Photocatalytic activity enhancement of two-step and one-pot synthesis of Pd/ZnO nanocomposites: an experimental and DFT study.

Pd/ZnO nanocomposites were successfully synthesized by means of one and two pot synthesis and applied in the photodegradation of Rh6G. The nanocomposites were characterized by XRD, SEM, TEM, FTIR and micro-Raman spectroscopies. It was found the presence of PdZn2, PdO and agglomerated particles in the support surface for the Palladium-based nanocomposites fabricated by one-pot route; the two-step method allowed the formation of spherical Pd nanoparticles, with homogeneous distribution in the nanocomposite matrix, with an average size of 2.16 nm. The results show higher photocatalytic efficiency for the samples fabricated under the two-step approach compared to the one-pot synthesis. Based on experimental results, density functional theory (DFT) calculations were carried out to understand the enhancement photocatalytic of Pd/ZnO nanocomposites. To achieve it, the ZnO (001) and (101) surfaces were built and decorated by different Pd coverages. The theoretical results indicated two different photocatalytic mechanisms. In ZnO (001) case, the electrons flowed from surface to Pd, generating the superoxide radical anion (⋅O2-). Furthermore, the density of states of the ZnO (001) surface was modified by impurity Pd-d states at proximity to the conduction states, which may work as electron acceptors states. On the other hand, we found that the electrons flow from Pd to ZnO (101) surface, inducing the formation of ⋅OH and ⋅O2- for the degradation of Rh6G. The density of states of the ZnO (101) revealed a reduction in its bandgap, due to Pd-d states localized above valence states. Hence, our theoretical results suggest that the Pd-d states may facilitate the mobility of electrons and holes in (001) and (101) surfaces, respectively, reducing the rate of charge recombination.

Validation of machine-learning model for first-trimester prediction of pre-eclampsia using cohort from PREVAL study.

OBJECTIVE: Effective first-trimester screening for pre-eclampsia (PE) can be achieved using a competing-risks model that combines risk factors from the maternal history with multiples of the median (MoM) values of biomarkers. A new model using artificial intelligence through machine-learning methods has been shown to achieve similar screening performance without the need for conversion of raw data of biomarkers into MoM. This study aimed to investigate whether this model can be used across populations without specific adaptations. METHODS: Previously, a machine-learning model derived with the use of a fully connected neural network for first-trimester prediction of early (< 34 weeks), preterm (< 37 weeks) and all PE was developed and tested in a cohort of pregnant women in the UK. The model was based on maternal risk factors and mean arterial blood pressure (MAP), uterine artery pulsatility index (UtA-PI), placental growth factor (PlGF) and pregnancy-associated plasma protein-A (PAPP-A). In this study, the model was applied to a dataset of 10 110 singleton pregnancies examined in Spain who participated in the first-trimester PE validation (PREVAL) study, in which first-trimester screening for PE was carried out using the Fetal Medicine Foundation (FMF) competing-risks model. The performance of screening was assessed by examining the area under the receiver-operating-characteristics curve (AUC) and detection rate (DR) at a 10% screen-positive rate (SPR). These indices were compared with those derived from the application of the FMF competing-risks model. The performance of screening was poor if no adjustment was made for the analyzer used to measure PlGF, which was different in the UK and Spain. Therefore, adjustment for the analyzer used was performed using simple linear regression. RESULTS: The DRs at 10% SPR for early, preterm and all PE with the machine-learning model were 84.4% (95% CI, 67.2-94.7%), 77.8% (95% CI, 66.4-86.7%) and 55.7% (95% CI, 49.0-62.2%), respectively, with the corresponding AUCs of 0.920 (95% CI, 0.864-0.975), 0.913 (95% CI, 0.882-0.944) and 0.846 (95% CI, 0.820-0.872). This performance was achieved with the use of three of the biomarkers (MAP, UtA-PI and PlGF); inclusion of PAPP-A did not provide significant improvement in DR. The machine-learning model had similar performance to that achieved by the FMF competing-risks model (DR at 10% SPR, 82.7% (95% CI, 69.6-95.8%) for early PE, 72.7% (95% CI, 62.9-82.6%) for preterm PE and 55.1% (95% CI, 48.8-61.4%) for all PE) without requiring specific adaptations to the population. CONCLUSIONS: A machine-learning model for first-trimester prediction of PE based on a neural network provides effective screening for PE that can be applied in different populations. However, before doing so, it is essential to make adjustments for the analyzer used for biochemical testing. © 2023 International Society of Ultrasound in Obstetrics and Gynecology.

Biochar as a sustainable alternative to carbon black in agricultural mulch films.

Examples of biochar as an alternative to traditional plastic fillers, like carbon black, are numerous and growing. However, in the agricultural mulch film application, both the polymer and its fillers are pushed to their mechanical limit to obtain an effective product, using the least amount of plastic. Through a combined techno-economic analysis (TEA) and life cycle assessment (LCA), this study characterizes the use of carbon-negative biochar as an opacity filler in mulch film applications. Due to its larger particle size, the biochar demands additional thickness to achieve equivalent opacity as carbon black in films. A thicker film translates to additional polymer demand, and a significant increase in price and environmental impact. A comparable formulation for an equal price ($623 per mulched ha) as a 2.6 wt % carbon black with 25 µm thickness was derived, needing 15 wt % biochar and a thickness of 30 µm. The biochar formulation resulted in a slightly higher global warming potential (3% increase), but much larger impact in the land use category (+339%), and the sample was deemed not fit for use in the intended mulch application. These results indicate that in applications where the polymeric matrix and its fillers are pushed to their mechanical limit, the displacement of traditional fillers by biochar is challenging. However, biochar derived from waste biomass (thus reducing land use impact) remains a valid, environmentally beneficial solution to displace traditional fillers for non-extreme plastic uses (commodity plastics) and thicker composites.

Are farmers motivated to select for heat tolerance? Linking attitudinal factors, perceived climate change impacts, and social trust to farmers' breeding desires.

This study provides an understanding of dairy farmers' willingness to include heat tolerance in breeding goals and the modulating effect of sociopsychological factors and farm profile. A survey instrument including a choice experiment was designed to specifically address the trade-off between heat tolerance and milk production level. A total of 122 farmers across cattle, goat, and sheep farms were surveyed face-to-face. The results of the experiment show that most farmers perceive that heat stress and climate change are increasingly important problems, and that farming communities should invest more in generating knowledge and resources on mitigation strategies. However, we found limited initial support for selection for heat tolerance. This attitude changed when farmers were presented with objective information on the benefits and limitations of the different breeding choices, after which most farmers supported selection for heat tolerance, but only if doing so would compromise milk production gains to a small extent. Our results show that farmers' selection choices are driven by the interactions between heat stress risk perception, attitudes toward breeding tools, social trust, the species reared, and farm production level. In general, farmers willing to support selection of heat-tolerant animals are those with positive attitudes toward genetic values and genomic information and a strong perception of climate change and heat stress impacts on farms. On the contrary, negative support for selection for heat tolerance is found among farmers with high milk production levels; high trust in farming magazines, livestock farmers' associations, and veterinarians; and low trust in environmental and animalist groups.

Adsorption of Ciprofloxacin on Clay Minerals in Argentinian Santa Rosa-Corrientes Soils.

The presence of antibiotics in soils is increasing drastically in last decades due to the intensive farming industry and excessive human consumption. Clay minerals are one of the soil components with great adsorption capacity for organic pollutants. The study of interactions between antibiotics and mineral surfaces will give us scientific knowledge of these pollutants through soils. In this work, we study the adsorption of the antibiotic ciprofloxacin in the clay mineral fraction of soils from the Argentinian zone of Santa Rosa (Corrientes), in a collaborative research of experiments and atomistic modelling calculations of the intercalation of ciprofloxacin in the interlayer space of montmorillonite. Adsorption and desorption isotherms were performed and compared with different isotherm models. Additionally, enthalpy, entropy, and free energy were determined from equilibrium constants at a function of temperature. All these experiments and calculations lead to the conclusions that two adsorption types of ciprofloxacin are found on clay minerals: one weakly sorbed that is released during the desorption experiments, and other one strongly joined that remains in the soil.

A microfluidic labyrinth self-assembled by a chemical garden.

Chemical gardens, self-assembling precipitates that spontaneously form when a metal salt is added to a solution of another precipitating anion, are of interest for various applications including producing reactive materials in controlled structures. Here, we report on two chemical garden reaction systems (CuCl2 and Cu(NO3)2 seed crystals submerged in sodium silicate) that produced self-assembled microfluidic labyrinths in a vertical 2D Hele-Shaw reactor. The formation of labyrinths as well as the specific growth modes of the precipitate were dependent on the silicate concentration: CuCl2 labyrinths formed only at 3 and 4 M silicate and Cu(NO3)2 labyrinths formed only at 4 and 5 M silicate. The labyrinth structures contained silicate on the exterior and crystalline material interpreted as hydrated minerals from the metal salt in their interiors. The bubble-guided tubes that form labyrinths can be controlled by changing the angle of the 2D reaction cell; this suggests that future experiments of this type could form self-organizing structures with controlled composition and orientation for use in microfluidics and various materials science applications.

Prevalence, risk factors and evolution of diabetes mellitus after treatment in primary aldosteronism. Results from the SPAIN-ALDO registry.

PURPOSE: To evaluate the prevalence, risk factors and evolution of diabetes mellitus (DM) after targeted treatment in patients with primary aldosteronism (PA). METHODS: A retrospective multicenter study of PA patients in follow-up at 27 Spanish tertiary hospitals (SPAIN-ALDO Register). RESULTS: Overall, 646 patients with PA were included. At diagnosis, 21.2% (n = 137) had DM and 67% of them had HbA1c levels < 7%. In multivariate analysis, family history of DM (OR 4.00 [1.68-9.53]), the coexistence of dyslipidemia (OR 3.57 [1.51-8.43]) and advanced age (OR 1.04 per year of increase [1.00-1.09]) were identified as independent predictive factors of DM. Diabetic patients were on beta blockers (46.7% (n = 64) vs. 27.5% (n = 140), P < 0.001) and diuretics (51.1% (n = 70) vs. 33.2% (n = 169), p < 0.001) more frequently than non-diabetics. After a median follow-up of 22 months [IQR 7.5-63.0], 6.9% of patients developed DM, with no difference between those undergoing adrenalectomy and those treated medically (HR 1.07 [0.49-2.36], p = 0.866). There was also no significant difference in the evolution of glycemic control between DM patients who underwent surgery and those medically treated (p > 0.05). CONCLUSION: DM affects about one quarter of patients with PA and the risk factors for its development are common to those of the general population. Medical and surgical treatment provides similar benefit in glycemic control in patients with PA and DM.

Cognitive outcomes following functional neurosurgery in refractory OCD patients: a systematic review.

Neurosurgery is a therapeutic option for patients with refractory obsessive-compulsive disorder who do not respond to previous treatments. Although its efficacy in reducing clinical symptomatology has been proven, few studies have analyzed its effects at the cognitive level. The aim of this systematic review was to describe the cognitive outcomes of functional neurosurgery in patients that went through capsulotomies or cingulotomies. PubMed, Medline, Scopus, PsycInfo, PsyArticles, and Web of Knowledge were searched for studies reporting cognitive outcomes in refractory obsessive-compulsive patients after capsulotomies and cingulotomies. The risk of bias was assessed with the Assessment Tool for Before-After (Pre-Post) Studies With No Control Group tool; 13 studies met inclusion criteria, including 205 refractory obsessive-compulsive disorder patients for both surgical procedures. Results showed a substantial number of studies that did report significant cognitive improvement after surgery, being this improvement specially related to memory and executive functions. The second-most frequent finding is the maintenance of cognitive performance (nor improvement or worsening). From a neuropsychological point of view, this outcome might be considered a success, given that it is accompanied by amelioration of obsessive-compulsive symptoms. Subtle cognitive adverse effects have also been reported. Neurosurgery procedures appear to be safe from a cognitive point of view. Methodological issues must be improved to draw clearer conclusions, but capsulotomies and cingulotomies constitute an effective alternative treatment for refractory obsessive-compulsive disorder patients.

Clinical Conundrum: Spontaneous Paravaginal Venous Plexus Thrombosis Presenting as Acute Lower Pelvic Pain.

Acute pelvic pain due to venous thrombosis can be encountered in the context of pelvic congestion syndrome. Some vascular anomalies such as nutcracker syndrome or May-Thurner syndrome may cause left ovarian vein or left iliofemoral vein thrombosis. Smaller parametrial or paravaginal vein thrombi have rarely been reported as aetiologies of acute pelvic pain. We present a case of spontaneous paravaginal venous plexus thrombosis presenting as acute lower pelvic pain in which thrombophilia was diagnosed. Small vein thrombosis or an unusual location of thrombus should prompt vascular studies and a thrombophilia work-up.

Psychological and functional impacts associated with restrictions in long-term care facilities (LTCF) due to the COVID-19 pandemic: A multicentre study.

Objectives: To analyze the impacts of the restrictions implemented in LTCF during the COVID-19 pandemic on the psychological and functional status of older adults. Design: A retrospective multicentre study is designed. We hypothesize that the negative effects of the restrictions will lead to a higher rate of decline between the measures taken immediately before and after the lockdown than between the two measures taken before the lockdown. Setting and participants: 365 participants recruited in four Spanish LTCFs in Galicia and Valencia.Methods: Impacts of restrictions on cognitive (MMSE), affective (GDS) and functional status (Barthel index, Tinetti) were analyzed by Linear Mixed Models with random intercepts, random slopes, and personal and contextual factors as covariates.Results: Social measures covaried significantly with the cognitive and functional status but did not predict longitudinal change. MMSE, Barthel index and Tinetti scores decreased significantly across pre- and post-lockdown measurement times, but only the Tinetti scores showed a specific impact of the restrictions.Conclusions: Only performance-based functional measures showed the real impact of restrictions. The findings highlight the importance of having data from several pre-lockdown measurements to enable identification of changes that can be causally attributed to the restrictions. The findings also support the resilience of older adults in mitigating the effect of the restrictions.

Doublecortin mutation leads to persistent defects in the Golgi apparatus and mitochondria in adult hippocampal pyramidal cells.

Human doublecortin (DCX) mutations are associated with severe brain malformations leading to aberrant neuron positioning (heterotopia), intellectual disability and epilepsy. DCX is a microtubule-associated protein which plays a key role during neurodevelopment in neuronal migration and differentiation. Dcx knockout (KO) mice show disorganized hippocampal pyramidal neurons. The CA2/CA3 pyramidal cell layer is present as two abnormal layers and disorganized CA3 KO pyramidal neurons are also more excitable than wild-type (WT) cells. To further identify abnormalities, we characterized Dcx KO hippocampal neurons at subcellular, molecular and ultrastructural levels. Severe defects were observed in mitochondria, affecting number and distribution. Also, the Golgi apparatus was visibly abnormal, increased in volume and abnormally organized. Transcriptome analyses from laser microdissected hippocampal tissue at postnatal day 60 (P60) highlighted organelle abnormalities. Ultrastructural studies of CA3 cells performed in P60 (young adult) and > 9 months (mature) tissue showed that organelle defects are persistent throughout life. Locomotor activity and fear memory of young and mature adults were also abnormal: Dcx KO mice consistently performed less well than WT littermates, with defects becoming more severe with age. Thus, we show that disruption of a neurodevelopmentally-regulated gene can lead to permanent organelle anomalies contributing to abnormal adult behavior.

The Effect of the Presence of Amino Acids on the Precipitation of Inorganic Chemical-Garden Membranes: Biomineralization at the Origin of Life.

If life developed in hydrothermal vents, it would have been within mineral membranes. The first proto-cells must have evolved to manipulate the mineral membranes that formed their compartments in order to control their metabolism. There must have occurred a biological takeover of the self-assembled mineral structures of the vents, with the incorporation of proto-biological molecules within the mineral membranes to alter their properties for life's purposes. Here, we study a laboratory analogue of this process: chemical-garden precipitation of the amino acids arginine and tryptophan with the metal salt iron chloride and sodium silicate. We produced these chemical gardens using different methodologies in order to determine the dependence of the morphology and chemistry on the growth conditions, as well as the effect of the amino acids on the formation of the iron-silicate chemical garden. We compared the effects of having amino acids initially within the forming chemical garden, corresponding to the internal zones of hydrothermal vents, or else outside, corresponding to the surrounding ocean. The characterization of the formed chemical gardens using X-ray diffraction, Fourier transform infrared spectroscopy, elemental analysis, and scanning electron microscopy demonstrates the presence of amino acids in these structures. The growth method in which the amino acid is initially in the tablet with the iron salt is that which generated chemical gardens with more amino acids in their structures.

Crystal polymorphism and spectroscopical properties of sulfonamides in solid state by means of First Principles calculations.

Sulfonamides are an important class of therapeutic agents. The increase in the number of new sulfonamide derivatives makes it necessary to study more rationally the chemical structure, because the solid forms often display different mechanical, thermal and physicochemical properties that can influence the bioavailability and stability of the drugs; consequently, the polymorphic structures are of great interest to the pharmaceutical industry because of their ability to modify the physical properties of the active pharmaceutical ingredient. The molecular interactions of these drugs in their crystal lattice are important for the stability of the crystals and polymorphism and for preparing composite complexes for optimizing the use of these drugs. In this work, the crystal structure of these drugs and crystal polymorphism is investigated. So, the crystal forms of antibiotics derivatives of the sulfonamides, sulfamethoxazole, sulfamethazine, sulfachloropyridazine, and sulfacetamide are studied at the molecular and supramolecular level by using computational modeling approach at quantum mechanical level. The spectroscopic properties of these systems are also studied explaining assignments of previous experimental data. The results of DFT calculations reproduce the crystal structures of sulfonamides determined experimentally and the polymorphism in these molecules have been clarified. Likewise, the main intermolecular interactions in all crystal forms of these sulfonamides are H-bonds among the sulfonic and amino groups and SNH groups, and also some π-π interactions. Also, these 3-D periodical models allow the exploration of the intermolecular interactions included in the crystal structures and some of these interactions can alter the vibration modes of the molecules. Therefore, the use of these models can be useful for experimental spectroscopy studies where use actual crystal solids.

Stereodynamics effects in grazing-incidence fast-molecule diffraction.

Grazing-incidence fast-projectile diffraction has been proposed both as a complement and an alternative to thermal-energy projectile scattering, which explains the interest that this technique has received in recent years, especially in the case of atomic projectiles. On the other hand, despite the richer physics involved, molecular projectiles have received much less attention. In this work, we present a theoretical study of grazing-incidence fast-molecule diffraction of H2 from KCl(001) using a six-dimensional density functional theory based potential energy surface and a time-dependent wavepacket propagation method. The analysis of the computed diffraction patterns as a function of the molecular alignment, and their comparison with the available experimental data, where the initial distribution of rotational states in the molecule is not known, reveals a puzzling stereodynamics effect of the diffracted projectiles: diffracted molecules aligned perpendicular, or quasi perpendicular, to the surface reproduce rather well the experimental diffraction pattern, whereas those molecules aligned parallel to or tilted with respect to the surface do not behave as in the experiments. These results call for more detailed investigations of the molecular beam generation process.

Downward fingering accompanies upward tube growth in a chemical garden grown in a vertical confined geometry.

Chemical gardens are self-assembled structures of mineral precipitates enabled by semi-permeable membranes. To explore the effects of gravity on the formation of chemical gardens, we have studied chemical gardens grown from cobalt chloride pellets and aqueous sodium silicate solution in a vertical Hele-Shaw cell. Through photography, we have observed and quantitatively analysed upward growing tubes and downward growing fingers. The latter were not seen in previous experimental studies involving similar physicochemical systems in 3-dimensional or horizontal confined geometry. To better understand the results, further studies of flow patterns, buoyancy forces, and growth dynamics under schlieren optics have been carried out, together with characterisation of the precipitates with scanning electron microscopy and X-ray diffractometry. In addition to an ascending flow and the resulting precipitation of tubular filaments, a previously not reported descending flow has been observed which, under some conditions, is accompanied by precipitation of solid fingering structures. We conclude that the physics of both the ascending and descending flows are shaped by buoyancy, together with osmosis and chemical reaction. The existence of the descending flow might highlight a limitation in current experimental methods for growing chemical gardens under gravity, where seeds are typically not suspended in the middle of the solution and are confined by the bottom of the vessel.

Association Between the Seed Storage Proteins 2S Albumin and 11S Globulin and Severe Allergic Reaction After Flaxseed Intake.

BACKGROUND: Given the increased popularity of flaxseed in meals, several cases of allergy to these seeds have been reported. Little is known about the allergens implicated in hypersensitivity reactions to flaxseed. The present study aimed to identify the allergens involved in IgE-mediated reactions in 5 patients with a clinical history of severe systemic symptoms after flaxseed consumption. METHODS: Proteins that were potential allergens with IgE-binding capacity were purified from flaxseed extract using chromatography and identified via MALDI-TOF mass spectrometry. Immunoassays were performed using the 5 allergic patients' sera tested individually and as a pool. RESULTS: Immunoblotting of the flaxseed extract revealed a low-molecular-mass protein (around 13 kDa) in 4 of the 5 patients, while a protein of approximately 55 kDa was detected in 2 patients. The proteins were identified by mass spectrometry as flaxseed 2S albumin, which is included in the WHO/IUIS allergen nomenclature as Lin u 1, and 11S globulin. Inhibition assays revealed in vitro IgE-mediated cross-reactivity between Lin u 1 and peanut and cashew nut proteins, while IgE-mediated recognition of 11S globulin by patients' sera was partially inhibited by several plant-derived sources. CONCLUSIONS: Seed storage proteins from flaxseed were involved in the development of severe symptoms in the 5 patients studied and exhibited cross-reactivity with other allergenic sources. Besides the severity of flaxseed allergy in patients sensitized to 2S albumin, this is the first time that 11S globulin has been identified as a potential allergen. Taking these data into account should ensure a more accurate diagnosis.

Unraveling the Diagnosis of Kiwifruit Allergy: Usefulness of Current Diagnostic Tests.

OBJECTIVES: To determine the usefulness of the in vitro and in vivo methods used in the diagnosis of kiwifruit allergy and to specifically assess the impact of seed proteins on sensitivity. METHODS: We performed skin prick tests (SPTs) using various commercial extracts, homemade pulp, and seed extracts and prick-prick tests with kiwifruit on 36 allergic patients. The presence of specific IgE (sIgE) was assessed using the ImmunoCAP (kiwifruit extract), ELISA (Act d 1, Act d 2), ISAC, and FABER assays. Immunoblotting of seed extract was carried out, and a single-blind oral food challenge was performed with whole seeds in seed-sensitized individuals. RESULTS: The prick prick test with kiwifruit demonstrated the highest diagnostic capacity (81.8% sensitivity and 94.1% specificity) among the in vivo tests. The sIgE levels measured using ImmunoCAP (kiwifruit extract) showed a similar sensitivity to that of global ISAC and FABER (63.9%, 59.5%, and 58.3%, respectively). Act d 1 was the major allergen. Sensitization to Act d 1 was associated with positive sIgE results to whole kiwifruit extract detected by ImmunoCAP (P<.000). A positive SPT result to kiwifruit seeds was associated with severe symptoms induced by kiwifruit (P=.019) as a marker of advanced disease, but not with clinically relevant sensitization. Challenge testing with kiwifruit seeds performed on 8 seed-sensitized patients yielded negative results. CONCLUSION: Sensitization to Act d 1 is associated with a positive result in conventional diagnostic techniques, whereas kiwifruit seed sensitization does not increase the sensitivity of the diagnostic techniques evaluated.

What mediates the racial/ethnic disparity in psychosocial stress among breast cancer patients?

BACKGROUND: Prior studies have observed greater levels of psychosocial stress (PSS) among non-Hispanic (nH) African American and Hispanic women when compared to nH White patients after a breast cancer diagnosis. We aimed to determine the independent and interdependent roles of socioeconomic position (SEP) and unmet support in the racial disparity in PSS among breast cancer patients. METHODS: Participants were recruited from the Breast Cancer Care in Chicago study (n = 989). For all recently diagnosed breast cancer patients, aged 25-79, income, education, and tract-level disadvantage and affluence were summed to create a standardized socioeconomic position (SEP) score. Three measures of PSS related to loneliness, perceived stress, and psychological consequences of a breast cancer diagnosis were defined based on previously validated scales. Five domains of unmet social support needs (emotional, spiritual, informational, financial, and practical) were defined from interviews. We conducted path models in MPlus to estimate the extent to which PSS disparities were mediated by SEP and unmet social support needs. RESULTS: Black and Hispanic patients reported greater PSS compared to white patients and greater unmet social support needs (p = 0.001 for all domains). Virtually all of the disparity in PSS could be explained by SEP. A substantial portion of the mediating influence of SEP was further transmitted by unmet financial and practical needs among Black patients and by unmet emotional needs for Hispanic patients. CONCLUSIONS: SEP appeared to be a root cause of the racial/ethnic disparities in PSS within our sample. Our findings further suggest that different interventions may be necessary to alleviate the burden of SEP for nH AA (i.e., more financial support) and Hispanic patients (i.e., more emotional support).

Analysis of outcomes of emergency general and gastrointestinal surgery during the COVID-19 pandemic.

BACKGROUND: Few surgical studies have provided adjusted comparative postoperative outcome data among contemporary patients with and without COVID-19 infection and patients treated before the pandemic. The aim of this study was to determine the impact of performing emergency surgery in patients with concomitant COVID-19 infection. METHODS: Patients who underwent emergency general and gastrointestinal surgery from March to June 2020, and from March to June 2019 in 25 Spanish hospitals were included in a retrospective study (COVID-CIR). The main outcome was 30-day mortality. Secondary outcomes included postoperative complications and failure to rescue (mortality among patients who developed complications). Propensity score-matched comparisons were performed between patients who were positive and those who were negative for COVID-19; and between COVID-19-negative cohorts before and during the pandemic. RESULTS: Some 5307 patients were included in the study (183 COVID-19-positive and 2132 COVID-19-negative during pandemic; 2992 treated before pandemic). During the pandemic, patients with COVID-19 infection had greater 30-day mortality than those without (12.6 versus 4.6 per cent), but this difference was not statistically significant after propensity score matching (odds ratio (OR) 1.58, 95 per cent c.i. 0.88 to 2.74). Those positive for COVID-19 had more complications (41.5 versus 23.9 per cent; OR 1.61, 1.11 to 2.33) and a higher likelihood of failure to rescue (30.3 versus 19.3 per cent; OR 1.10, 0.57 to 2.12). Patients who were negative for COVID-19 during the pandemic had similar rates of 30-day mortality (4.6 versus 3.2 per cent; OR 1.35, 0.98 to 1.86) and complications (23.9 versus 25.2 per cent; OR 0.89, 0.77 to 1.02), but a greater likelihood of failure to rescue (19.3 versus 12.9 per cent; OR 1.56, 95 per cent 1.10 to 2.19) than prepandemic controls. CONCLUSION: Patients with COVID-19 infection undergoing emergency general and gastrointestinal surgery had worse postoperative outcomes than contemporary patients without COVID-19. COVID-19-negative patients operated on during the COVID-19 pandemic had a likelihood of greater failure-to-rescue than prepandemic controls.

Normal and off-normal incidence dissociative dynamics of O2(v,J) on ultrathin Cu films grown on Ru(0001).

The dissociative adsorption of molecular oxygen on metal surfaces has long been controversial, mostly due to the spin-triplet nature of its ground state, to possible non-adiabatic effects, such as an abrupt charge transfer from the metal to the molecule, or even to the role played by the surface electronic state. Here, we have studied the dissociative adsorption of O2 on CuML/Ru(0001) at normal and off-normal incidence, from thermal to super-thermal energies, using quasi-classical dynamics, in the framework of the generalized Langevin oscillator model, and density functional theory based on a multidimensional potential energy surface. Our simulations reveal a rather intriguing behavior of dissociative adsorption probabilities, which exhibit normal energy scaling at incidence energies below the reaction barriers and total energy scaling above, irrespective of the reaction channel, either direct dissociation, trapping dissociation, or molecular adsorption. We directly compare our results with existing scanning tunneling spectroscopy and microscopy measurements. From this comparison, we infer that the observed experimental behavior at thermal energies may be due to ligand and strain effects, as already found for super-thermal incidence energies.