Elemental Anisotropic Growth and Atomic-Scale Structure of Shape-Controlled Octahedral Pt–Ni–Co Alloy Nanocatalysts

Multimetallic shape-controlled nanoparticles offer great opportunities to tune the activity, selectivity, and stability of electrocatalytic surface reactions. However, in many cases, our synthetic control over particle size, composition, and shape is limited requiring trial and error. Deeper atomic-scale insight in the particle formation process would enable more rational syntheses. Here we exemplify this using a family of trimetallic PtNiCo nanooctahedra obtained via a low-temperature, surfactant-free solvothermal synthesis. We analyze the competition between Ni and Co precursors under coreduction “one-step” conditions when the Ni reduction rates prevailed. To tune the Co reduction rate and final content, we develop a “two-step” route and track the evolution of the composition and morphology of the particles at the atomic scale. To achieve this, scanning transmission electron microscopy and energy dispersive X-ray elemental mapping techniques are used. We provide evidence of a heterogeneous element distribution caused by element-specific anisotropic growth and create octahedral nanoparticles with tailored atomic composition like Pt1.5M, PtM, and PtM1.5 (M = Ni + Co). These trimetallic electrocatalysts have been tested toward the oxygen reduction reaction (ORR), showing a greatly enhanced mass activity related to commercial Pt/C and less activity loss than binary PtNi and PtCo after 4000 potential cycles.

How monuments shape urban identity

Monuments in our society commemorate historical events, acts or heroes, and educate people about them. Monuments are landmarks that stand out from other buildings to give the city identity and order. This thesis asks how a monument can be designed to project a clear image at a distance and articulate a spatial experience at close range. Two important monuments that form part of the life of America serve as examples: (1) The Statue of Liberty, in the New York Harbor, that has become the visual icon of New York if not the nation and (2) The Holocaust Memorial in Miami Beach, Florida, that leads the visitor through a poignant experience at close range. The second part of the thesis is the design of a monument and museum for The Port of Miami, as part of the Port Boulevard Enhancement Project, sponsored by the Florida Foreign Trade Association, to celebrate the trade pioneers who helped Miami-Dade County achieve its prominence. The site for the monument is located at Biscayne Boulevard and Fifth Street, between Bayside Market Place and The American Airlines Arena in downtown Miami, at the Biscayne Bay.

Theoretical and experimental study on electron interactions with chlorobenzene: Shape resonances and differential cross sections

In this work, we report theoretical and experimental cross sections for elastic scattering of electrons by chlorobenzene (ClB). The theoretical integral and differential cross sections (DCSs) were obtained with the Schwinger multichannel method implemented with pseudopotentials (SMCPP) and the independent atom method with screening corrected additivity rule (IAM-SCAR). The calculations with the SMCPP method were done in the static-exchange (SE) approximation, for energies above 12 eV, and in the static-exchange plus polarization approximation, for energies up to 12 eV. The calculations with the IAM-SCAR method covered energies up to 500 eV. The experimental differential cross sections were obtained in the high resolution electron energy loss spectrometer VG-SEELS 400, in Lisbon, for electron energies from 8.0 eV to 50 eV and angular range from 7 degrees to 110 degrees. From the present theoretical integral cross section (ICS) we discuss the low-energy shape-resonances present in chlorobenzene and compare our computed resonance spectra with available electron transmission spectroscopy data present in the literature. Since there is no other work in the literature reporting differential cross sections for this molecule, we compare our theoretical and experimental DCSs with experimental data available for the parent molecule benzene. Published by AIP Publishing.

An allometric modelling approach to identify the optimal body shape sssociated with, and differences between brazilian and peruvian youth motor performance

Children fromdevelopedanddevelopingcountriesdifferintheirbodysizeandshapedueto markeddifferencesacrosstheirlifehistorycausedbysocial,economicandculturaldifferenceswhicharealsolinkedtotheirmotorperformance(MP).Weusedallometricmodelsto identifysize/shapecharacteristicsassociatedwithMPtestsbetweenBrazilianandPeruvianschoolchildren.Atotalof4,560subjects,2,385girlsand2,175boysaged9–15years werestudied.Heightandweightweremeasured;biological maturation wasestimated with thematurityoffsettechnique;MPmeasuresincludedthe12minuterun(12MR),handgrip strength(HG),standinglongjump(SLJ)andtheshuttlerunspeed(SR)tests;physicalactivity(PA)wasassessedusingtheBaeckequestionnaire.Amultiplicativeallometricmodel wasadoptedtoadjustforbodysizedifferencesacrosscountries.Reciprocalponderalindex (RPI)wasfoundtobethemostsuitablebodyshapeindicatorassociatedwiththe12MR, SLJ,HGandSRperformance.Apositivematurationoffset parameterwasalsoassociated withabetterperformanceinSLJ,HGandSRtests.Sexdifferenceswerefoundinallmotor tests.BrazilianyouthshowedbetterscoresinMPthantheirPeruvianpeers,evenwhen controlling fortheirbodysizedifferencesThecurrentstudyidentifiedthekeybodysize associatedwithfourbodymass-dependentMPtests.Biological maturationandPAwere associatedwithstrengthandmotorperformance.Sexdifferenceswerefoundinallmotor tests,aswellasacrosscountriesfavoringBrazilianchildrenevenwhenaccountingfortheir bodysize/shapedifferences.

An allometric modelling approach to identify the optimal body shape associated with, and differences between brazilian and peruvian youth motor performance

Children fromdevelopedanddevelopingcountriesdifferintheirbodysizeandshapedueto markeddifferencesacrosstheirlifehistorycausedbysocial,economicandculturaldifferenceswhicharealsolinkedtotheirmotorperformance(MP).Weusedallometricmodelsto identifysize/shapecharacteristicsassociatedwithMPtestsbetweenBrazilianandPeruvianschoolchildren.Atotalof4,560subjects,2,385girlsand2,175boysaged9–15years werestudied.Heightandweightweremeasured;biological maturation wasestimated with thematurityoffsettechnique;MPmeasuresincludedthe12minuterun(12MR),handgrip strength(HG),standinglongjump(SLJ)andtheshuttlerunspeed(SR)tests;physicalactivity(PA)wasassessedusingtheBaeckequestionnaire.Amultiplicativeallometricmodel wasadoptedtoadjustforbodysizedifferencesacrosscountries.Reciprocalponderalindex (RPI)wasfoundtobethemostsuitablebodyshapeindicatorassociatedwiththe12MR, SLJ,HGandSRperformance.Apositivematurationoffset parameterwasalsoassociated withabetterperformanceinSLJ,HGandSRtests.Sexdifferenceswerefoundinallmotor tests.BrazilianyouthshowedbetterscoresinMPthantheirPeruvianpeers,evenwhen controlling fortheirbodysizedifferencesThecurrentstudyidentifiedthekeybodysize associatedwithfourbodymass-dependentMPtests.Biological maturationandPAwere associatedwithstrengthandmotorperformance.Sexdifferenceswerefoundinallmotor tests,aswellasacrosscountriesfavoringBrazilianchildrenevenwhenaccountingfortheir bodysize/shapedifferences.

How do medium naturalness and personality traits shape academic achievement and perceived learning? An experimental study of face-to-face and synchronous e-learning

This controlled experiment examined how academic achievement and cognitive, emotional and social aspects of perceived learning are affected by the level of medium naturalness (face-to-face, one-way and two-way videoconferencing) and by learners’ personality traits (extroversion–introversion and emotional stability–neuroticism). The Media Naturalness Theory explains the degree of medium naturalness by comparing its characteristics to face-to-face communication, considered to be the most natural form of communication. A total of 76 participants were randomly assigned to three experimental conditions: face-to-face, one-way and two-way videoconferencing. E-learning conditions were conducted through Zoom videoconferencing, which enables natural and spontaneous communication. Findings shed light on the trade-off involved in media naturalness: one-way videoconferencing, the less natural learning condition, enhanced the cognitive aspect of perceived learning but compromised the emotional and social aspects. Regarding the impact of personality, neurotic students tended to enjoy and succeed more in face-to-face learning, whereas emotionally stable students enjoyed and succeeded in all of the learning conditions. Extroverts tended to enjoy more natural learning environments but had lower achievements in these conditions. In accordance with the ‘poor get richer’ principle, introverts enjoyed environments with a low level of medium naturalness. However, they remained focused and had higher achievements in the face-to-face learning.

Nuclear shape instability caused by lamin A deregulation promotes invasiveness in pediatric bone sarcomas: from nucleo-cytoskeleton dynamics to novel therapeutic opportunities

Osteosarcoma (OS) and Ewing sarcoma (EWS) are the two most frequent primary bone tumors, in which metastases remain the most relevant adverse prognostic factor. Lamin A is the main constituent of the nuclear lamina, with a fundamental role in maintaining the connection between nucleus and cytoskeleton (through LINC complex proteins interactions), and its alterations can be implicated in tumor progression. We investigated how nucleo-cytoskeleton dynamics is influenced by lamin A modulation in OS and EWS, demonstrating that both these cancer models had low levels of lamin A, which are linked to a significantly more marked nuclear misshaping. In our in vitro studies, reduced levels of lamin A promoted migratory abilities in these tumors. Moreover, these findings were corroborated by gene expression analyses on EWS patient samples, showing that LMNA levels were significantly lower in metastatic lesions compared to primary tumors and that patients with low LMNA had a significant worse overall survival. We also found that LMNA expression significantly impaired EWS metastases formation in vivo. We demonstrated that low lamin A expression was linked to a severe mislocalization of LINC complex proteins, thus disrupting nucleo-cytoskeleton interactions, with a corresponding gain in malignant properties, which resulted in increased invasiveness. Lamin A overexpression or its accumulation by a statin-based pharmacological treatment allowed us to reconstitute a functional nucleo-cytoskeleton interplay, which resulted in significant downmodulation of ROCK2 and YAP, two crucial drivers of EWS aggressiveness. Our study demonstrated that lamin A is a favorable mediator of nuclear shape stability in bone sarcomas, and its modulation rescues LINC complex protein localization and regulates mechano-signaling pathways, thus promoting a less aggressive cancer phenotype. We also identified statins, already employed in clinical practice, as a tool capable to increase lamin A levels, and to reconstitute functional nucleo-cytoskeletal dynamics, resulting in reduced cellular migration.

Different dietary fibres included in the gestation and lactation diet shape sow's microbiota, modify colostrum and milk composition and affect piglet growth and health

This thesis reports three experimental studies that may contribute to understand how the sources or types of dietary fibres (DFs) included in sow diet with similar level of total DFs influence the composition of colostrum and milk and their related effects on offspring performance and gut microbiota. The first study showed that decreasing the level of hemicelluloses (HCs) in sow’s lactation diet increased the proportion of butyrate and the concentration of volatile fatty acids (VFAs), copper and threonine in milk. Simultaneously, the post-weaning growth of low birthweight piglets was improved, and the diarrhoea occurrence was reduced during the second week post-weaning. The second study showed that the level of HCs in the diet of lactating sows affected their faecal microbiota, modified the VFA profile in sow’s faeces during lactation and barely impacted the faecal microbiota of slow and fast growing piglets. The third study showed that replacing a source soluble DFs by one of insoluble DFs in sow’s diet during late gestation and lactation reduced farrowing duration, increased total VFAs and lactoferrin concentrations in colostrum, improved growth performance from birth to 1 day of lactation, during the post-weaning period and throughout the study, and reduced diarrhoea occurrence during the first week post-weaning. Finally, a fourth study proposed a workflow to analyse low biomass samples from the umbilical cord blood aiming at investigating the existence of a pre-birth microbiota with no substantial findings to confirm this hypothesis. Overall, the results of these studies confirmed that, besides the level of DFs, the sources, and the types of DFs included in the sow's diet shape the sow's microbiota, influence the composition of colostrum and milk, and improve offspring performance, but with limited impacts on the microbiota of piglets.

A Trans-dimensional inversion algorithm to model deformation sources with unconstrained shape in finite element domains

Ground deformation provides valuable insights on subsurface processes with pattens reflecting the characteristics of the source at depth. In active volcanic sites displacements can be observed in unrest phases; therefore, a correct interpretation is essential to assess the hazard potential. Inverse modeling is employed to obtain quantitative estimates of parameters describing the source. However, despite the robustness of the available approaches, a realistic imaging of these reservoirs is still challenging. While analytical models return quick but simplistic results, assuming an isotropic and elastic crust, more sophisticated numerical models, accounting for the effects of topographic loads, crust inelasticity and structural discontinuities, require much higher computational effort and information about the crust rheology may be challenging to infer. All these approaches are based on a-priori source shape constraints, influencing the solution reliability. In this thesis, we present a new approach aimed at overcoming the aforementioned limitations, modeling sources free of a-priori shape constraints with the advantages of FEM simulations, but with a cost-efficient procedure. The source is represented as an assembly of elementary units, consisting in cubic elements of a regular FE mesh loaded with a unitary stress tensors. The surface response due to each of the six stress tensor components is computed and linearly combined to obtain the total displacement field. In this way, the source can assume potentially any shape. Our tests prove the equivalence of the deformation fields due to our assembly and that of corresponding cavities with uniform boundary pressure. Our ability to simulate pressurized cavities in a continuum domain permits to pre-compute surface responses, avoiding remeshing. A Bayesian trans-dimensional inversion algorithm implementing this strategy is developed. 3D Voronoi cells are used to sample the model domain, selecting the elementary units contributing to the source solution and those remaining inactive as part of the crust.

Pulse shape studies of neutral particles with a liquid scintillator

The hadrontherapy exploits beams of charged particles against deep cancers. These ions have a depth-dose profile in which there is a little release of energy at the beginning of their path, whereas there is a sharp maximum, the Bragg Peak, near its end path. However, if heavy ions are used, the fragmentation of the projectile can happen and the fragments can release some dose outside the treatment volume beyond the Bragg peak. The fragmentation process takes place also when the Galactic Cosmic Rays at high energy hit the spaceship during space missions. In both cases some neutrons can be produced and if they interact with the absorbing materials nuclei some secondary particles are generated which can release energy. For this reason, studies about the cross section measurements of the fragments generated during the collisions of heavy ions against the tissues nuclei are very important. In this context, the FragmentatiOn Of Target (FOOT) experiment was born, and aims at measuring the differential and double differential fragmentation cross sections for different kinetic energies relevant to hadrontherapy and space radioprotection with high accuracy. Since during fragmentation processes also neutrons are produced, tests of a neutron detection system are ongoing. In particular, recently a neutron detector made up of a liquid organic scintillator, BC-501A with neutrons/gammas discrimination capability was studied, and it represents the core of this thesis. More in details, an analysis of the data collected at the GSI laboratory, in Darmstadt, Germany, is effectuated which consists in discriminating neutral and charged particles and then to separate neutrons from gammas. From this analysis, a preliminary energy-differential reaction cross-section for the production of neutrons in the 16O + (C_2H_4)_(n) and 16O + C reactions was estimated.

Comparison Of Postoperative Stability Of Three Rigid Internal Fixation Techniques After Sagittal Split Ramus Osteotomy For Mandibular Advancement.

The aim of this investigation was to compare the skeletal stability of three different rigid fixation methods after mandibular advancement. Fifty-five class II malocclusion patients treated with the use of bilateral sagittal split ramus osteotomy and mandibular advancement were selected for this retrospective study. Group 1 (n = 17) had miniplates with monocortical screws, Group 2 (n = 16) had bicortical screws and Group 3 (n = 22) had the osteotomy fixed by means of the hybrid technique. Cephalograms were taken preoperatively, 1 week within the postoperative care period, and 6 months after the orthognathic surgery. Linear and angular changes of the cephalometric landmarks of the chin region were measured at each period, and the changes at each cephalometric landmark were determined for the time gaps. Postoperative changes in the mandibular shape were analyzed to determine the stability of fixation methods. There was minimum difference in the relapse of the mandibular advancement among the three groups. Statistical analysis showed no significant difference in postoperative stability. However, a positive correlation between the amount of advancement and the amount of postoperative relapse was demonstrated by the linear multiple regression test (p < 0.05). It can be concluded that all techniques can be used to obtain stable postoperative results in mandibular advancement after 6 months.

Direct Visualization Of The Action Of Triton X-100 On Giant Vesicles Of Erythrocyte Membrane Lipids.

The raft hypothesis proposes that microdomains enriched in sphingolipids, cholesterol, and specific proteins are transiently formed to accomplish important cellular tasks. Equivocally, detergent-resistant membranes were initially assumed to be identical to membrane rafts, because of similarities between their compositions. In fact, the impact of detergents in membrane organization is still controversial. Here, we use phase contrast and fluorescence microscopy to observe giant unilamellar vesicles (GUVs) made of erythrocyte membrane lipids (erythro-GUVs) when exposed to the detergent Triton X-100 (TX-100). We clearly show that TX-100 has a restructuring action on biomembranes. Contact with TX-100 readily induces domain formation on the previously homogeneous membrane of erythro-GUVs at physiological and room temperatures. The shape and dynamics of the formed domains point to liquid-ordered/liquid-disordered (Lo/Ld) phase separation, typically found in raft-like ternary lipid mixtures. The Ld domains are then separated from the original vesicle and completely solubilized by TX-100. The insoluble vesicle left, in the Lo phase, represents around 2/3 of the original vesicle surface at room temperature and decreases to almost 1/2 at physiological temperature. This chain of events could be entirely reproduced with biomimetic GUVs of a simple ternary lipid mixture, 2:1:2 POPC/SM/chol (phosphatidylcholine/sphyngomyelin/cholesterol), showing that this behavior will arise because of fundamental physicochemical properties of simple lipid mixtures. This work provides direct visualization of TX-100-induced domain formation followed by selective (Ld phase) solubilization in a model system with a complex biological lipid composition.

Dielectron Mass Spectra From Au+au Collisions At √[s(nn)]=200 gev.

We report the STAR measurements of dielectron (e(+)e(-)) production at midrapidity (|y(ee)|<1) in Au+Au collisions at √[s(NN)]=200  GeV. The measurements are evaluated in different invariant mass regions with a focus on 0.30-0.76 (ρ-like), 0.76-0.80 (ω-like), and 0.98-1.05 (ϕ-like)   GeV/c(2). The spectrum in the ω-like and ϕ-like regions can be well described by the hadronic cocktail simulation. In the ρ-like region, however, the vacuum ρ spectral function cannot describe the shape of the dielectron excess. In this range, an enhancement of 1.77±0.11(stat)±0.24(syst)±0.33(cocktail) is determined with respect to the hadronic cocktail simulation that excludes the ρ meson. The excess yield in the ρ-like region increases with the number of collision participants faster than the ω and ϕ yields. Theoretical models with broadened ρ contributions through interactions with constituents in the hot QCD medium provide a consistent description of the dilepton mass spectra for the measurement presented here and the earlier data at the Super Proton Synchrotron energies.

Communication: Transient Anion States Of Phenol…(h₂o)n (n = 1, 2) Complexes: Search For Microsolvation Signatures.

We report on the shape resonance spectra of phenol-water clusters, as obtained from elastic electron scattering calculations. Our results, along with virtual orbital analysis, indicate that the well-known indirect mechanism for hydrogen elimination in the gas phase is significantly impacted on by microsolvation, due to the competition between vibronic couplings on the solute and solvent molecules. This fact suggests how relevant the solvation effects could be for the electron-driven damage of biomolecules and the biomass delignification [E. M. de Oliveira et al., Phys. Rev. A 86, 020701(R) (2012)]. We also discuss microsolvation signatures in the differential cross sections that could help to identify the solvated complexes and access the composition of gaseous admixtures of these species.

Growth Factor Stimulation Improves The Structure And Properties Of Scaffold-free Engineered Auricular Cartilage Constructs.

The reconstruction of the external ear to correct congenital deformities or repair following trauma remains a significant challenge in reconstructive surgery. Previously, we have developed a novel approach to create scaffold-free, tissue engineering elastic cartilage constructs directly from a small population of donor cells. Although the developed constructs appeared to adopt the structural appearance of native auricular cartilage, the constructs displayed limited expression and poor localization of elastin. In the present study, the effect of growth factor supplementation (insulin, IGF-1, or TGF-β1) was investigated to stimulate elastogenesis as well as to improve overall tissue formation. Using rabbit auricular chondrocytes, bioreactor-cultivated constructs supplemented with either insulin or IGF-1 displayed increased deposition of cartilaginous ECM, improved mechanical properties, and thicknesses comparable to native auricular cartilage after 4 weeks of growth. Similarly, growth factor supplementation resulted in increased expression and improved localization of elastin, primarily restricted within the cartilaginous region of the tissue construct. Additional studies were conducted to determine whether scaffold-free engineered auricular cartilage constructs could be developed in the 3D shape of the external ear. Isolated auricular chondrocytes were grown in rapid-prototyped tissue culture molds with additional insulin or IGF-1 supplementation during bioreactor cultivation. Using this approach, the developed tissue constructs were flexible and had a 3D shape in very good agreement to the culture mold (average error <400 µm). While scaffold-free, engineered auricular cartilage constructs can be created with both the appropriate tissue structure and 3D shape of the external ear, future studies will be aimed assessing potential changes in construct shape and properties after subcutaneous implantation.