Efficient Alkyne Semihydrogenation Catalysis Enabled by Synergistic Chemical and Thermal Modifications of a PdIn MOF

[EN] Recently, there has been a growing interest in using MOF templating to synthesize heterogeneous catalysts based on metal nanoparticles on carbonaceous supports. Unlike the common approach of direct pyrolysis of PdIn-MOFs at high temperatures, this work proposes a reductive chemical treatment under mild conditions before pyrolysis (resulting in PdIn-QT). The resulting material (PdIn-QT) underwent comprehensive characterization via state-of-the-art aberration-corrected electron microscopy, N2 physisorption, X-ray absorption spectroscopy, Raman, X-ray photoelectron spectroscopy, and X-ray diffraction. These analyses have proven the existence of PdIn bimetallic nanoparticles supported on N-doped carbon. In situ DRIFT spectroscopy reveals the advantageous role of indium (In) in regulating Pd activity in alkyne semihydrogenation. Notably, incorporating a soft nucleation step before pyrolysis enhances surface area, porosity, and nitrogen content compared to direct MOF pyrolysis. The optimized material exhibits outstanding catalytic performance with 96% phenylacetylene conversion and 96% selectivity to phenylethylene in the fifth cycle under mild conditions (5 mmol phenylacetylene, 7 mg cat, 5 mL EtOH, R.T., 1 H2 bar).The authors thank the financial support from the Spanish Government (RTI2018-096399-A-I00, PID2022-140111OB-I00, PID2020-113006-RB-I00, TED2021-130191B-C41, and TED2021-130191B-C44) funded by MCIN/AEI/10.13039/501100011033. This project has received funding from the European Union's Horizon 2020 research and innovation programme under grant agreement No 101022507 and NextGenerationEU/PRTR). HR-STEM studies were performed at the DME-UCA node of the ELECMI Spanish Unique Infrastructure (ICTS) for Electron Microscopy of Materials. Some of these experiments were performed at CLAESS and NOTOS beamlines at ALBA Synchrotron with the collaboration of ALBA staff (Carlos Escudero, Carlo Marini). J.M. Salas is acknowledged for experimental contributions to FTIR measurements.Martínez, JS.; Mazarío, J.; Wittee Lopes, C.; Trasobares, S.; Calvino Gamez, JJ.; Agostini, G.; Oña-Burgos, P. (2024). Efficient Alkyne Semihydrogenation Catalysis Enabled by Synergistic Chemical and Thermal Modifications of a PdIn MOF. ACS Catalysis. 14(7):4768-4785. https://doi.org/10.1021/acscatal.4c003104768478514

A tandem process for in situ H2O2 formation coupled with benzyl alcohol oxidation using Pd-Au bimetallic catalysts

[EN] Alcohol oxidation is one of the most important industrial organic reactions. Traditionally, the best-suited catalysts are Pd, Pt and Au supported nanoparticles. The research community has recently started developing strategies for synthesizing carbon-supported Pd/Au bimetallic nanoparticles (NPs), leading to higher activities and selectivities. However, the metallic active species in these catalysts are usually generated using sodium borohydride (NaBH4), which is not synthetically easy to reproduce. In fact, minor modifications in pH, concentration and/or other parameters have a prominent effect on the nature of the promoted material. In this work, a robust process involving dihydrogen flow (H2) at 200 °C as a reducing agent for synthesizing Pd/Au supported bimetallic materials was considered an alternative to the common pathway. The physicochemical properties of the materials derived from different reducing reagents and of varying composition ranges were studied using HR-TEM, XRD, CO chemisorption, and XPS. Their stability and activity were also tested for benzyl alcohol oxidation to benzaldehyde under mild reaction conditions (60 °C, water as the solvent, and PO2 = 1.5 bar). Notably, a catalyst from the hydrogen reduction process with a metal composition of 0.8%Pd¿0.2%Au/C consisting of bimetallic clusters (¿1.5 nm) proved to be the best material (C = 94%, S = 99%). Catalytic performances were strongly correlated with structural properties, such as nanoparticle size and distribution, which, in turn, were affected by the reduction step and the metal composition range. Finally, the influence of oxidants on benzyl alcohol oxidation has also been studied, along with the first approach for the tandem in situ formation of H2O2 coupled with alcohol oxidation.The authors are thankful for the financial support by the Spanish Government (RTI2018-096399-A-I00 and PGC2018-097277-B-I00 funded by MICINN/AEI/10.13039/501100011033) and Junta de Andalucia (P20 01027 and PYC 20 RE 060 UAL). The electron microscopy service of the UPV is acknowledged for their help in sample characterization.Martínez, JS.; Mazarío, J.; Gutiérrez-Tarriño, S.; Galdeano-Ruano, CP.; Gaona Miguélez, JA.; Domine, ME.; Oña-Burgos, P. (2022). A tandem process for in situ H2O2 formation coupled with benzyl alcohol oxidation using Pd-Au bimetallic catalysts. Dalton Transactions. 51(46):17567-17578. https://doi.org/10.1039/D2DT02831J1756717578514

Clonal chromosomal mosaicism and loss of chromosome Y in elderly men increase vulnerability for SARS-CoV-2

The pandemic caused by severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2, COVID-19) had an estimated overall case fatality ratio of 1.38% (pre-vaccination), being 53% higher in males and increasing exponentially with age. Among 9578 individuals diagnosed with COVID-19 in the SCOURGE study, we found 133 cases (1.42%) with detectable clonal mosaicism for chromosome alterations (mCA) and 226 males (5.08%) with acquired loss of chromosome Y (LOY). Individuals with clonal mosaic events (mCA and/or LOY) showed a 54% increase in the risk of COVID-19 lethality. LOY is associated with transcriptomic biomarkers of immune dysfunction, pro-coagulation activity and cardiovascular risk. Interferon-induced genes involved in the initial immune response to SARS-CoV-2 are also down-regulated in LOY. Thus, mCA and LOY underlie at least part of the sex-biased severity and mortality of COVID-19 in aging patients. Given its potential therapeutic and prognostic relevance, evaluation of clonal mosaicism should be implemented as biomarker of COVID-19 severity in elderly people. Among 9578 individuals diagnosed with COVID-19 in the SCOURGE study, individuals with clonal mosaic events (clonal mosaicism for chromosome alterations and/or loss of chromosome Y) showed an increased risk of COVID-19 lethality

Varying constants, Gravitation and Cosmology

Fundamental constants are a cornerstone of our physical laws. Any constant varying in space and/or time would reflect the existence of an almost massless field that couples to matter. This will induce a violation of the universality of free fall. It is thus of utmost importance for our understanding of gravity and of the domain of validity of general relativity to test for their constancy. We thus detail the relations between the constants, the tests of the local position invariance and of the universality of free fall. We then review the main experimental and observational constraints that have been obtained from atomic clocks, the Oklo phenomenon, Solar system observations, meteorites dating, quasar absorption spectra, stellar physics, pulsar timing, the cosmic microwave background and big bang nucleosynthesis. At each step we describe the basics of each system, its dependence with respect to the constants, the known systematic effects and the most recent constraints that have been obtained. We then describe the main theoretical frameworks in which the low-energy constants may actually be varying and we focus on the unification mechanisms and the relations between the variation of different constants. To finish, we discuss the more speculative possibility of understanding their numerical values and the apparent fine-tuning that they confront us with.Comment: 145 pages, 10 figures, Review for Living Reviews in Relativit

Penilaian Kinerja Keuangan Koperasi di Kabupaten Pelalawan

This paper describe development and financial performance of cooperative in District Pelalawan among 2007 - 2008. Studies on primary and secondary cooperative in 12 sub-districts. Method in this stady use performance measuring of productivity, efficiency, growth, liquidity, and solvability of cooperative. Productivity of cooperative in Pelalawan was highly but efficiency still low. Profit and income were highly, even liquidity of cooperative very high, and solvability was good

Juxtaposing BTE and ATE – on the role of the European insurance industry in funding civil litigation

One of the ways in which legal services are financed, and indeed shaped, is through private insurance arrangement. Two contrasting types of legal expenses insurance contracts (LEI) seem to dominate in Europe: before the event (BTE) and after the event (ATE) legal expenses insurance. Notwithstanding institutional differences between different legal systems, BTE and ATE insurance arrangements may be instrumental if government policy is geared towards strengthening a market-oriented system of financing access to justice for individuals and business. At the same time, emphasizing the role of a private industry as a keeper of the gates to justice raises issues of accountability and transparency, not readily reconcilable with demands of competition. Moreover, multiple actors (clients, lawyers, courts, insurers) are involved, causing behavioural dynamics which are not easily predicted or influenced. Against this background, this paper looks into BTE and ATE arrangements by analysing the particularities of BTE and ATE arrangements currently available in some European jurisdictions and by painting a picture of their respective markets and legal contexts. This allows for some reflection on the performance of BTE and ATE providers as both financiers and keepers. Two issues emerge from the analysis that are worthy of some further reflection. Firstly, there is the problematic long-term sustainability of some ATE products. Secondly, the challenges faced by policymakers that would like to nudge consumers into voluntarily taking out BTE LEI

Search for stop and higgsino production using diphoton Higgs boson decays

Results are presented of a search for a "natural" supersymmetry scenario with gauge mediated symmetry breaking. It is assumed that only the supersymmetric partners of the top-quark (stop) and the Higgs boson (higgsino) are accessible. Events are examined in which there are two photons forming a Higgs boson candidate, and at least two b-quark jets. In 19.7 inverse femtobarns of proton-proton collision data at sqrt(s) = 8 TeV, recorded in the CMS experiment, no evidence of a signal is found and lower limits at the 95% confidence level are set, excluding the stop mass below 360 to 410 GeV, depending on the higgsino mass

Severe early onset preeclampsia: short and long term clinical, psychosocial and biochemical aspects

Preeclampsia is a pregnancy specific disorder commonly defined as de novo hypertension and proteinuria after 20 weeks gestational age. It occurs in approximately 3-5% of pregnancies and it is still a major cause of both foetal and maternal morbidity and mortality worldwide1. As extensive research has not yet elucidated the aetiology of preeclampsia, there are no rational preventive or therapeutic interventions available. The only rational treatment is delivery, which benefits the mother but is not in the interest of the foetus, if remote from term. Early onset preeclampsia (<32 weeks’ gestational age) occurs in less than 1% of pregnancies. It is, however often associated with maternal morbidity as the risk of progression to severe maternal disease is inversely related with gestational age at onset2. Resulting prematurity is therefore the main cause of neonatal mortality and morbidity in patients with severe preeclampsia3. Although the discussion is ongoing, perinatal survival is suggested to be increased in patients with preterm preeclampsia by expectant, non-interventional management. This temporising treatment option to lengthen pregnancy includes the use of antihypertensive medication to control hypertension, magnesium sulphate to prevent eclampsia and corticosteroids to enhance foetal lung maturity4. With optimal maternal haemodynamic status and reassuring foetal condition this results on average in an extension of 2 weeks. Prolongation of these pregnancies is a great challenge for clinicians to balance between potential maternal risks on one the eve hand and possible foetal benefits on the other. Clinical controversies regarding prolongation of preterm preeclamptic pregnancies still exist – also taking into account that preeclampsia is the leading cause of maternal mortality in the Netherlands5 - a debate which is even more pronounced in very preterm pregnancies with questionable foetal viability6-9. Do maternal risks of prolongation of these very early pregnancies outweigh the chances of neonatal survival? Counselling of women with very early onset preeclampsia not only comprises of knowledge of the outcome of those particular pregnancies, but also knowledge of outcomes of future pregnancies of these women is of major clinical importance. This thesis opens with a review of the literature on identifiable risk factors of preeclampsia

Measurement of t(t)over-bar normalised multi-differential cross sections in pp collisions at root s=13 TeV, and simultaneous determination of the strong coupling strength, top quark pole mass, and parton distribution functions

Peer reviewe

Measurement of the top quark forward-backward production asymmetry and the anomalous chromoelectric and chromomagnetic moments in pp collisions at √s = 13 TeV

Abstract The parton-level top quark (t) forward-backward asymmetry and the anomalous chromoelectric (d̂ t) and chromomagnetic (μ̂ t) moments have been measured using LHC pp collisions at a center-of-mass energy of 13 TeV, collected in the CMS detector in a data sample corresponding to an integrated luminosity of 35.9 fb−1. The linearized variable AFB(1) is used to approximate the asymmetry. Candidate t t ¯ events decaying to a muon or electron and jets in final states with low and high Lorentz boosts are selected and reconstructed using a fit of the kinematic distributions of the decay products to those expected for t t ¯ final states. The values found for the parameters are AFB(1)=0.048−0.087+0.095(stat)−0.029+0.020(syst),μ̂t=−0.024−0.009+0.013(stat)−0.011+0.016(syst), and a limit is placed on the magnitude of | d̂ t| &lt; 0.03 at 95% confidence level. [Figure not available: see fulltext.