Caracterización fundamental de superficies metálicas a condiciones relevantes para la catálisis

Heterogeneous catalysis involves chemisorption, reactions of chemisorbed species, and desorption of the products formed. The enthalpies and entropies for these elementary steps and their transition states provide the thermodynamic context that allows rigorous interpretations of the rates and selectivities of chemical reactions mediated by surfaces. The measurement of rates and/or thermodynamic properties at conditions relevant for catalysts and in the absence of mass and heat transport limitations are required for the proper reactor and catalyst design. Different challenging examples are provided, in which chemical rates and/or thermodynamic properties are measured under rigorous kinetic or thermodynamic conditions, giving information regarding the nature of the active metal surfaces and their role at reaction conditions. Among the cases to be presented are the alkane oxidation reactions on noble metals, Pd-PdO phase transition and its consequences for catalysis, and the surface characterization of metals by H2 chemisorption at elevated temperatures. Alkane-O2 (CH4 and C2H6) reactions are highly exothermic and tend to occur within the length scale of conductive or convective heat and mass transfer, which lead to severe gradients within undiluted catalyst pellets and reactors. Extensive dilution within the pellets and reactor has been used to get kinetic and isotopic data for Alkane-O2 reactions on supported Pt, Rh and Pd. These data have shown that CO and H2 do not form via direct alkane partial oxidation but instead via sequential combustion-reforming pathways. Alkane-O2 reactants form CO2 and H2O on Pt in three kinetic regimes (KR), each with distinct rate equations, kinetically-relevant steps, most abundant surface intermediates (MASI), and cluster size effects. Transitions among these regimes are determined by the prevalent steady-state coverages of chemisorbed oxygen (O*), which are given by O2 pressure when O2 dissociation is equilibrated and by O2 to Alkane ratios when it is irreversible. Mechanistic interpretations remain valid for other metals such as Pd, and the difference in reactivity among metals is correlated to O* binding strengths when O* is involved in the kinetically-relevant steps. On Pd and Rh, however, the clusters undergo phase transition to PdO and RhO2, leading to an additional kinetic regime characterized by an abrupt increase in reactivity caused by the transition from metal to oxide. Ex-situ O2 uptake measurements, at equilibrium, were performed to correlate the oxygen content during the phase transition with the measured rates at reaction conditions. Another example is given by the use of dissociative H2 chemisorption methods at conditions relevant for catalysis as a thermodynamic probe instead of mere site counting technique, in which differential enthalpies and entropies of adsorption are obtain to probe the non-uniformity of cluster surfaces. H-atoms formed via H2 dissociation are attractive titrants because of the reversible nature of the adsorption processes and the well-defined adsorption stoichiometry, but also because of the ubiquitous involvement of H-atoms in hydrogenation-dehydrogenation catalysis.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Hacia la diversificación energética: Bioenergía

La apuesta por la sostenibilidad, el aumento de la producción interna, la exploración de otras fuentes de energía y, en la medida de lo posible, la conservación de recursos son una receta a tener en cuenta para reducir facotres como la contaminación y evitar además la excesiva dependencia externa

¿Qué evalúan los instrumentos de evaluación?. Valoraciones de estudiantes

The instruments used for information gathering provide the information to assess whether students have achieved the competences set out in the training plan. Therefore, knowing how they understand and describe the capabilities and skills they are demonstrating is useful information to be considered at times of change and curriculum restructuring.&#13; In this paper we describe the results of study in which students describe what is involved in each of the assessment techniques they have undergone during their undergraduate studies and what skills were used in each case. With this information, we have tried to organise the types of tools to collect information with skills developed from the perceptions of students, presenting a continuum of cognitive abilities.<br><br>Los instrumentos empleados para la recogida de información aportan la información para evaluar si se han logrado las competencias previstas en un plan formativo. Por ello, conocer cómo entienden y describen los estudiantes las capacidades y destrezas que están demostrando en ellos, es una información a tener en cuenta en momentos de cambio y reestructuraciones de los planes de estudio.&#13; &#13; En este artículo mostramos los resultados obtenidos en una investigación, en la que los estudiantes describen qué implica cada una de las técnicas de evaluación que han realizado a lo largo de sus estudios de licenciatura y qué destrezas debían emplear en cada una de ellas. Con la información recogida, hemos intentado organizar las tipologías de instrumentos de recogida de información con las capacidades desarrolladas desde las percepciones de los estudiantes, presentando un continuo de habilidades cognitivas

Hacia la diversificación energética: Bioenergía

La apuesta por la sostenibilidad, el aumento de la producción interna, la exploración de otras fuentes de energía y, en la medida de lo posible, la conservación de recursos son una receta a tener en cuenta para reducir facotres como la contaminación y evitar además la excesiva dependencia externa

Mujeres y escritoras no canónicas de la literatura española e hispanoamericana: Fuentes bibliográficas para su didáctica e investigación en formato digital

Repositorio abierto de editoras y escritoras de la literatura española e hispanoamericana no canónicas, con fuentes de información bibliográficas necesarias para su investigación y su didáctica en las aulas.Depto. de Literaturas Hispánicas y BibliografíaFac. de FilologíaFALSEsubmitte

Non-motor symptoms burden, mood, and gait problems are the most significant factors contributing to a poor quality of life in non-demented Parkinson's disease patients: Results from the COPPADIS Study Cohort

[Objective] To identify factors related to a poor health-related and global quality of life (QoL) in a cohort of non-demented Parkinson's disease (PD) patients and compare to a control group.[Methods] The data correspond to the baseline evaluation of the COPPADIS-2015 Study, an observational, 5-year follow-up, multicenter, evaluation study. Three instruments were used to assess QoL: (1) the 39-item Parkinson's disease Questionnaire (PDQ-39), (2) a subjective rating of global QoL (PQ-10), and (3) the EUROHIS-QOL 8-item index (EUROHIS-QOL8). Multiple linear regression methods were used to evaluate the direct impact of different variables on these QoL measures.[Results] QoL was worse in PD patients (n = 692; 62.6 ± 8.9 years old, 60.3% males) than controls (n = 206; 61 ± 8.3 years old, 49.5% males): PDQ-39, 17.1 ± 13.5 vs 4.4 ± 6.3 (p < 0.0001); PQ-10, 7.3 ± 1.6 vs 8.1 ± 1.2 (p < 0.0001); EUROHIS-QOL8, 3.8 ± 0.6 vs 4.2 ± 0.5 (p < 0.0001). A high correlation was observed between PDQ-39 and Non-Motor Symptoms Scale (NMSS) (r = 0.72; p < 0.0001), and PDQ-39 and Beck Depression Inventory-II (BDI-II) (r = 0.65; p < 0.0001). For health-related QoL (PDQ-39), non-motor symptoms burden (NMSS), mood (BDI-II), and gait problems (Freezing Of Gait Questionnaire [FOGQ]) provided the highest contribution to the model (β = 0.32, 0.28, and 0.27, respectively; p < 0.0001); whereas mood and gait problems contributed the most to global QoL (PQ-10, β = -0.46 and −0.21, respectively; EUROHIS-QOL8, β = -0.44 and −0.23, respectively).[Conclusions] QoL is worse in PD patients than in controls. Mood, non-motor symptoms burden, and gait problems seem to be the most relevant factors affecting health-related and global perceived QoL in non-demented PD patients.Peer reviewe

Clinical and genetic characteristics of late-onset Huntington's disease

Background: The frequency of late-onset Huntington's disease (&gt;59 years) is assumed to be low and the clinical course milder. However, previous literature on late-onset disease is scarce and inconclusive. Objective: Our aim is to study clinical characteristics of late-onset compared to common-onset HD patients in a large cohort of HD patients from the Registry database. Methods: Participants with late- and common-onset (30–50 years)were compared for first clinical symptoms, disease progression, CAG repeat size and family history. Participants with a missing CAG repeat size, a repeat size of ≤35 or a UHDRS motor score of ≤5 were excluded. Results: Of 6007 eligible participants, 687 had late-onset (11.4%) and 3216 (53.5%) common-onset HD. Late-onset (n = 577) had significantly more gait and balance problems as first symptom compared to common-onset (n = 2408) (P &lt;.001). Overall motor and cognitive performance (P &lt;.001) were worse, however only disease motor progression was slower (coefficient, −0.58; SE 0.16; P &lt;.001) compared to the common-onset group. Repeat size was significantly lower in the late-onset (n = 40.8; SD 1.6) compared to common-onset (n = 44.4; SD 2.8) (P &lt;.001). Fewer late-onset patients (n = 451) had a positive family history compared to common-onset (n = 2940) (P &lt;.001). Conclusions: Late-onset patients present more frequently with gait and balance problems as first symptom, and disease progression is not milder compared to common-onset HD patients apart from motor progression. The family history is likely to be negative, which might make diagnosing HD more difficult in this population. However, the balance and gait problems might be helpful in diagnosing HD in elderly patients

Global variation in postoperative mortality and complications after cancer surgery: a multicentre, prospective cohort study in 82 countries

© 2021 The Author(s). Published by Elsevier Ltd. This is an Open Access article under the CC BY-NC-ND 4.0 licenseBackground: 80% of individuals with cancer will require a surgical procedure, yet little comparative data exist on early outcomes in low-income and middle-income countries (LMICs). We compared postoperative outcomes in breast, colorectal, and gastric cancer surgery in hospitals worldwide, focusing on the effect of disease stage and complications on postoperative mortality. Methods: This was a multicentre, international prospective cohort study of consecutive adult patients undergoing surgery for primary breast, colorectal, or gastric cancer requiring a skin incision done under general or neuraxial anaesthesia. The primary outcome was death or major complication within 30 days of surgery. Multilevel logistic regression determined relationships within three-level nested models of patients within hospitals and countries. Hospital-level infrastructure effects were explored with three-way mediation analyses. This study was registered with ClinicalTrials.gov, NCT03471494. Findings: Between April 1, 2018, and Jan 31, 2019, we enrolled 15 958 patients from 428 hospitals in 82 countries (high income 9106 patients, 31 countries; upper-middle income 2721 patients, 23 countries; or lower-middle income 4131 patients, 28 countries). Patients in LMICs presented with more advanced disease compared with patients in high-income countries. 30-day mortality was higher for gastric cancer in low-income or lower-middle-income countries (adjusted odds ratio 3·72, 95% CI 1·70–8·16) and for colorectal cancer in low-income or lower-middle-income countries (4·59, 2·39–8·80) and upper-middle-income countries (2·06, 1·11–3·83). No difference in 30-day mortality was seen in breast cancer. The proportion of patients who died after a major complication was greatest in low-income or lower-middle-income countries (6·15, 3·26–11·59) and upper-middle-income countries (3·89, 2·08–7·29). Postoperative death after complications was partly explained by patient factors (60%) and partly by hospital or country (40%). The absence of consistently available postoperative care facilities was associated with seven to 10 more deaths per 100 major complications in LMICs. Cancer stage alone explained little of the early variation in mortality or postoperative complications. Interpretation: Higher levels of mortality after cancer surgery in LMICs was not fully explained by later presentation of disease. The capacity to rescue patients from surgical complications is a tangible opportunity for meaningful intervention. Early death after cancer surgery might be reduced by policies focusing on strengthening perioperative care systems to detect and intervene in common complications. Funding: National Institute for Health Research Global Health Research Unit

Effects of hospital facilities on patient outcomes after cancer surgery: an international, prospective, observational study

© 2022 The Author(s). Published by Elsevier Ltd. This is an Open Access article under the CC BY 4.0 licenseBackground: Early death after cancer surgery is higher in low-income and middle-income countries (LMICs) compared with in high-income countries, yet the impact of facility characteristics on early postoperative outcomes is unknown. The aim of this study was to examine the association between hospital infrastructure, resource availability, and processes on early outcomes after cancer surgery worldwide. Methods: A multimethods analysis was performed as part of the GlobalSurg 3 study—a multicentre, international, prospective cohort study of patients who had surgery for breast, colorectal, or gastric cancer. The primary outcomes were 30-day mortality and 30-day major complication rates. Potentially beneficial hospital facilities were identified by variable selection to select those associated with 30-day mortality. Adjusted outcomes were determined using generalised estimating equations to account for patient characteristics and country-income group, with population stratification by hospital. Findings: Between April 1, 2018, and April 23, 2019, facility-level data were collected for 9685 patients across 238 hospitals in 66 countries (91 hospitals in 20 high-income countries; 57 hospitals in 19 upper-middle-income countries; and 90 hospitals in 27 low-income to lower-middle-income countries). The availability of five hospital facilities was inversely associated with mortality: ultrasound, CT scanner, critical care unit, opioid analgesia, and oncologist. After adjustment for case-mix and country income group, hospitals with three or fewer of these facilities (62 hospitals, 1294 patients) had higher mortality compared with those with four or five (adjusted odds ratio [OR] 3·85 [95% CI 2·58–5·75]; p<0·0001), with excess mortality predominantly explained by a limited capacity to rescue following the development of major complications (63·0% vs 82·7%; OR 0·35 [0·23–0·53]; p<0·0001). Across LMICs, improvements in hospital facilities would prevent one to three deaths for every 100 patients undergoing surgery for cancer. Interpretation: Hospitals with higher levels of infrastructure and resources have better outcomes after cancer surgery, independent of country income. Without urgent strengthening of hospital infrastructure and resources, the reductions in cancer-associated mortality associated with improved access will not be realised. Funding: National Institute for Health and Care Research