H2O2 adsorption and dissociation on various CeO2(111) surface models: a first-principles study

Periodic density functional theory (DFT) calculations using the hybrid PBE0 functional and atom-centered Gaussian functions as basis sets were carried out to investigate the absorption and the first steps involved in the decomposition of hydrogen peroxide (H2O2) on three different models of the ceria (111) surface. One of the models is a clean surface, and the others are defective and partially hydroxylated ceria surfaces. On the clean surface, we found that the minimum energy path of hydrogen peroxide decomposition involves a three-step process, i.e., adsorption, deprotonation, and formation of the peroxide anion, stabilized through its interaction with the surface at a Ce (IV) site, with activation barriers of less than about 0.5 eV. The subsequent formation of superoxide anions and molecular oxygen species is attributed to electron transfer from the reactants to the Ce (IV) ions underneath. On the defective surface, H2O2dissociation is an energetically downhill reaction thermodynamically driven by the healing of the O vacancies, after the reduction and decomposition of H2O2into oxygen and water. On the hydroxylated surface, H2O2is first adsorbed by forming a favorable H-bond and then undergoes heterolytic dissociation, forming two hydroxyl groups at two vicinal Ce sites

Folding mechanisms steer the amyloid fibril formation propensity of highly homologous proteins

Significant advances in the understanding of the molecular determinants of fibrillogenesis can be expected from comparative studies of the aggregation propensities of proteins with highly homologous structures but different folding pathways. Here, we fully characterize, by means of stopped-flow, T-jump, CD and DSC experiments, the unfolding mechanisms of three highly homologous proteins, zinc binding Ros87 and Ml153-149 and zinc-lacking Ml452-151. The results indicate that the three proteins significantly differ in terms of stability and (un)folding mechanisms. Particularly, Ros87 and Ml153-149 appear to be much more stable to guanidine denaturation and are characterized by folding mechanisms including the presence of an intermediate. On the other hand, metal lacking Ml452-151 folds according to a classic two-state model. Successively, we have monitored the capabilities of Ros87, Ml452-151 and Ml153-149 to form amyloid fibrils under native conditions. Particularly, we show, by CD, fluorescence, DLS, TEM and SEM experiments, that after 168 hours, amyloid formation of Ros87 has started, while Ml153-149 has formed only amorphous aggregates and Ml452-151 is still monomeric in solution. This study shows how metal binding can influence protein folding pathways and thereby control conformational accessibility to aggregation-prone states, which in turn changes aggregation kinetics, shedding light on the role of metal ions in the development of protein deposition diseases

Nonlinear static procedures for state-dependent seismic fragility analysis of reinforced concrete buildings

This paper introduces a simplified methodology to develop state-dependent fragility relationships, based on nonlinear static analyses combined with the Cloud Capacity Spectrum Method. Capacity reduction factors for structural members are applied to simulate the attainment of a specific damage state under a mainshock. A cloud-based procedure is adopted to compute fragility analyses. The procedure is illustrated for a case-study building designed for gravity loads only. Results highlight the importance of considering the effect of cumulative damage in the fragility analysis of buildings. The proposed methodology may be used for seismic-risk assessment studies accounting for ground-motion sequences

Energy refurbishment planning of Italian school buildings using data-driven predictive models

In the current practice, the design of energy refurbishment interventions for existing buildings is typically addressed by performing time-consuming software-based numerical simulations. However, this approach may be not suitable for preliminary assessment studies, especially when large building portfolios are involved. Therefore, this research work aims at developing simplified data-driven predictive models to estimate the energy consumption of existing school buildings in Italy and support the decision-making process in energy refurbishment intervention planning at a large scale. To accomplish this, an extensive database is assembled through comprehensive on-site surveys of school buildings in Southern Italy. For each school, a Building Information Modelling (BIM) model is developed and validated considering real energy consumption data. These BIM models serve in the design of suitable energy refurbishment interventions. Moreover, a comprehensive parametric investigation based on refined energy analyses is carried out to significantly improve and integrate the dataset. To derive the predictive models, firstly the most relevant parameters for energy consumption are identified by performing sensitivity analyses. Based on these findings, predictive models are generated through a multiple linear regression method. The suggested models provide an estimation of the energy consumption of the “as-built” configuration, as well as the costs and benefits of alternative energy refurbishment scenarios. The reliability of the proposed simplified relationships is substantiated through a statistical analysis of the main error indices. Results highlight that the building's shape factor (i.e., the ratio between the building's envelope area and its volume) and the area-weighted average of the thermal properties of the building envelope significantly affect both the energy consumption of school buildings and the achievable savings through retrofitting interventions. Finally, a framework for the preliminary design of energy refurbishment of buildings, based on the implementation of the herein developed predictive model, is proposed and illustrated through a worked example application. Worth noting that, while the proposed approach is currently limited to school buildings, the methodology can conceptually be extended to any building typology, provided that suitable data on energy consumption are available

Energy-based procedures for seismic fragility analysis of mainshock-damaged buildings

In recent decades, significant research efforts have been devoted to developing fragility and vulnerability models for mainshock-damaged buildings, i.e., depending on the attained damage state after a mainshock ground motion (state-dependent fragility/vulnerability relationships). Displacement-based peak quantities, such as the maximum interstory drift ratio, are widely adopted in fragility analysis to define both engineering demands and structural capacities at the global and/or local levels. However, when considering ground-motion sequences, the use of peak quantities may lead to statistical inconsistencies (e.g., fragility curves’ crossings) due to inadequate consideration of damage accumulation. In this context, energy-based engineering demand parameters (EDPs), explicitly accounting for cumulative damage, can help address this issue. This paper provides an overview of recent findings on the development of aftershock-fragility models of mainshock-damaged buildings. Particular focus is given to state-of-the-art frameworks for fragility analyses based on cumulative damage parameters. Moreover, a literature review on damage indices and energy-based concepts and approaches in earthquake engineering is reported to better understand the main advantages of the mostly adopted energy-based parameters, as well as their limitations. Different refinement levels of seismic response analyses to derive fragility relationships of mainshock-damaged buildings are also discussed. Finally, the benefits of adopting energy-based EDPs rather than, or in addition to, peak quantities in state-dependent fragility analyses are demonstrated on a reinforced concrete frame building. Specifically, a refined lumped plasticity modeling approach is adopted, and sequential cloud-based time-history analyses of a Multi-Degree-of-Freedom (MDoF) model are carried out. The results highlight that energy-based approaches for fragility analysis effectively capture damage accumulation during earthquake sequences without inconsistencies in the obtained statistical models. On the other hand, estimating global or local structural capacity in terms of cumulative EDPs is still challenging. Further experimental data are needed to better calibrate the quantification of energy-based damaged states

A sensitivity study on the mechanical properties of interface elements adopted in finite element analyses to simulate the interaction between soil and laterally loaded piles

An increasing number of offshore energy structures have been built recently on driven piles, ranging from jack- et piles with typical length-to-diameter (L/D) ratios of 10-40 to monopiles with far lower L/D ratios. The load-displacement behaviour of these foundations can be investigated by means of Finite Element (FE) analyses, for instance following the design methodology developed by the PISA Joint Industry Project (JIP). A challenging aspect of the modelling, for piles loaded either axially or laterally, is the simulation of the behaviour at the soil-pile interface with the adoption of suitable formulations for the interface elements and with representative mechanical properties. This paper presents a sensitivity study conducted on both the elastic and plastic properties of interface elements adopted in FE analyses of laterally loaded piles driven in chalk. The study benefited from the extensive field and laboratory test results collected during the ALPACA JIP and the corresponding pile tests. The aim of the paper is to provide guidance for numerical modelling on the selection of the most appropriate mechanical properties of interface elements to be used in the analyses of soil-pile interaction under lateral loading

O2Activation over Ag-Decorated CeO2(111) and TiO2(110) Surfaces: A Theoretical Comparative Investigation

Periodic spin-polarized hybrid density functional theory calculations have been performed to investigate the reactivity of pristine, O-defective, and Ag-decorated CeO2(111) and TiO2(110) surfaces with a small Ag10 cluster toward O2. The adsorption of O2 and its subsequent dissociation have been studied in order to provide a better understanding of the role of the oxide, the metallic nanoparticle, and their interaction in the reactivity of composite metal/metal oxide materials toward O2, as potential catalysts to this reaction. Structural, energetic, electronic, and vibrational properties of all species involved in the different reaction paths considered have been fully characterized. On the stoichiometric surfaces, Ag10 is oxidized and reduces surface Ce4+/Ti4+ ions, while on the O-defective surfaces, the adhesion of silver is promoted only on CeO2 but unfavored on TiO2. On the other hand, on the silver-free supports, O2 strongly adsorbs at vacancies and preferentially reduces to peroxide. When no O vacancies are considered on the Ag10-decorated supports, the net positive charge on Ag10 actually prevents the adsorption and reduction of O2. Instead, when O vacancies are included, two reaction pathways are observed; oxygen molecules can weakly absorb on the silver cluster as a superoxide moiety or strongly adsorb at the vacancy as peroxide. The dissociation of the O-O bond of the peroxide is favored both from the thermodynamic and kinetic points of view in silver-decorated surfaces, in contrast with the silver-free cases. In addition, Ag10/CeO2 shows higher activity toward the O2 adsorption and dissociation than Ag10/TiO2, which can be related both to the higher ionicity and superior electron storage/release ability of ceria with respect to titania, thus leading to the weakening of the O-O bond and providing lower activation barriers for oxygen reduction. These results deepen the current understanding of the reactivity of metal/metal oxide composites toward O2, especially elucidating how the surface stoichiometry affects the charge state of the metal clusters, and hence the reactivity of these interfaces toward O2, with potential important consequences when such composites are considered for catalytic applications

Supramolecular aggregates containing lipophilic Gd(III) complexes as contrast agents in MRI

Magnetic resonance imaging (MRI) contrast agents based on paramagnetic gadolinium complexes are widely used in biomedical research and diagnosis. Their application is intended to improve efficacy of MRI providing physiological information along with the impressive anatomical detail already obtained by images without contrast. The classical gadolinium complexes currently used for MRI contrast enhancement are all lowmolecularweightcompounds that rapidly equilibrate between the intra and extravascular spaces after intravenous administration. In order to obtain gadolinium-based agents with different pharmacokinetic properties, supramolecular aggregates such as micelles and liposomes have been recently proposed. Micelles and liposomes, obtained by the aggregation of lipophilic gadolinium complexes are here described, with the aim to correlate their structural and relaxometric properties.We report on the state of the art in the development of supramolecular aggregates obtained by self-assembly of lipophilic gadolinium complexes and aggregates in which lipophilic gadolinium complexes are assembled with surfactants. Moreover aggregates derivatized with bioactive molecules, such as peptides and antibodies, acting as target selective MRI contrast agents are described

Assignment of the binding site for Haptoglobin on Apolipoprotein A-I

Haptoglobin (Hpt) was previously found binding the high-density lipoprotein (HDL) Apolipoprotein A-I (ApoA-I) and able to inhibit the ApoA-I-dependent activity of the enzyme Lecithin:Cholesterol Acyl-Transferase (LCAT), which plays a major role in the reverse cholesterol transport. The ApoA-I structure was analyzed for detecting the site bound by Hpt. ApoA-I was treated by cyanogen bromide or hydroxylamine and the resulting fragments, separated by electrophoresis or gel filtration, were tested by Western blotting or ELISA for their ability to bind Hpt. The ApoA-I sequence from Glu113 to Asn184 harbored the binding site for Hpt. Biotinylated peptides were synthesized overlapping such a sequence, and their Hpt binding activity was determined by avidin-linked peroxidase. The highest activity was exhibited by the peptide P2a, containing the ApoA-I sequence from Leu141 to Ala164. Such a sequence contains an ApoA-I domain required for binding cells, promoting cholesterol efflux, and stimulating LCAT. The peptide P2a effectively prevented both binding of Hpt to HDL-coated plastic wells and Hpt-dependent inhibition of LCAT, measured by anti-Hpt antibodies and cholesterol esterification activity respectively. The enzyme activity was not influenced, in the absence of Hpt, by P2a. Differently from ApoA-I or HDL, the peptide did not compete with Hemoglobin for Hpt binding in ELISA experiments. The results suggest that Hpt might mask the ApoA-I domain required for LCAT stimulation, thus impairing the HDL function. Synthetic peptides, able to displace Hpt from ApoA-I without altering its property of binding Hemoglobin, might be used for treatment of diseases associated with defective LCAT function