Estimating the probability of occurrence of African dust outbreaks over regions of the western Mediterranean basin from thermodynamic atmospheric parameters.

Desert dust is currently recognized as a health risk factor. Therefore, the World Health Organization (WHO) is actively promoting the establishment of early warning systems for sand and dust storms. This study introduces a methodology to estimate the probability of African dust outbreaks occurring in eight different regions of the Iberian Peninsula and the Balearic Islands. In each region, a multilinear regression model was developed to calculate daily probabilities of dust events using three thermodynamic variables (geopotential thickness in the 1000-500 hPa layer, mean potential temperature between 925 and 700 hPa, and temperature anomalies at 850 hPa) as assessment parameters. All days with African dust transport over each study region were identified in the period 2001-2021 using a proven procedure. This information was then utilized to establish a functional relationship between the values of the thermodynamic parameters and the probability of African dust outbreaks occurring. The validation of this methodology involved comparing the daily probabilities of dust events generated by the models in 2001-2021 with the daily African dust contributions to PM10 regional background levels in each region. On average, daily dust contributions increased proportionally with the increase in daily probabilities, reaching zero for days with low probabilities. Furthermore, a well-defined seasonal evolution of probability values was observed in all regions, with the highest values in the summer months and the lowest in the winter period, ensuring the physical relevance of the models' results. Finally, upward trends were observed in all regions for the three thermodynamic parameters over 1940-2021. Thus, the probability of dust events development also increased in this period. It demonstrates that the aggravation of warm conditions in southern Europe in the last decades, have modified the frequency of North-African dust outbreaks over the western Mediterranean basin.

Air quality and characterization of synoptic circulation weather patterns in a South American city from Argentina.

The potential cause-effect relationship between synoptic meteorological conditions and levels of criteria air pollutants, including CO, NO2, O3, PM10, PM2.5 and SO2, in Bahia Blanca, Argentina, was assessed for the period of 2018-2019. Daily back-trajectories and global meteorological data fields were employed to characterize the primary transport paths of air masses reaching the study site, and to identify the synoptic meteorological patterns responsible for these atmospheric circulations. Time series of surface-level meteorological parameters and midday mixing layer height were collected to examine the impact of the synoptic meteorological patterns on local meteorology. Furthermore, the NAAPS global aerosol model was utilized to identify days when contributions from long-range transport processes, such as dust and/or biomass burning smoke, impacted air quality. By applying this methodology, it was determined that the air masses coming from the N, NW and W regions significantly contributed to increased mean concentrations of coarse particles in this area through long-range transport events involving dust and smoke. Indeed, the high average levels of PM10 recorded in 2018-2019 (annual mean values of 47 and 52 µg/m3, respectively) represent the main air quality concern in Bahía Blanca. Moreover, PM10, PM2.5 and NO2 emissions should be reduced in order to meet recommended air quality guidelines. On the other hand, the results from this study suggest that the sources and meteorological processes leading to the increase in the concentrations of CO and SO2 have a local-regional origin, although these air pollutants did not reach high values probably as a consequence of the strong wind speed registered in this region during any synoptic meteorological pattern.

Ti(III) Catalysts for CO2/Epoxide Copolymerization at Unusual Ambient Pressure Conditions.

Titanium compounds in low oxidation states are highly reducing species and hence powerful tools for the functionalization of small molecules. However, their potential has not yet been fully realized because harnessing these highly reactive complexes for productive reactivity is generally challenging. Advancing this field, herein we provide a detailed route for the formation of titanium(III) orthophenylendiamido (PDA) species using [LiBHEt3] as a reducing agent. Initially, the corresponding lithium PDA compounds [Li2(ArPDA)(thf)3] (Ar = 2,4,6-trimethylphenyl (MesPDA), 2,6-diisopropylphenyl (iPrPDA)) are combined with [TiCl4(thf)2] to form the heterobimetallic complexes [{TiCl(ArPDA)}(µ-ArPDA){Li(thf)n}] (n = 1, Ar = iPr 3 and n = 2, Ar = Mes 4). Compound 4 evolves to species [Ti(MesPDA)2] (6) via thermal treatment. In contrast, the transformation of 3 into [Ti(iPrPDA)2] (5) only occurs in the presence of [LiNMe2], through a lithium-assisted process, as revealed by density functional theory (DFT). Finally, the Ti(IV) compounds 3-6 react with [LiBHEt3] to give rise to the Ti(III) species [Li(thf)4][Ti(ArPDA)2] (Ar = iPr 8, Mes 9). These low-valent compounds in combination with [PPN]Cl (PPN = bis(triphenylphosphine)iminium) are proved to be highly selective catalysts for the copolymerization of CO2 and cyclohexene epoxide. Reactions occur at 1 bar pressure with activity/selectivity levels similar to Salen-Cr(III) compounds.

Influence of synoptic meteorology on airborne allergenic pollen and spores in an urban environment in Northeastern Iberian Peninsula.

The influence of the most frequent patterns of synoptic circulation on the dynamics of airborne pollen/spores recorded at the Barcelona Aerobiological Station (BCN) was analysed. Six pollen types (Platanus, Cupressaceae, Olea, Poaceae, Urticaceae and Amaranthaceae), and one fungal spore (Alternaria) were selected for their high allergenic effect in sensitive people. Six synoptic meteorological patterns were identified through cluster analysis of sea level pressure fields as the main responsible of the weather conditions in the Iberian Peninsula. The local meteorological conditions in Barcelona associated with each one of the synoptic types were also stablished. Different statistical methods were applied to analyse possible relationships between concentrations and timing of the recorded aerobiological particles and specific synoptic types. The study, focused in the 19-year period 2001-2019, shows that one of the scenarios, frequent in winter and linked to high stability and air-mass blockage, registered the highest mean and median values for Platanus and Cupressaceae, but it was not very relevant for the other taxa. It was also this scenario that turned out to be the most influent on the pollination timing showing a significant influence on the start occurrence of Urticaceae flowering and on the peak date of Platanus. On the other hand, the most frequent synoptic type in the period, relevant in spring and summer, was linked to sporadic episodes of levels considered to be of high risk of allergy to Platanus, Poaceae, and Urticaceae pollen, and Alternaria fungal spore. This synoptic pattern, characterized by the presence of the Azores anticyclone and the Atlantic low located in the north of the United Kingdom, was associated with high temperatures, low relative humidity and moderate winds from the NW in Barcelona. The identification of an interaction between synoptic meteorology and pollen/spore dynamics will allow better abatement measures, reducing adverse health effects on sensitive population.

Exact decompositions of the total KS-DFT exchange-correlation energy into one- and two-center terms.

In the so-called Interacting Quantum Atoms (IQA) approach, the molecular energy is numerically decomposed as a sum of atomic and diatomic contributions. While proper formulations have been put forward for both Hartree-Fock and post-Hartree-Fock wavefunctions, this is not the case for the Kohn-Sham density functional theory (KS-DFT). In this work, we critically analyze the performance of two fully additive approaches for the IQA decomposition of the KS-DFT energy, namely, the one from Francisco et al., which uses atomic scaling factors, and that from Salvador and Mayer based upon the bond order density (SM-IQA). Atomic and diatomic exchange-correlation (xc) energy components are obtained for a molecular test set comprising different bond types and multiplicities and along the reaction coordinate of a Diels-Alder reaction. Both methodologies behave similarly for all systems considered. In general, the SM-IQA diatomic xc components are less negative than the Hartree-Fock ones, which is in good agreement with the known effect of electron correlation upon (most) covalent bonds. In addition, a new general scheme to minimize the numerical error of the sum of two-electron energy contributions (i.e., Coulomb and exact exchange) in the framework of overlapping atoms is described in detail.

Does Serial Femtosecond Crystallography Depict State-Specific Catalytic Intermediates of the Oxygen-Evolving Complex?

Recent advances in serial femtosecond crystallography (SFX) of photosystem II (PSII), enabled by X-ray free electron lasers (XFEL), provided the first geometric models of distinct intermediates in the catalytic S-state cycle of the oxygen-evolving complex (OEC). These models are obtained by flash-advancing the OEC from the dark-stable state (S1) to more oxidized intermediates (S2 and S3), eventually cycling back to the most reduced S0. However, the interpretation of these models is controversial because geometric parameters within the Mn4CaO5 cluster of the OEC do not exactly match those expected from coordination chemistry for the spectroscopically verified manganese oxidation states of the distinct S-state intermediates. Here we focus on the first catalytic transition, S1 → S2, which represents a one-electron oxidation of the OEC. Combining geometric and electronic structure criteria, including a novel effective oxidation state approach, we analyze existing 1-flash (1F) SFX-XFEL crystallographic models that should depict the S2 state of the OEC. We show that the 1F/S2 equivalence is not obvious, because the Mn oxidation states and total unpaired electron counts encoded in these models are not fully consistent with those of a pure S2 state and with the nature of the S1 → S2 transition. Furthermore, the oxidation state definition in two-flashed (2F) structural models is practically impossible to elucidate. Our results advise caution in the extraction of electronic structure information solely from the literal interpretation of crystallographic models and call for re-evaluation of structural and mechanistic interpretations that presume exact correspondence of such models to specific catalytic intermediates of the OEC.

Merging the Energy Decomposition Analysis with the Interacting Quantum Atoms Approach.

Energy decomposition analysis (EDA) is a well-established approach to dissect the interaction energy into chemically sound components. Despite the inherent requirement of reference states has been a long-standing object of debate, the direct relation with the molecular orbital analysis helps in building up predictive models. The alternative molecular energy decomposition schemes that decompose the total energy into atomic and diatomic contributions, such as the interacting quantum atoms (IQA), has no external reference requirements and also the intra- and intermolecular interactions are treated on equal footing. However, a connection with heuristic chemical models are limited, bringing about a somewhat narrower predictive power. While efforts to reconcile the bonding picture obtained by both methodologies have been discussed in the past, a synergic combination of them has not been tackled yet. Herein, we present the use of IQA decomposition of the individual terms arising from the EDA in the context of intermolecular interactions, henceforth EDA-IQA. The method is applied to a molecular set covering a wide range of interaction types, including hydrogen bonding, charge-dipole, π-π and halogen interactions. We find that the electrostatic energy from EDA, entirely seen as intermolecular, leads to meaningful and non-negligible intra-fragment contributions upon IQA decomposition, originated from charge penetration. EDA-IQA also affords the decomposition of the Pauli repulsion term into intra- and inter-fragment contributions. The intra-fragment term is destabilizing, particularly for the moieties that are net acceptors of charge, while the inter-fragment Pauli term is actually stabilizing. In the case of the orbital interaction term, the sign and magnitude of the intra-fragment contribution at equilibrium geometries is largely driven by the amount of charge transfer, while the inter-fragment contribution is clearly stabilizing. EDA-IQA terms show a smooth behavior along the intermolecular dissociation path of selected systems. The new EDA-IQA methodology provides a richer energy decomposition scheme that aims at bridging the gap between the two main distinct real-space and Hilbert-space methodologies. Via this approach, the partitioning can be used directionally on all the EDA terms aiding in identifying the causal effects on geometries and/or reactivity.

Force Decomposition Analysis: A Method to Decompose Intermolecular Forces into Physically Relevant Component Contributions.

Computational quantum chemistry can be more than just numerical experiments when methods are specifically adapted to investigate chemical concepts. One important example is the development of energy decomposition analysis (EDA) to reveal the physical driving forces behind intermolecular interactions. In EDA, typically the interaction energy from a good-quality density functional theory (DFT) calculation is decomposed into multiple additive components that unveil permanent and induced electrostatics, Pauli repulsion, dispersion, and charge-transfer contributions to noncovalent interactions. Herein, we formulate, implement, and investigate decomposing the forces associated with intermolecular interactions into the same components. The resulting force decomposition analysis (FDA) is potentially useful as a complement to the EDA to understand chemistry, while also providing far more information than an EDA for data analysis purposes such as training physics-based force fields. We apply the FDA based on absolutely localized molecular orbitals (ALMOs) to analyze interactions of water with sodium and chloride ions as well as in the water dimer. We also analyze the forces responsible for geometric changes in carbon dioxide upon adsorption onto (and activation by) gold and silver anions. We also investigate how the force components of an EDA-based force field for water clusters, namely MB-UCB, compare to those from force decomposition analysis.

Reply to the 'Comment on "The oxidation state in low-valent beryllium and magnesium compounds"' by S. Pan and G. Frenking, Chem. Sci., 2022, 13, DOI: 10.1039/D2SC04231B.

A recent article by Pan and Frenking challenges our assignment of the oxidation state of low valent group 2 compounds. With this reply, we show that our assignment of Be(+2) and Mg(+2) oxidation states in Be(cAACDip)2 and Mg(cAACDip)2 is fully consistent with our data. Some of the arguments exposed by Pan and Frenking were based on visual inspection of our figures, rather than a thorough numerical analysis. We discuss with numerical proof that some of the statements made by the authors concerning our reported data are erroneous. In addition, we provide further evidence that the criterion of the lowest orbital interaction energy in the energy decomposition analysis (EDA) method is unsuitable as a general tool to assess the valence state of the fragments. Other indicators based on natural orbitals for chemical valence (NOCV) deliver a more reliable bonding picture. We also emphasize the importance of using stable wavefunctions for any kind of analysis, including EDA.

Heart Failure with Preserved Ejection Fraction: a Pharmacotherapeutic Update.

While guidelines for management of heart failure with reduced ejection fraction (HFrEF) are consensual and have led to improved survival, treatment options for heart failure with preserved ejection fraction (HFpEF) remain limited and aim primarily for symptom relief and improvement of quality of life. Due to the shortage of therapeutic options, several drugs have been investigated in multiple clinical trials. The majority of these trials have reported disappointing results and have suggested that HFpEF might not be as simply described by ejection fraction as previously though. In fact, HFpEF is a complex clinical syndrome with various comorbidities and overlapping distinct phenotypes that could benefit from personalized therapeutic approaches. This review summarizes the results from the most recent phase III clinical trials for HFpEF and the most promising drugs arising from phase II trials as well as the various challenges that are currently holding back the development of new pharmacotherapeutic options for these patients.

Cage-size effects on the encapsulation of P2 by fullerenes.

The classic pnictogen dichotomy stands for the great contrast between triply bonding very stable N2 molecules and its heavier congeners, which appear as dimers or oligomers. A banner example involves phosphorus as it occurs in nature as P4 instead of P2 , given its weak π-bonds or strong σ-bonds. The P2 synthetic value has brought Lewis bases and metal coordination stabilization strategies. Herein, we discuss the unrealized encapsulation alternative using the well-known fullerenes' capability to form endohedral and stabilize otherwise unstable molecules. We chose the most stable fullerene structures from Cn (n = 50, 60, 70, 80) and experimentally relevant from Cn (n = 90 and 100) to computationally study the thermodynamics and the geometrical consequences of encapsulating P2 inside the fullerene cages. Given the size differences between P2 and P4 , we show that the fullerenes C70 -C100 are suitable cages to side exclude P4 and host only one molecule of P2 with an intact triple bond. The thermodynamic analysis indicates that the process is favorable, overcoming the dimerization energy. Additionally, we have evaluated the host-guest interaction to explain the origins of their stability using energy decomposition analysis.

Mechanistic Insights into the Oxidative and Reductive Quenching Cycles of Transition Metal Photoredox Catalysts through Effective Oxidation State Analysis.

The electronic structures of the ground and excited electronic states involved in the oxidative and reductive quenching cycles of 12 relevant ruthenium, iridium, and copper photoredox catalysts (S0, T1, Dox, and Dred) are characterized using the recently developed effective oxidation state (EOS) analysis, allowing the monitoring of metal and ligand oxidation states (OSs) along the catalytic cycles. The formal oxidation state assignments derived from the EOS analysis are in agreement with those commonly assumed for these complexes in both ground and excited states. Rather clean and separate ligand- and metal-centered redox events along the different quenching cycles are observed in most of the studied molecular systems. The reliability index obtained for the OS assignations can be readily interpreted in terms of the ionic/covalent character of metal-ligand interactions and ligand non-innocent character. In addition, EOS analysis reveals the high-degree localization of the ligand-centered redox event to one or two redox-active ligand(s) in heteroleptic complexes. Ligand- and metal-condensed spin populations were also computed and analyzed for all the open-shell species involved in this study, showing promises for rapid oxidation state assignments in certain systems, especially Ru complexes, however, suffering from severe defects in other cases.

Csp2-H Amination Reactions Mediated by Metastable Pseudo-Oh Masked Aryl-CoIII-nitrene Species.

Cobalt-catalyzed C-H amination via M-nitrenoid species is spiking the interest of the research community. Understanding this process at a molecular level is a challenging task, and here we report a well-defined macrocyclic system featuring a pseudo-Oh aryl-CoIII species that reacts with aliphatic azides to effect intramolecular Csp2-N bond formation. Strikingly, a putative aryl-Co═NR nitrenoid intermediate species is formed and is rapidly trapped by a carboxylate ligand to form a carboxylate masked-nitrene, which functions as a shortcut to stabilize and guide the reaction to productive intramolecular Csp2-N bond formation. On one hand, several intermediate species featuring the Csp2-N bond formed have been isolated and structurally characterized, and the essential role of the carboxylate ligand has been proven. Complementarily, a thorough density functional theory study of the Csp2-N bond formation mechanism explains at the molecular level the key role of the carboxylate-masked nitrene species, which is essential to tame the metastability of the putative aryl-CoIII═NR nitrene species to effectively yield the Csp2-N products. The solid molecular mechanistic scheme determined for the Csp2-N bond forming reaction is fully supported by both experimental and computation complementary studies.

The oxidation state in low-valent beryllium and magnesium compounds.

Low-valent group 2 (E = Be and Mg) stabilized compounds have been long synthetically pursued. Here we discuss the electronic structure of a series of Lewis base-stabilized Be and Mg compounds. Despite the accepted zero(0) oxidation state nature of the group 2 elements of some recent experimentally accomplished species, the analysis of multireference wavefunctions provides compelling evidence for a strong diradical character with an oxidation state of +2. Thus, we elaborate on the distinction between a description as a donor-acceptor interaction L(0) ⇆ E(0) ⇄ L(0) and the internally oxidized situation, better interpreted as a diradical L(-1) → E(+2) ← L(-1) species. The experimentally accomplished examples rely on the strengthened bonds by increasing the π-acidity of the ligand; avoiding this interaction could lead to an unprecedented low-oxidation state.

Síndrome de platinea-ortodeoxia en una señora mayor: un desafío diagnóstico / Platypnea-orthodeoxia syndrome in an old lady – a clinical challenge

Introduction: Platypnea-orthodeoxia syndrome (POS) is a rare disordercharacterized by dyspnoea and oxygen desaturation in the upright position which improves in the supine position.Clinical case: 84 years old woman with hypertension and Parkinson disease. She came to the emergency department complainingof dyspnoea. At admission she was polypneic (35 bpm), spO2 80%,157/108mmHg, 115bpm, apyretic, normal pulmonary auscultation andwithout peripheral oedema. Oxygen supplementation was started withlack of response. The patient, which at first was lying in the bed withthe headboard at 45º, recovered the peripheral oxygen saturation to96-97% when the bed was placed at 0º. Diagnostic tests were performed, excluding cardiac myocardial infarction, pulmonary embolismand pneumonia. Transthoracic echocardiogram revealed an aneurysmatic interauricular septum with transoesophageal echocardiogramshowing an interauricular communication ostium secundum type witha septal aneurysm that led to a right to left shunt. The anatomical andclinical features did not allowed percutaneous or surgical closure. Aftera group discussion we decided for palliative care.Discussion: POS due to a septal aneurysm with right-to-left shunt is arare and difficult diagnose because it requires a detailed medical examination and exclusion of any other possible diseases. Besides that, itis a very rare presentation in such an old person. (AU)

Introducción: El síndrome de platipnea-ortodesoxia (SPO) es un trastorno poco común caracterizado por disnea y desaturación de oxígenoen posición erguida que mejora en posición supina.Caso clínico: mujer de 84 años con hipertensión y enfermedad de Parkinson. Acudió al servicio de urgencias quejándose de disnea. Al ingreso se encontraba taquipneica (35cpm), spO2 80%, 157/108mmHg,115bpm, apirética, auscultación pulmonar normal y sin edema periférico. La suplementación con oxígeno se inició con ausencia de respuesta. La paciente, que al principio estaba acostada en la cama con elcabecero a 45º, recuperó la saturación de oxígeno periférico al 96-97%cuando la cama se colocó a 0º. Se realizaron pruebas diagnósticas,excluyendo infarto de miocardio, embolia pulmonar y neumonía. Elecocardiograma transtorácico reveló un septo interauricular aneurismático con ecocardiograma transesofágico que mostraba comunicacióninterauricular tipo ostium secundum con aneurisma septal que conducíaa un shunt de derecha a izquierda. Las características anatómicas yclínicas no permitieron el cierre percutáneo o quirúrgico. Después deuna discusión en grupo, nos decidimos por los cuidados paliativos.Discusión: El SPO por aneurisma septal con derivación de derecha aizquierda es un diagnóstico raro y difícil porque requiere un examenmédico detallado y la exclusión de cualquier otra posible enfermedad. Además de eso, es una presentación muy rara en una personatan mayor. (AU)

Oxidation State Localized Orbitals: A Method for Assigning Oxidation States Using Optimally Fragment-Localized Orbitals and a Fragment Orbital Localization Index.

Oxidation states represent the ionic distribution of charge in a molecule and are significant in tracking redox reactions and understanding chemical bonding. While effective algorithms already exist based on formal Lewis structures as well as using localized orbitals, they exhibit differences in challenging cases where effects such as redox noninnocence are at play. Given a density functional theory (DFT) calculation with chosen total charge and spin multiplicity, this work reports a new approach to obtaining fragment-localized orbitals that is termed oxidation state localized orbitals (OSLO), together with an algorithm for assigning the oxidation state using the OSLOs and an associated fragment orbital localization index (FOLI). Evaluating the FOLI requires fragment populations, and for this purpose a new version of the intrinsic atomic orbital (IAO) scheme is introduced in which the IAOs are evaluated using a reference minimal basis formed from on-the-fly superposition of atomic density (IAO-AutoSAD) calculations in the target basis set and at the target level of theory. The OSLO algorithm is applied to a range of challenging cases including high valent metal oxide complexes, redox noninnocent NO and dithiolate transition metal complexes, a range of carbene-containing TM complexes, and other examples including the potentially inverted ligand field in [Cu(CF3)4]-. Across this range of cases, OSLO produces generally satisfactory results. Furthermore, in borderline cases, the OSLOs and associated FOLI values provide direct evidence of the emergence of covalent interactions between fragments that nicely complements existing approaches.

Eficacia y seguridad del misoprostol vaginal comparado con dinoprostona en maduración cervical e inducción del parto / Effectiveness and safety of vaginal misoprostol vs dinoprostone for cervical ripening and labour induction

Resumen OBJETIVO: Comparar la eficacia del misoprostol intravaginal con el dispositivo vaginal de liberación prolongada de dinoprostona en la inducción del parto. Además, analizar el perfil de seguridad en relación con los desenlaces maternos y perinatales. MATERIALES Y MÉTODOS: Estudio retrospectivo y comparativo efectuado en pacientes atendidas entre 2018 y 2020 en el Área Sanitaria de Ferrol, La Coruña, España, con partos que se iniciaron con inducción con prostaglandinas. Las pacientes se dividieron en dos cohortes, en función de la prostaglandina sintética administrada (misoprostol por vía vaginal o dinoprostona en dispositivo intravaginal). Para la comparación entre ambos grupos se aplicó la prueba U de Mann-Whitney. Para las variables cualitativas se describió su cantidad total y el porcentaje, que se compararon con prueba de χ2 de Pearson. RESULTADOS: Se analizaron 508 pacientes con inducción del parto. En las indicaciones de ésta no se encontraron diferencias entre uno y otro grupo, aunque destacó la indicación del misoprostol en pacientes con embarazo cronológicamente prolongado (63%) y de dinoprostona en rotura prematura de membranas (49%). En relación con los desenlaces perinatales, se registró un Apgar menor de 7 a los 5 minutos en 2 pacientes tratadas con dinoprostona y 1 con misoprostol; así como un pH arterial umbilical menor de 7.10 en 8 pacientes tratadas con dinoprostona y 7 con misoprostol. CONCLUSIONES: Los datos aquí reportados hacen suponer que ambas prostaglandinas consiguen una tasa de inicio del parto similar, aunque la dinoprostona parece reducir el tiempo hasta el inicio del parto en mujeres con indicación de inducción.

Abstract OBJECTIVE: To compare the efficacy of intravaginal misoprostol with the dinoprostone extended-release vaginal device in labor induction. In addition, to analyze the safety profile in relation to maternal and perinatal outcomes. MATERIALS AND METHODS: Retrospective and comparative study performed in patients attended between 2018 and 2020 in the Health Area of Ferrol, La Coruña, Spain, with deliveries that were initiated with prostaglandin induction. The patients were divided into two cohorts, depending on the synthetic prostaglandin administered (misoprostol vaginally or dinoprostone in intravaginal device). The Mann-Whitney U test was used to compare the two groups. For qualitative variables, the total number and percentage were described and compared with Pearson's 2 test. RESULTS: A total of 508 patients undergoing labor induction were analyzed. No differences were found in the indications for induction of labor between one group and the other, although the indication for misoprostol in patients with chronologically prolonged pregnancy (63%) and for dinoprostone in premature rupture of membranes (49%) stood out. In relation to perinatal outcomes, an Apgar of less than 7 at 5 minutes was recorded in 2 patients treated with dinoprostone and 1 with misoprostol; as well as an umbilical arterial pH of less than 7.10 in 8 patients treated with dinoprostone and 7 with misoprostol. CONCLUSIONS: The data reported here suggest that both prostaglandins achieve a similar rate of onset of labor, although dinoprostone appears to reduce the time to onset of labor in women indicated for induction.

Learning from the COVID-19 lockdown in berlin: Observations and modelling to support understanding policies to reduce NO2.

Urban air pollution is a substantial threat to human health. Traffic emissions remain a large contributor to air pollution in urban areas. The mobility restrictions put in place in response to the COVID-19 pandemic provided a large-scale real-world experiment that allows for the evaluation of changes in traffic emissions and the corresponding changes in air quality. Here we use observational data, as well as modelling, to analyse changes in nitrogen dioxide, ozone, and particulate matter resulting from the COVID-19 restrictions at the height of the lockdown period in Spring of 2020. Accounting for the influence of meteorology on air quality, we found that reduction of ca. 30-50 % in traffic counts, dominated by changes in passenger cars, corresponded to reductions in median observed nitrogen dioxide concentrations of ca. 40 % (traffic and urban background locations) and a ca. 22 % increase in ozone (urban background locations) during weekdays. Lesser reductions in nitrogen dioxide concentrations were observed at urban background stations at weekends, and no change in ozone was observed. The modelled reductions in median nitrogen dioxide at urban background locations were smaller than the observed reductions and the change was not significant. The model results showed no significant change in ozone on weekdays or weekends. The lack of a simulated weekday/weekend effect is consistent with previous work suggesting that NOx emissions from traffic could be significantly underestimated in European cities by models. These results indicate the potential for improvements in air quality due to policies for reducing traffic, along with the scale of reductions that would be needed to result in meaningful changes in air quality if a transition to sustainable mobility is to be seriously considered. They also confirm once more the highly relevant role of traffic for air quality in urban areas.

Restoring oak forests through direct seeding or planting: Protocol for a continental-scale experiment.

The choice of revegetating via direct seeding or planting nursery-grown seedlings influences the potential stresses suffered by seedlings such as herbivory and drought. The outcome of the balance between both revegetation methods may ultimately depend on how species identity and traits such as seed and seedling size interact with environmental conditions. To test this, we will conduct a continental-scale experiment consisting of one mini-experiment replicated by multiple participants across Europe. Each participant will establish a site with seeded and planted individuals of one or more native, locally growing oak (Quercus) species; the selection of this genus aims to favour continental-scale participation and to allow testing the response of a widely distributed genus of broad ecological and economic relevance. At each site, participants will follow the present protocol for seed collection, seeding in the field, nursery cultivation, outplanting, protection against herbivores, site maintenance, and measurement of seedling performance and environmental variables. Each measurement on each species at each site will produce one effect size; the data will be analysed through mixed-effects meta-analysis. With this approach we will assess the main effect of revegetation method, species, plant functional traits, and the potential effect of site-specific effect moderators. Overall, we will provide a continental-scale estimate on the seeding vs. planting dilemma and analyse to what extent the differences in environmental conditions across sites, seed size, functional traits, and the phylogenetic relatedness of species can account for the differences in the effect of revegetation method on seedling performance across study sites and species.

Unveiling the Electronic Structure of the Bi(+1)/Bi(+3) Redox Couple on NCN and NNN Pincer Complexes.

Low-valent group 15 compounds stabilized by pincer ligands have gained particular interest, given their direct access to fine-tune their reactivity by the coordination pattern. Recently, bismuth has been employed in a variety of catalytic transformations by taking advantage of the (+1/+3) redox couple. In this work, we present a detailed quantum-chemical study on the electronic structure of bismuth pincer complexes from two different families, namely, bis(ketimine)phenyl (NCN) and triamide bismuthinidene (NNN). The use of the so-called effective oxidation state analysis allows the unambiguous assignation of the bismuth oxidation state. In contrast to previous studies, our calculations suggest a Bi(+1) assignation for NCN pincer ligands, while Bi(+3) character is found for NNN pincer complexes. Notably, regardless of its oxidation state, the central bismuth atom disposes of up to two lone pairs for coordinating Lewis acids, as indicated by very high first and second proton affinity values. Besides, the Bi-NNN systems can also accommodate two Lewis base ligands, indicating also ambiphilic behavior. The effective fragment orbital analysis of Bi and the ligand allows monitoring of the intricate electron flow of these processes, revealing the noninnocent nature of the NNN ligand, in contrast with the NCN one. By the dissection of the electron density into effective fragment orbitals, we are able to quantify and rationalize the Lewis base/acid character.