Synergism of Au and Ru Nanoparticles in Low-Temperature Photoassisted CO2 Methanation

This is the peer reviewed version of the following article:Mateo-Mateo, Diego, De Masi, Deborah , Albero-Sancho, Josep, Lacroix, Lisa-Marie , Fazzini, Pier-Francesco , Chaudret, Bruno , García Gómez, Hermenegildo. (2018). Synergism of Au and Ru Nanoparticles in Low-Temperature Photoassisted CO2 Methanation.Chemistry - A European Journal, 24, 69, 18436-18443. DOI: 10.1002/chem.201803022, which has been published in final form at http://doi.org/10.1002/chem.201803022. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions[EN] Au and Ru nanoparticles have been deposited on Siralox® substrate by impregnation and chemical reduction, respectively (Au-Ru-S). The as-prepared material has demonstrated to be very active for the selective CO2 metanation to CH4 at temperatures below 250 oC. In addition, Au-Ru-S exhibits CH4 production enhancement upon UV-Vis light irradiation starting at temepratures higher than 200 oC, although the contribution of the photoassisted pathway of CH4 production decreases as temperature increases. Thus, a maximum CH4 production of 204 mmol/gRu at 250 oC upon 100 mW/cm2 irradiation was achieved. Control experiments using Ru-S and Au-S materials revealed that Ru nanoparticles are the CO2 methanation active sites, while Au NPs contribute harvesting light, mainly visible as consequence of the strong Au plasmon band centrered at 529 nm. The visible light absorbed by Au NPs plasmon could act as local heaters of neighbouring Ru NPs, increasing their temperature and enhancing CH4 production.D. M., J.A., and H.G. thank the Spanish Ministry of Economy and Competitiveness (Severo Ochoa SEV2016-0683 and CTQ2015-69563-CO2-1), Generalitat Valenciana (Prometeo 2017-083) for financial support. J.A. and D.M. also thank UPV for a postdoctoral scholarship and the Spanish Ministry of Science for a PhD Scholarship, respectively. This project has received funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (grant agreement No GA694159 MONACAT).Mateo-Mateo, D.; De Masi, D.; Albero-Sancho, J.; Lacroix, L.; Fazzini, P.; Chaudret, B.; García Gómez, H. (2018). Synergism of Au and Ru Nanoparticles in Low-Temperature Photoassisted CO2 Methanation. Chemistry - A European Journal. 24(69):18436-18443. https://doi.org/10.1002/chem.201803022S1843618443246

Technology-Mediated Communication in Familial Relationships: Moderated-Mediation Models of Isolation and Loneliness

Background and ObjectivesWe examined whether technology-mediated communication has functional or emotional equivalence to face-to-face (FtF) contact in familial relationships, by scrutinizing the effects of phone, text/e-mail, and video contact on isolation and loneliness.Research Design and MethodsWe tested whether FtF contact with a relative would mediate the pathway between proximity to family and (i) isolation and (ii) loneliness. We then tested hypotheses that telephone, text/e-mails, and video contact would moderate this mediated pathway. We compared models for younger (<75) and older (≥75) cohorts, expecting to observe moderation effects for text/e-mail and video contact in the younger cohort only. Data were drawn from Wave 2 of CFAS Wales (United Kingdom) study (N = 2,099).ResultsProximity to a relative had a significant indirect effect on isolation and loneliness through the mediating variable FtF contact. Phone and text/e-mail contact moderated the effect of FtF contact on isolation for all samples. None of the technologies moderated the impact of FtF contact on loneliness for the full sample. Telephone contact had a moderating influence on loneliness for the younger cohort only. Video calls had no significant moderation effect.Discussion and ImplicationsTelephone and text/e-mail contact have functional equivalence to FtF contact in familial relationships. None of the forms of technological communication have emotional equivalence to the “gold standard” of embodied presence. The study demonstrates the importance of theorizing about the pathways to isolation and loneliness to better understand the likelihood of implementing successful interventions using technology-mediated communication within families

Genetic analysis of blood molecular phenotypes reveals common properties in the regulatory networks affecting complex traits

We evaluate the shared genetic regulation of mRNA molecules, proteins and metabolites derived from whole blood from 3029 human donors. We find abundant allelic heterogeneity, where multiple variants regulate a particular molecular phenotype, and pleiotropy, where a single variant associates with multiple molecular phenotypes over multiple genomic regions. The highest proportion of share genetic regulation is detected between gene expression and proteins (66.6%), with a further median shared genetic associations across 49 different tissues of 78.3% and 62.4% between plasma proteins and gene expression. We represent the genetic and molecular associations in networks including 2828 known GWAS variants, showing that GWAS variants are more often connected to gene expression in trans than other molecular phenotypes in the network. Our work provides a roadmap to understanding molecular networks and deriving the underlying mechanism of action of GWAS variants using different molecular phenotypes in an accessible tissue

Genetic analysis of blood molecular phenotypes reveals common properties in the regulatory networks affecting complex traits

We evaluate the shared genetic regulation of mRNA molecules, proteins and metabolites derived from whole blood from 3029 human donors. We find abundant allelic heterogeneity, where multiple variants regulate a particular molecular phenotype, and pleiotropy, where a single variant associates with multiple molecular phenotypes over multiple genomic regions. The highest proportion of share genetic regulation is detected between gene expression and proteins (66.6%), with a further median shared genetic associations across 49 different tissues of 78.3% and 62.4% between plasma proteins and gene expression. We represent the genetic and molecular associations in networks including 2828 known GWAS variants, showing that GWAS variants are more often connected to gene expression in trans than other molecular phenotypes in the network. Our work provides a roadmap to understanding molecular networks and deriving the underlying mechanism of action of GWAS variants using different molecular phenotypes in an accessible tissue

New genetic loci link adipose and insulin biology to body fat distribution.

Body fat distribution is a heritable trait and a well-established predictor of adverse metabolic outcomes, independent of overall adiposity. To increase our understanding of the genetic basis of body fat distribution and its molecular links to cardiometabolic traits, here we conduct genome-wide association meta-analyses of traits related to waist and hip circumferences in up to 224,459 individuals. We identify 49 loci (33 new) associated with waist-to-hip ratio adjusted for body mass index (BMI), and an additional 19 loci newly associated with related waist and hip circumference measures (P < 5 × 10(-8)). In total, 20 of the 49 waist-to-hip ratio adjusted for BMI loci show significant sexual dimorphism, 19 of which display a stronger effect in women. The identified loci were enriched for genes expressed in adipose tissue and for putative regulatory elements in adipocytes. Pathway analyses implicated adipogenesis, angiogenesis, transcriptional regulation and insulin resistance as processes affecting fat distribution, providing insight into potential pathophysiological mechanisms

Bimetallic nanoparticles combining catalytic and physical properties for CO2 and biomass valorization

Les réactions réalisées en catalyse hétérogène nécessitent des températures et pressions élevées. Une façon originale pour améliorer ces conditions de réaction est de générer des températures élevées directement à la surface des catalyseurs par des stimuli physiques (magnétiques ou plasmoniques). L’objectif de cette thèse a été la mise en place de la synthèse de nanoparticules complexes combinant des propriétés physiques et des propriétés catalytiques. Ainsi, deux types de nanoparticules ont été synthétisées, des nanoparticules de fer-nickel pour le chauffage magnétique et des nanoparticules bimétalliques or-ruthénium pour le chauffage plasmonique. Dans le contexte actuel de développement durable et de stockage des énergies renouvelables, nous avons étudié deux réactions catalytiques : la réaction de Sabatier et l’hydrodésoxygénation de molécules plateformes issues de la biomasse lignocellulosique. Sous champ magnétique, la génération au voisinage des nanoparticules de fer-nickel de très hautes températures a permis de créer un environnement hétérogène à la surface des nanoparticules. Ainsi, la conversion totale du furfural et de l’hydroxyméthylfurfural en biocarburants (le méthylfurane et le diméthylfurane) a pu être réalisée en solution dans des conditions très douces. Les propriétés de chauffe et les propriétés catalytiques des nanoparticules de fer-nickel ont permis d’activer la réaction de Sabatier, et d’atteindre pour la première fois des rendements en méthane de 100 %. Dans la même optique, les propriétés plasmoniques et catalytiques des nanoparticules d’or-ruthénium ont été étudiées pour la réaction de Sabatier. Un couplage entre chauffage classique et irradiation lumineuse a permis de mettre en évidence un effet synergique entre le ruthénium et l’or pour l’activation de la réaction.Heterogeneous catalytic reactions require often very harsh conditions, i.e. high temperature and high pressure in the overall system. An original way to lower these reaction conditions consists in generating a local heating directly at the surface of the catalysts by the means of physical stimuli (magnetic or plasmonics). However, up to now, the catalytic sites and the heating agents were spatially separated, reducing the efficiency of the heat transfer. The aim of this thesis is thus to elaborate complex bimetallic nanoparticles combining physical properties and catalytic properties in the very same object. Two types of nanoparticles have been synthesized, iron-nickel nanoparticles for magnetic heating and gold-ruthenium nanoparticles for plasmonic heating. In the current context of sustainable development and storage of renewable energies, we studied two catalytic reactions: the Sabatier reaction, to valorize CO2 gas and the hydrodeoxygenation of platforms molecules from lignocellulosic biomass to yield biofuel. Under alternating magnetic field, iron-nickel nanoparticles generate high temperatures creating a heterogeneous environment at their surface. Thanks to these peculiar conditions, the furfural and the hydroxymethylfurfural could be totally converted, in liquid phase, into biofuels (methylfurane and dimethylfurane) under mild conditions. Moreover, heat properties of iron-nickel nanoparticles combining with their catalytic properties have made possible the total conversion of carbon dioxide into methane. Similarly, plasmonic and catalytic properties of gold-ruthenium nanoparticles were studied for the Sabatier reaction. By coupling classical heating and light irradiation a synergetic effect between ruthenium and gold was observed leading to the efficient activation of the reaction

Structural Dissection of Viral Spike-Protein Binding of SARS-CoV-2 and SARS-CoV-1 to the Human Angiotensin-Converting Enzyme 2 (ACE2) as Cellular Receptor

An outbreak by a new severe acute respiratory syndrome betacoronavirus (SARS-CoV-2) has spread CoronaVirus Disease 2019 (COVID-19) all over the world. Immediately, following studies have confirmed the human Angiotensin-Converting Enzyme 2 (ACE2) as a cellular receptor of viral Spike-Protein (Sp) that mediates the CoV-2 invasion into the pulmonary host cells. Here, we compared the molecular interactions of the viral Sp from previous SARS-CoV-1 of 2002 and SARS-CoV-2 with the host ACE2 protein by in silico analysis of the available experimental structures of Sp-ACE2 complexes. The K417 amino acid residue, located in the region of Sp Receptor-Binding Domain (RBD) of the new coronavirus SARS-CoV-2, showed to have a key role for the binding to the ACE2 N-terminal region. The R426 residue of SARS-CoV-1 Sp-RBD also plays a key role, although by interacting with the central region of the ACE2 sequence. Therefore, our study evidenced peculiarities in the interactions of the two Sp-ACE2 complexes. Our outcomes were consistent with previously reported mutagenesis studies on SARS-CoV-1 and support the idea that a new and different RBD was acquired by SARS-CoV-2. These results have interesting implications and suggest further investigations

Molecular Aspects of Spike&ndash;ACE2 Interaction

A new betacoronavirus (CoV-2) is responsible for the pandemic of severe acute respiratory syndrome (SARS) that began in China at the end of 2019, today known as COronaVIrus Disease 2019 (COVID-19). Subsequent studies confirmed the human angiotensin-converting enzyme 2 (hACE2) as the main cell receptor of spike trimeric glycoprotein, located on the viral envelope, mediating the CoV-2 invasion into the host cells through the receptor-binding domain (RBD) of the spike. Computational analysis of the known experimental 3D structures of spike&ndash;ACE2 complexes evidenced distinguishing features in the molecular interactions at the RBD-cell receptor binding interface between CoV-2 and previous CoV-1. The spike represents a key target for drug design as well as an optimal antigen for RNA/viral vector vaccines and monoclonal antibodies in order to maximize prevention and therapy of COVID-19

Corrigendum: Optimizing the use of lenvatinib in combination with pembrolizumab in patients with advanced endometrial carcinoma

: [This corrects the article DOI: 10.3389/fonc.2022.979519.]