomyces pombe. The expression and activity of Cdc25 is dependent on the activity of the Target of Rapamycin Complex 1 (TORC1). TORC1 inhibition leads to the activation of Cdc25 and repression of Wee1, leading to advanced entry into mitosis. Withdrawal of nitrogen leads to rapid Cdc25 degradation via the ubiquitin- dependent degradation pathway by the Pub1 E3- ligase. Caffeine is believed to mediate the override of DNA damage checkpoint signalling, by inhibiting the activity of the ataxia telangiectasia mutated (ATM)/Rad3 homologues. This model remains controversial, as TORC1 appears to be the preferred target of caffeine in vivo. Recent studies suggest that caffeine induces DNA damage checkpoint override by inducing the nuclear accumulation of Cdc25 in S. pombe. Caffeine may thus modulate Cdc25 activity and stability via inhibition of TORC1. A clearer understanding of the mechanisms by which caffeine stabilises Cdc25, may provide novel insights into how TORC1 and DNA damage signalling is integrated

MEGARA, the new intermediate-resolution optical IFU and MOS for GTC: getting ready for the telescope

MEGARA (Multi-Espectrógrafo en GTC de Alta Resolución para Astronomía) is an optical Integral-Field Unit (IFU) and Multi-Object Spectrograph (MOS) designed for the GTC 10.4m telescope in La Palma that is being built by a Consortium led by UCM (Spain) that also includes INAOE (Mexico), IAA-CSIC (Spain), and UPM (Spain). The instrument is currently finishing AIV and will be sent to GTC on November 2016 for its on-sky commissioning on April 2017. The MEGARA IFU fiber bundle (LCB) covers 12.5x11.3 arcsec2 with a spaxel size of 0.62 arcsec while the MEGARA MOS mode allows observing up to 92 objects in a region of 3.5x3.5 arcmin2 around the IFU. The IFU and MOS modes of MEGARA will provide identical intermediate-to-high spectral resolutions (RFWHM~6,000, 12,000 and 18,700, respectively for the low-, mid- and high-resolution Volume Phase Holographic gratings) in the range 3700-9800ÅÅ. An x-y mechanism placed at the pseudo-slit position allows (1) exchanging between the two observing modes and (2) focusing the spectrograph for each VPH setup. The spectrograph is a collimator-camera system that has a total of 11 VPHs simultaneously available (out of the 18 VPHs designed and being built) that are placed in the pupil by means of a wheel and an insertion mechanism. The custom-made cryostat hosts a 4kx4k 15-μm CCD. The unique characteristics of MEGARA in terms of throughput and versatility and the unsurpassed collecting are of GTC make of this instrument the most efficient tool to date to analyze astrophysical objects at intermediate spectral resolutions. In these proceedings we present a summary of the instrument characteristics and the results from the AIV phase. All subsystems have been successfully integrated and the system-level AIV phase is progressing as expected

Persistent Pulmonary Hypertension in Corrected Valvular Heart Disease: Hemodynamic Insights and Long-Term Survival.

Background The determinants and consequences of pulmonary hypertension after successfully corrected valvular heart disease remain poorly understood. We aim to clarify the hemodynamic bases and risk factors for mortality in patients with this condition. Methods and Results We analyzed long-term follow-up data of 222 patients with pulmonary hypertension and valvular heart disease successfully corrected at least 1 year before enrollment who had undergone comprehensive hemodynamic and imaging characterization as per the SIOVAC (Sildenafil for Improving Outcomes After Valvular Correction) clinical trial. Median (interquartile range) mean pulmonary pressure was 37 mm Hg (32-44 mm Hg) and pulmonary artery wedge pressure was 23 mm Hg (18-26 mm Hg). Most patients were classified either as having combined precapillary and postcapillary or isolated postcapillary pulmonary hypertension. After a median follow-up of 4.5 years, 91 deaths accounted for 4.21 higher-than-expected mortality in the age-matched population. Risk factors for mortality were male sex, older age, diabetes mellitus, World Health Organization functional class III and higher pulmonary vascular resistance-either measured by catheterization or approximated from ultrasound data. Higher pulmonary vascular resistance was related to diabetes mellitus and smaller residual aortic and mitral valve areas. In turn, the latter correlated with prosthetic nominal size. Six-month changes in the composite clinical score and in the 6-minute walk test distance were related to survival. Conclusions Persistent valvular heart disease-pulmonary hypertension is an ominous disease that is almost universally associated with elevated pulmonary artery wedge pressure. Pulmonary vascular resistance is a major determinant of mortality in this condition and is related to diabetes mellitus and the residual effective area of the corrected valve. These findings have important implications for individualizing valve correction procedures. Registration URL: https://www.clinicaltrials.gov; Unique identifier: NCT00862043.This study was funded by the Instituto de Salud Carlos III, Ministerio de Ciencia e Innovación, Spain, the European Union–European Regional Development Fund (EC07/90772 and PI19/00649), and the Consorcio de Investigación Biomédica en Red de Enfermedades Cardiovasculares (CIBERCV).S

Tautomerism, structure in solution and in the solid state of 1:9,5:10-anthradipyrazole

By means of DFT calculations [B3LYP/6-311++G(d,p), GIAO], the properties of the three tautomers of 1:9,5:10-anthradipyrazole were analyzed and compared with Maspero's crystal structures and NMR results. The agreement is fairly good and in agreement with indazole tautomers. Besides, the aromaticity of these interesting five-membered ring systems was explored. © 2014 Springer Science+Business Media New York.Peer Reviewe