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12 pags., 6 figs., Sub-nanometer Metal clusters have special physical and chemical properties, significantly different from those of nanoparticles. However, there is a major concern about their thermal stability and susceptibility to oxidation. In situ X-ray Absorption spectroscopy and Near Ambient Pressure X-ray Photoelectron spectroscopy results reveal that supported Cu5 clusters are resistant to irreversible oxidation at least up to 773 K, even in the presence of 0.15 mbar of oxygen. These experimental findings can be formally described by a theoretical model which combines dispersion-corrected DFT and first principles thermochemistry revealing that most of the adsorbed O2 molecules are transformed into superoxo and peroxo species by an interplay of collective charge transfer within the network of Cu atoms and large amplitude "breathing" motions. A chemical phase diagram for Cu oxidation state of the Cu5-oxygen system is presented, clearly different from the already known bulk and nano-structured chemistry of Cu., This work has been partly supported by the Spanish Ministerio de Ciencia e Innovación (TED2021-131899BI00/MCIN/AEI/10.13039/501100011033/ Unión Europea NextGenerationEU/PRTR), and the Agencia Estatal de Investigación (AEI) and the Fondo Europeo de Desarrollo Regional (FEDER, UE) under Grants Nos, PID2019-107115GBC21, and PID2020-117605GB-I00; the EU Doctoral Network PHYMOL 101073474 (project call reference HORIZON-MSCA2021-DN-01); the Austrian Science Fund (FWF) under Grant P29893-N36; XUNTA DE GALICIA (Spain) (Grupos Ref. Comp. 2021 - ED431C 2021/16); ANPCyT PICT (2017-1220 and 2017- 3944) and UNLP (Project 11/X937), Argentina. This publication is also based upon work of COST Action CA21101 "Confined molecular systems: from a new generation of materials to the stars" (COSY) supported by COST (European Cooperation in Science and Technology).

Silicon dioxide (SiO2) obtained by Sol–Gel methods is widely used as adsorbents, catalytic supports, filter membranes and in drugs delivery, among others. For most of the applications, surface area and porosity are key parameters that should be controlled, depending on the purpose of the material. These characteristics depend on the chemistry of the precursors in solution. Silicon alkoxides are commonly used as precursors, where the chemical pathway to produce sols and then gels depends on several factors such as water/alcohol ratio, pH, type of catalyst, temperature, etc. In order to control the microstructural characteristics of SiO2, it is necessary to understand the effect of the different chemical components on the hydrolysis-condensation reactions. In this work, we explored the acid-catalyzed hydrolysis and condensation reactions of silicon tetra-ethyl-alkoxide (TEOS) employing three common acids: HF, HCl, and HNO3. Gel formation kinetics was studied by low field nuclear magnetic resonance. Structural evolution of gels and xerogels at the nanoscale was determined by small angle X-ray scattering (SAXS). The microstructure of xerogels was determined by nitrogen adsorption (BET method), and by scanning and transmission electron microscopy (SEM and TEM, respectively). The final SiO2 products revealed different porosity type and texture depending on the acid employed, which are related to the chemical pathway during the sol–gel transition.

Hydrogen bonding plays a critical role in the self-assembly of peptide amphiphiles (PAs). Herein, we studied the effect of replacing the amide linkage between the peptide and lipid portions of the PA with a urea group, which possesses an additional hydrogen bond donor. We prepared three PAs with the peptide sequence Phe-Phe-Glu-Glu (FFEE): two are amide-linked with hydrophobic tails of different lengths and the other possesses an alkylated urea group. The differences in the self-assembled structures formed by these PAs were assessed using diverse microscopies, nuclear magnetic resonance (NMR), and dichroism techniques. We found that the urea group influences the morphology and internal arrangement of the assemblies. Molecular dynamics simulations suggest that there are about 50% more hydrogen bonds in nanostructures assembled from the urea-PA than those assembled from the other PAs. Furthermore

The hydrothermal synthesis of the perovskites NaNbO3, NaTaO3 and the intermediate composition NaNb0.5Ta0.5O3, as CO2 conversion photocatalysts is reported. Among them, the niobate shows the most promising performance under UV irradiation not only in terms of conversion and light utilization ability, but also regarding the selectivity towards CO2 reduction against hydrogen evolution from water protons. Further modification of NaNbO3 with silver as co-catalyst results in an increase of the selectivity towards highly reduced products, primarily methanol, against the carbon monoxide production mainly observed with the bare semiconductor. A thorough structural, electronic, electrochemical characterization, together with in-situ surface analysis by APXPS, was undertaken to gain deeper insight into the reasons that account for such changes. On the one hand, for the bare semiconductors, increased light absorption and the sole presence of Nb in +4 state at the surface seem to drive the superior activity of NaNbO3. On the other hand, electronic and surface chemistry modifications induced by 0.1 wt.% silver deposition are proposed to govern the higher selectivity towards methanol. Excessive metal loading, in turn, enhances the selectivity effect but at the expense of conversion, in such a way that light utilization becomes poorer than with the bare niobate.

Polycaprolactone (PCL)-based nanocomposites reinforced with different clay loadings (1.5, 3 and 5 wt%) of neat and organo-modified bentonites were successfully fabricated using twin-screw melt extrusion followed by melt compression. The whole processing of the materials, including the organic modification of bentonite with benzalkonium chloride (CBK), which is a mixture of cationic surfactants with biocide properties, and the preparation of the nanocomposites by melt extrusion, was fully carried out at pilot scale. The resulting materials were structurally, thermally and mechanically characterized. Our results suggest that while raw natural bentonite acted as a regular inorganic reinforcement, CBK intercalation enhanced the compatibility of the clay with the polymeric matrix, evidenced in an increase in the tensile strength and Young's modulus in a factor of ca. 2 respect to neat PCL values, with only a 3 wt% organoclay loading. The modified clay presented a strong orientation within the matrix due to the material processing and manufacture, registered by small-angle X-ray scattering experiments.

Siloxane-pHEMA hybrid coatings with the addition of calcium chloride and calcium sulfate during the synthesis of the material were produced by the sol–gel method and deposited on Ti-6Al-4V alloy by dip-coating. The structural characteristics of the hybrid materials were analyzed by means of Nuclear Magnetic Resonance and Small/Wide Angle X-ray Scattering; their morphological properties were analyzed by means of Scanning Electron Microscopy and Atomic Force Microscopy. The electrochemical behavior and resistance to corrosion of hybrid coatings with and without addition of calcium salts were analyzed by means of Electrochemical Impedance Spectroscopy. The results showed that the coatings were homogeneous due to the rigid silica network formed during the polymerization, hydrolysis and reactions of condensation. In the sample, into which calcium sulfate was added, there was a decrease of the average roughness value (15.0 nm), while exhibiting regular topography and good adhesion to the substrate, suggesting that this coating has appealing characteristics for anticorrosive applications. Electrochemical tests in simulated body fluid (that underwent simulation) showed that the coatings with hybrid system showed better properties of a barrier with up to 96 h of immersion, in comparison to samples without coating. Therefore, these coatings showed promising features suitable for anticorrosion applications in biomaterials. Moreover, due to the addition of calcium sulfate, coatings made it possible to convey a good balance between biological and anticorrosion properties and, which in itself allows biocompatibility without compromising resistance to corrosion.

Direct back-face transmission steady-state fluorescence was successfully applied to the study of aggregation of ibuprofen and ibuprofenate anion in solution taking advantage of its own fluorescence. The analysis of the experimental data involves the use of the differential reabsorption model to account for re-absorption phenomenon and the closed association model to describe aggregation. The fluorescence quantum yield of ibuprofenate increases when it aggregates in the presence of sodium, but it markedly decreases when 1-butyl-3-methylimidazolium is used as counterion. The proposed methodology allows the accurate determination of the critical aggregation concentrations and the mean aggregation numbers. Results were supported by complementary techniques such as time-resolved fluorescence

A new one-pot homogeneous methodology at room temperature to obtain Au nanoparticles (AuNP) on the basis of the epoxide route is presented. The proposed method takes advantage of the homogenous generation of OH- moieties driven by epoxide ring-opening, mediated by chloride nucleophilic attack. Once reached alkaline conditions, the reducing medium allows the quantitative formation of AuNP under well-defined kinetic control. A stabilizing agent, such as polyvinylpyrrolidone (PVP) or cetyltrimethylammonium chloride (CTAC), is required to maintain the AuNP stable. Meanwhile their presence dramatically affects the reduction kinetics and pathway, as demonstrated by the evolution of the UV/Vis spectra, small-angle X-ray scattering (SAXS) patterns, and pH value along the reaction. In the presence of PVP nanogold spheroids are obtained following a similar reduction mechanism as that observed for control experiments in the absence of PVP. However, if CTAC is employed a stable complex with AuIII is formed, leading to a different reaction pathway and resulting in ellipsoidal-like shaped AuNP. Moreover, the proposed methodology allows stabilize the growing AuNP, by coupling their formation with nonalkoxidic sol-gel reactions, leading to nanocomposite gels with embedded metallic nanoparticles. The epoxide route thus offers a versatile scenario for the one-pot preparation of new metal nanoparticles-inorganic/hybrid matrices nanocomposites with valuable optical properties.

A series of three triphenylene compounds – denoted 2,7-THTP-DiCnOH – bearing four hexyloxy ancillary chains and two variable-length alkoxy chains terminally functionalized with hydroxyl groups have been synthesized and characterized. The studied compounds exhibited thermotropic mesomorphism; the detailed nature of the mesophases was found to depend on the relative positions of the terminal functional groups relative to the crown formed by the ancillary chains. All the studied compounds were able to act as supramolecular gelators in a variety of alcohols; their organogelating ability has been rationalized in terms of physicochemical parameters like the dielectric constant, which allowed us to establish very precise predictive “solvent gelation windows” for each compound. Remarkably stable gels have been detected for 2,7-THTP-DiC6OH in methanol. As a proof of principle, we present the water sensing performance as a rapid method for the assessment of water content in alcohol samples based on the influence that the water content exerts on the gels’ thermostability., Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas

Supramolecular nanostructures with tunable properties can have applications in medicine, pharmacy, and biotechnology. In this work, we show that the self-assembly behavior of peptide amphiphiles (PAs) can be effectively tuned by replacing the carboxylic acids exposed to the aqueous media with isosteres, functionalities that share key physical or chemical properties with another chemical group. Transmission electron microscopy, atomic force microscopy, and small-angle X-ray scattering studies indicated that the nanostructure's morphologies are responsive to the ionization states of the side chains, which are related to their pKa values. Circular dichroism studies revealed the effect of the isosteres on the internal arrangement of the nanostructures. The interactions between diverse surfaces and the nanostructures and the effect of salt concentration and temperature were assessed to further understand the properties of these self-assembled systems. These results indicate that isosteric replacements allow the pH control of supramolecular morphology by manipulating the pKa of the charged groups located on the nanostructure's surface. Theoretical studies were performed to understand the morphological transitions that the nanostructures underwent in response to pH changes, suggesting that the transitions result from alterations in the Coulomb forces between PA molecules. This work provides a strategy for designing biomaterials that can maintain or change behaviors based on the pH differences found within cells and tissues.

21 pags., 5 figs., Subnanometer-sized metal clusters often feature a molecule-like electronic structure, which makes their physical and chemical properties significantly different from those of nanoparticles and bulk material. Considering potential applications, there is a major concern about their thermal stability and susceptibility towards oxidation. Cu clusters of only 5 atoms (Cu5 clusters) are first synthesized in high concentration using a new-generation wet chemical method. Next, it is shown that, contrary to what is currently assumed, Cu5 clusters display nobility, beyond resistance to irreversible oxidation, at a broad range of temperatures and oxygen pressures. The outstanding nobility arises from an unusual reversible oxidation which is observed by in situ X-ray Absorption Spectroscopy and X-ray Photoelectron Spectroscopy on Cu5 clusters deposited onto highly oriented pyrolitic graphite at different oxygen pressures and up to 773 K. This atypical property is explained by a theoretical approach combining different state-of-the-art first principles theories. It reveals the essential role of collective quantum effects in the physical mechanism responsible for the nobility of Cu5 clusters, encompassing a structural ‘breathing’ through concerted Cu–Cu elongations/contractions upon O2 uptake/release, and collective charge transfer as well. A predictive phase diagram of their reversible oxidation states is also delivered, agreeing with the experimental observations. The collective quantum effects responsible of the observed nobility are expected to be general in subanometer-sized metal clusters, pushing this new generation of materials to an upper level., This work has been partly supported by the European Union’s Horizon 2020 Research and Innovation Programme un-der Grant Agreement No. 825999; the Spanish Agencia Estatal de Investigación (AEI) and the Fondo Europeo de Desarrollo Regional (FEDER, UE) under Grant No. MAT2016-75354-P; the Austrian Science Fund (FWF) under Grant P29893-N36; the CMST COST Action CM1405 “Molecules in Motion” (MOLIM); the Xunta de Galicia, Spain (Grupos Ref. Comp.ED431C 2017/22 and AEMAT ED431E 2018/08); Obra Social Fundación La Caixa: Ref.LCF/PR/PR12/11070003; ANPCyT PICT (2017-1220 and 2017-3944) and UNLP (Project11/X790), Argentina.

Superparamagnetic iron oxide nanoparticles (SPIONs) are great adsorbents of toxic arsenic in water. However, SPIONs efficiency is limited by a tendency towards agglomeration, and an extra filtering process is required in actual applications to avoid possible harmful effects of nanoparticles released to the environment. Here, we show a novel green method to confine and disperse SPIONs (10 nm) inside insoluble electrospun PVA nanofibers (final concentration 0.14 wt. %). We found that the resulting membrane has an enhanced arsenic adsorption capacity (> 52 mg/g) and presents a new adsorption mechanism, involving a high swelling of the superhydrophilic nanofibers before actual solution interchange can occur. A suitable heat treatment provided water insolubility to the membrane while maintaining hydrophilicity and active sites in the SPIONs. We show the excellent dispersion and homogeneous distribution of the SPIONs inside the nanofibers using electron microscopies and scale this analysis to an area of statistical significance via magnetic studies and novel Small and Wide Angle X-Ray Scattering SAXS/WAXS 2D scannings. The production process is environmentally friendly, given that only PVA was used as SPIONs dispersant and no chemicals were added for crosslinking. This work presents a novel material that expands the broad technological applications of both iron oxide nanoparticles and electrospinning, opening a route to new horizons in water purification., We kindly acknowledge the financial support of UBA (UBACYT 2018-2020 No 20020170100381BA), ANPCyT (PICT 2017-2362, PICT 2017-3150) and the Ministerio de Ciencia, Innovación y Universidades code PID2019-104650GB-C21 (MCIU/AEI/FEDER, UE).

Calcium phosphates stand among the most promising nanobiomaterials in key biomedical applications, such as bone repairment, signalling or drug/gene delivery. Their intrinsic properties as crystalline structure, composition, particle shape and size define their successful use. Among these compounds, metastable amorphous calcium phosphate (ACP) is currently gaining particular attention due to its inherently high reactivity in solution, which is crucial in bone development mechanisms. However, the preparation of this highly desired (bio)material with control over its shape, size and phase purity remains as a synthetic challenge. In this work, the epoxide route was adapted for the synthesis of pure and stable ACP colloids. By using biocompatible solvents, such as ethylene glycol and/or glycerine, it was possible to avoid the natural tendency of ACP to maturate into more stable and crystalline apatites. Moreover, this procedure offers size control, ranging from small nanoparticles (60 nm) to micrometric spheroids (>500 nm). The eventual fractalization of the internal mesostructured can be tuned, by simply adjusting the composition of the ethylene glycol:glycerine solvent mixture. These findings introduce the use of green solvents as a new tool to control crystallinity and/or particle size in the synthesis of nanomaterials, avoiding the use of capping agents and preserving the natural chemical reactivity of the pristine surface.

In this work, the preparation and thermal evolution of sputtered semicontinuous gold thin films obtained over ordered mesoporous TiO2 films are presented. The controlled surface topography of the ordered mesoporous TiO2 substrate was used as template for obtaining plasmonic hotspots for Surface Enhanced Raman Spectroscopy (SERS) applications. Plasmonic thin film was obtained by Au sputtering when film thickness was under circa 10 nm. Above this value, the porosity effects from the substrate were lost and Raman signal enhancement with it. Moreover, heat treatment was explored in order to obtain gold nanoislands that can also provide very efficient Raman enhancement. Hence, a very straightforward synthesis procedure is presented for sensing application, even for large scale production. Fil: Zalduendo, María Mercedes. Comisión Nacional de Energía Atómica. Gerencia del Área de Seguridad Nuclear y Ambiente. Gerencia de Química (CAC); Argentina. Comisión Nacional de Energía Atómica. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología. - Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología; Argentina Fil: Steinberg, Paula Yael. Comisión Nacional de Energía Atómica. Gerencia del Área de Seguridad Nuclear y Ambiente. Gerencia de Química (CAC); Argentina. Comisión Nacional de Energía Atómica. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología. - Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología; Argentina Fil: Prudente, Tomás. Universidad Nacional de San Martín. Escuela de Ciencia y Tecnología; Argentina Fil: Di Liscia, Emiliano Javier. Comisión Nacional de Energía Atómica. Gerencia de Área Investigaciones y Aplicaciones No Nucleares. Gerencia Física (CAC). Departamento de Física de la Materia Condensada; Argentina Fil: Morrone, Josefina. Comisión Nacional de Energía Atómica. Gerencia del Área de Seguridad Nuclear y Ambiente. Gerencia de Química (CAC); Argentina. Comisión Nacional de Energía Atómica. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología. - Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología; Argentina Fil: Angelome, Paula Cecilia. Comisión Nacional de Energía Atómica. Gerencia del Área de Seguridad Nuclear y Ambiente. Gerencia de Química (CAC); Argentina. Comisión Nacional de Energía Atómica. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología. - Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología; Argentina Fil: Huck Iriart, Cristián. Universidad Nacional de San Martín. Escuela de Ciencia y Tecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina

Hydrogels obtained by acidification with glucono-δ-lactone (GDL), starting from nanoemulsions formulated with different concentrations of sodium caseinate (1–4 wt%) or 4 wt% sodium caseinate and sucrose (2–8 wt%), were prepared with the aim of quantifying structural parameters of both, initial nanoemulsions and hydrogels after 2.5 h of GDL addition, using the Guinier-Porod (GP) or the generalized GP models. Gelation process was followed by performing in situ temperature-controlled X-ray small angle scattering experiments (SAXS) using synchrotron radiation. In nanoemulsions, the calculated radius of gyration for oil nanodroplets (Rgoil) decreased with increasing protein concentration and for the 4 wt% protein nanoemulsion, with increasing sucrose content. Calculated values of Rgoil were validated correlating them with experimental Z-average values as measured by dynamic light scattering (DLS). For hydrogels, radii of gyration for the sphere equivalent to the hydrogel scattering object (Rgsph) were close to 3 nm while correlation distances among building blocks (Rg2) were dependent on formulation. They increased with increasing contents of sodium caseinate and sucrose. Rg2 parameter linearly correlated with hydrogel strength (G’∞): a more connected nanostructure led to a stronger hydrogel., Graphical abstract Image 1, Highlights • Nanodroplets gyration ratio decreased with increasing protein and sucrose contents • Nanodroplets coverage increased with increasing protein and sucrose contents • Building blocks gyration ratio of gels were independent on composition • Building blocks correlation distances were significantly affected by composition • Rg2 distances correlated with asymptotic values of G’ (G’∞)

Objectives At the end of 2019 the SARS-CoV-2 outbreak spread around the globe with a late arrival to South America. The objective of this study was to evaluate the impact of the long period of mandatory social isolation that took place in Argentina on the general psychological well-being of healthcare workers due to the COVID-19 pandemic. Methods A survey was conducted during June 2020, in healthcare workers. Pittsburgh Sleep Quality Index, Insomnia Severity Index, Sleepiness-Wakefulness Inability and Fatigue Test, and Goldberg depression and anxiety scale, were used to analyze the effects of the SARS-Cov 2 outbreak after three months of mandatory social isolation. Analyses were performed by logistic regression and a clustering algorithm in order to classify subjects in the function of their outcome's severity. Results From 1059 surveys, the majority reported symptoms of depression (81.0%), anxiety (76.5%), poor sleep quality (84.7%), and insomnia (73.7%) with 68.9% suffering from nightmares. Logistic regression showed that being in contact with COVID-19 patients, age, gender and the consumption of sleep medication during the mandatory social isolation were relevant predictors for insomnia, anxiety, and depression. Clustering analysis classified healthcare workers in three groups with healthy/mild, moderate, and severe outcomes. The most vulnerable group was composed mainly of younger people, female, non-medical staff, or physicians in training. Conclusion An extremely high proportion of Argentinian healthcare workers suffered from sleep problems, anxiety, and depression symptoms. The clustering algorithm successfully separates vulnerable from non-vulnerable populations suggesting the need to carry out future studies involving resilience and vulnerability factors., Highlights • COVID-19 social isolation is related to insomnia, anxiety, and depression symptoms. • Nightmares were correlated with high levels of anxiety during COVID-19 outbreak. • Younger people, women, and non-medical health workers were the most affected population. • K-means algorithm successfully separates vulnerable from non-vulnerable populations.

The synthesis of Au nanowires (NWs) in hexane solution of HAuCl4·3H2O, oleylamine and triisopropylsilane at room temperature was "in situ" monitored by means of X-ray absorption fine structure spectroscopies and small-angle X-ray scattering to determine, under identical synthesis conditions, both the changes in the oxidation state of gold atoms and the evolution of the size and shape of the objects involved in the formation of Au NWs. We propose a multistage process for the formation of the NWs: first, Au(III) atoms form a planar-square geometry complex that is continuously reduced to give Au(I) disk-like structures with diameters bigger than that of the final NWs. In a second stage, characteristic length/thickness ratio of these disk-like objects increases to form cylinders, presumably through aurophilic interactions between Au(I) centers and stacking of the disks. When most of the Au atoms have been reduced to Au(I), the reduction to Au(0) begins (third stage), and the NWs grow to form an hexagonal arrangement, separated by a bilayer of oleylamine molecules (fourth stage). Finally, a slow reduction leads the reaction to the final product, formed by bundles of long, ultrathin Au NWs. Fil: Pschunder, Fernando. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina Fil: Puig, Julieta. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; Argentina Fil: Giovanetti, Lisandro Jose. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina Fil: Huck Iriart, Cristián. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de San Martín; Argentina Fil: Requejo, Felix Gregorio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina Fil: Buceta, David. Universidad de Santiago de Compostela; España Fil: Hoppe, Cristina Elena. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; Argentina Fil: Ramallo Lopez, Jose Martin. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina

The redox chemistry of the N-nitrosamine complexes [IrCl5(RN(H)NO)]2- (R = benzyl or n-butyl) was studied in detail. One-electron oxidations at around 200 mV vs. ferrocene/ferrocenium were reversible in cyclic voltammograms. UV-vis spectroelectrochemistry reveals spectra characteristic of IrIV species but also partial decomposition of the oxidised species [IrIVCl5(RN(H)NO)]- on this timescale (minutes). Detailed studies on chemically oxidised solutions of the parent IrIII complexes gave evidence for paramagnetic IrIV from NMR spectra. Final products of the decomposition were the corresponding alcohols and presumably [IrIIICl5(L)]2- (L = N2, solvent, amine) complexes. Similar decomposition reactions of acidic DMSO solutions of [IrCl5(RN(H)NO)]2-revealed that this combination produces the so-called "activated" DMSO (Me2S+-O- or Me2S+-OE, with "E" being an electrophile) which oxidises the parent IrIII complexes. Finally, with the very reactive purple IrIV compound (PPh4)[IrCl5(BnN(H)NO)], the first primary N-nitrosamine coordinated to [IrIVCl5]- was isolated and characterised by UV-vis absorption, FTIR, NMR spectroscopy, ultra-high resolution electrospray mass spectrometry (UHR-ESI-MS) and iridium L3 X-ray absorption near-edge spectroscopy (XANES)., Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas

We have studied for the first time the relevant features of the thermally activated nanostructural transformations occurring in a material initially consisting of a flat Si(001) wafer in which a nanoporous Ni-doped silica film is deposited. Two simultaneous transformation processes occur, and both were investigated by in situ grazing-incidence small-angle X-ray scattering during isothermal annealing at 405 °C, namely the kinetics of formation of (i) oriented NiSi2 hexagonal nanoplates endotaxially buried in a Si(001) wafer, and (ii) a set of randomly oriented spherical Ni nanocrystals with a two-mode radius distribution embedded in a Ni-doped silica thin film deposited on the Si wafer and in an intermediate layer between SiO2 film and the layer in which NiSi2 nanoplates are embedded. The analyses of the successive 2D scattering patterns measured in situ during isothermal annealing led us to establish the time invariances of the average radii of the spherical Ni nanocrystals and the time dependence of their number, together with the time dependences of the maximum diameter, thickness, number and total volume of the hexagonal NiSi2 nanoplates buried in the Si wafer.

In this work, we analyze Sm2O3-doped CeO2 (SDC) nanopowders and NiO/SDC nanocomposites in terms of sample reducibility and catalytic activity for partial oxidation of methane. We assess the role of the average crystallite size and specific surface area in Ni and Ce reduction kinetics by in-situ X-ray absorption spectroscopy experiments in diluted H2 and CH4/O2 mixtures. Our results indicate that crystallite size and surface area play a key role in CH4 activation through modification of the sample redox behavior. The oxidation of the metallic phase is the main cause of sample deactivation. A clear relationship is established between the temperature of maximum Ni oxidation rate and grain size. An interplay between Ce atoms from the support and Ni from the active phase was observed during the experiments, evidencing a complex relationship between oxygen vacancy concentration and catalytic activity. A high Ce3+ content in catalyst support was detrimental to catalytic activity

Legislation and concerns about health effects of trans and saturated fatty acids have led to elimination or reduction of them in foods formulation. One of the alternatives for structuring food with healthy ingredients is using food-grade biopolymers such as proteins or polysaccharides to formulate hydrogels. The aim of the present work was to study the relationship among formulation, gelation kinetics, structure, and rheological properties of sodium caseinate (NaCas)/sunflower oil hydrogels prepared from nanoemulsions. NaCas was used as stabilizer in concentrations of 1, 2, 3, or 4 wt.%. Sucrose was also added in 2, 4, 6, or 8 wt.% to the 4-wt.% nanoemulsion. Gelation kinetics was studied by two methods: oscillatory rheometry and Turbiscan. Although gelation time values were significantly different between methods, tendencies were similar: values decreased with increasing protein and sucrose contents. However, the most influential factor on gelation time was the ratio glucono-delta-lactone (GDL)/NaCas. Structure was analyzed by confocal laser scanning microscopy and synchrotron X-ray microtomography. Low-protein content hydrogels (1 or 2 wt.%) had an inhomogeneous structure containing nano- and conventional-size droplets while the 4-wt.% hydrogel kept the initial structural characteristics: homogeneity in dispersed phase distribution and non-aggregated nanodroplets. Sucrose improved structure in terms of homogeneity. Analyses of X-ray microtomoghraphy data showed that while the porosity diminished, the wall width increased with increasing protein and sucrose contents. The hydrogel formulated with 4 wt.% NaCas and 8 wt.% sucrose showed a structure with nanodroplets evenly distributed and the highest G′∞ values of all hydrogels., Centro de Investigación y Desarrollo en Criotecnología de Alimentos

Cocoa butter (CB) is the preferred fat for chocolates and confections. However, for technological and economic reasons, there have been strong efforts for partially replacing it. As shea butter (SB) has become an important natural source of symmetrical stearic-rich triacylglycerols (TAG), the aim of this work was to study physical chemical behavior of blends of CB and SB and the dynamic mechanical and polymorphic behaviors of chocolates prepared with these systems as added fat. The compatibility of SB and CB blends was studied using the isosolid diagram. Data showed that softening occurred due to both dilution effects and a slight eutectic formation. Chocolates formulated with a fat phase consisting in CB, or SB, or blends with 10, 20, or 30 wt.% SB in CB showed different polymorphic behaviors during storage. The polymorphic transition from β 2 to β 1 occurred to a greater extent with increasing content of SB in formulation. Dynamic mechanical analysis (DMA) results agree with X-ray findings. E′ modulus significantly increased during storage most likely due to formation of β 1 form. As shown by Grazing incidence wide-angle X-ray scattering (GIWAXS) studies, crystals preferred growing on the chocolate surface than on bulk chocolate. However, even after a year at 18°C, chocolates had good appearance indicating that SB was a good CB extender. Fil: Rodriguez Negrette, Ana Carolina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Instituto de Tecnología en Polímeros y Nanotecnología. Universidad de Buenos Aires. Facultad de Ingeniería. Instituto de Tecnología en Polímeros y Nanotecnología; Argentina Fil: Huck Iriart, Cristián. Universidad Nacional de San Martín. Escuela de Ciencia y Tecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Herrera, Maria Lidia. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Instituto de Tecnología en Polímeros y Nanotecnología. Universidad de Buenos Aires. Facultad de Ingeniería. Instituto de Tecnología en Polímeros y Nanotecnología; Argentina

The anti-inflammatory, antifibrotic and antimicrobial activities of curcumin (CUR) are missed because of its low solubility in aqueous media, low bioavailability, and structural lability upon oral intake. Soft nanoparticles such as nanoliposomes are not efficient as CUR carriers, since crystalline CUR is expelled from them to physiological media. Nanostructures to efficiently trap and increase the aqueous solubility of CUR are needed to improve both oral or nebulized delivery of CUR. Here we showed that SRA1 targeted nanoarchaeosomes (nATC) [1:0.4 w:w:0.04] archaeolipids, tween 80 and CUR, 155 ± 16 nm sized of −20.7 ± 3.3 z potential, retained 0.22 mg CUR ± 0.09 per 12.9 mg lipids ± 4.0 (~600 μM CUR) in front to dilution, storage, and nebulization. Raman and fluorescence spectra and SAXS patterns were compatible with a mixture of enol and keto CUR tautomers trapped within the depths of nATC bilayer. Between 20 and 5 µg CUR/mL, nATC was endocytosed by THP1 and A549 liquid–liquid monolayers without noticeable cytotoxicity. Five micrograms of CUR/mL nATC nebulized on an inflamed air–liquid interface of A549 cells increased TEER, normalized the permeation of LY, and decreased il6, tnfα, and il8 levels. Overall, these results suggest the modified pharmacodynamics of CUR in nATC is useful for epithelia repair upon inflammatory damage, deserving further deeper exploration, particularly related to its targeting ability.

In this work, we described an image processing procedure for the measurement of surface tension of the air-liquid interface using isothermal capillary action. The experiment, designed for an undergraduate course, is based on the analysis of a series of solutions with diverse surfactant concentrations at different ionic strengths. The objective of the work is to illustrate some concepts such as Gibbs isotherm and surface excess for the case of ionic surfactants. To perform the experiment, it is necessary to use glassware commonly found in a chemistry lab along with an USB microscope and digital image processing program (available in the public domain). The experiment can be completed in a 4 h laboratory session. Fil: Huck Iriart, Cristián. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de San Martín. Escuela de Ciencia y Tecnología; Argentina Fil: de Candia, Ariel Gustavo. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de San Martín. Escuela de Ciencia y Tecnología; Argentina Fil: Rodriguez, Javier. Universidad Nacional de San Martín. Escuela de Ciencia y Tecnología; Argentina. Comisión Nacional de Energía Atómica; Argentina Fil: Rinaldi, Carlos Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de San Martín. Escuela de Ciencia y Tecnología; Argentina

Interest in polymer technology based on biodegradable and edible films has increased dramatically, in hopes of creating a circular economy with little to no environmental impact. In this study nanocomposite films with a glycerol/WPC ratio of 4/5 were prepared from emulsions containing 2.5, 5.0, or 7.5 wt.% WPC and 2 wt.% corn oil. Films also contained a load of 0.5 wt.% TiO2. Emulsions were prepared with two different droplet sizes: conventional (from 300 to 700 nm) and nano (from 60 to 80 nm). Films were analyzed for color, water vapor permeability, thermogravimetric, mechanical/tensile properties, infrared behavior, and structure. Advanced X-ray microscopy based on small and wide-angle scattering contrast was used to investigate the nanocomponents in the films, allowing the identification of the main scattering species. Film that was prepared from starting systems with nano droplets (60 nm), the highest protein concentration (7.5 wt.% WPC), and TiO2 loading had the greatest E’ (elastic modulus, 19.2 MPa), E (Young modulus, 19.4 MPa), and eb (elongation at break, 119 %) values. This nano-based film had suitable physical properties for cheese packaging and other similar applications. In all films, data showed a close correlation between film structure and mechanical/tensile properties.

Single-phased La0.6Sr0.4Co1-yFeyO3-d (y = 0.2, 0.5, 0.8) nanorods exhibiting the rhombohedral perovskite-type phase were synthesized by a pore-wetting technique. We studied their chemical composition, crystal and electronic structures, morphology and hyperfine properties as a function of the Co/Fe content of the samples. Our results demonstrate that Co cations exhibit a slightly lower oxidation state than Fe ones, resulting in a higher oxygen non-stoichiometry d for Co-rich samples. In addition, the values of d determined in this work for nanostructured samples are much higher than those reported in the literature for bulk materials. This can be attributed to the high degree of defects in nanomaterials and is probably one important factor in the high electrochemical performance for the oxygen reduction reaction of nanostructured La0.6Sr0.4Co1-yFeyO3-d IT-SOFC cathodes, which have been reported in a previous work. Keywords: electrode materials; nanostructured materials; X-ray diffraction; NEXAFS; M\"ossbauer spectroscopy, Comment: 18 pages, 8 figures, accepted for publication

The stability and photo Fenton activity of nanoarchitectured silicates modified with Fe by the wet impregnation method were studied as a function of the used solvent, calcination temperature and iron loading. The physicochemical properties were characterized by SAXS, XRD, N2 physisorption, SEM, AA, UV–Vis DR, XPS and TPR. All solids showed long-range structural order typical of SBA-15 with high specific surface, PV and a narrow distribution of PD. The proper choice of impregnation solvent allowed tuning the iron speciation in order to obtain catalysts highly stable and efficient for their use in the azo dyes photo-Fenton degradation at pH = 3.5. Calcination temperature does not seem influence on such speciation. Isolated iron cations finely dispersed and strongly anchored on the mesoporous channels, whose formation is promoted by the use of ethanol and the low iron loading, are proposed as active sites for the photo-Fenton process. Likewise, low iron loadings also favor the higher accessibility of these sites to the reactant molecules (AO7 and H2O2). Thus, the highest dye mineralization degree was obtained by an actual iron loading of 1.31% wt. The heterogeneity of the process was confirmed. The more active solid also showed a high stability and reuse capacity, maintaining its performance. Fil: Elías, Verónica Rita. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Centro de Investigación y Tecnología Química. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación y Tecnología Química; Argentina Fil: Ochoa Rodríguez, Pablo Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Centro de Investigación y Tecnología Química. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación y Tecnología Química; Argentina Fil: Vaschetto, Eliana Gabriela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Centro de Investigación y Tecnología Química. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación y Tecnología Química; Argentina Fil: Pecchi, Gina A.. Universidad de Concepción; Chile Fil: Huck Iriart, Cristián. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de San Martín. Escuela de Ciencia y Tecnología; Argentina Fil: Casuscelli, Sandra Graciela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Centro de Investigación y Tecnología Química. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación y Tecnología Química; Argentina Fil: Eimer, Griselda Alejandra. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Centro de Investigación y Tecnología Química. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación y Tecnología Química; Argentina

Protein gels have attired attention since they allow structuring foods with no trans or saturated fats. The effects of protein concentration and sucrose addition on gelation kinetics and on physical properties of sodium caseinate (NaCas)/sunflower oil emulsion-based gels were studied by two methods: a new application of backscattering of light (BS) using a Turbiscan equipment and by dynamic oscillatory rheology. Structure of gels was also described by confocal laser scanning microscopy (CLSM) and small angle X-ray scattering (SAXS). T gel values decreased with increasing sucrose or NaCas concentration. BS method sensed early changes in structure, while rheological measurements were less sensitive to those changes. However, tendencies found by rheological measurements were the same as the ones found by BS experiments. CLSM images of gels formed from emulsions containing high sucrose and protein concentrations had big oil droplets that were not present in initial emulsions. Gels with sucrose concentrations between 15 and 30 wt/wt% released oil. SAXS patterns showed that NaCas nanoaggregate sizes in the aqueous phase were smaller with increasing sucrose concentration. Polar groups of protein interacted with sucrose, and therefore, interactions among protein molecules diminished. As a result of weaker protein molecule interactions, nanoaggregates were smaller. However, this effect was beneficial. In the macroscale, rheological properties and visual appearance of gels were improved. The gel formulated with 5 wt/wt% NaCas and 10 wt/wt% sucrose had a smooth surface and was stable to syneresis and oil release. This formulation was a good alternative to trans fat.

The steam reforming of ethanol (ESR) has been studied by near ambient pressure XPS (NAP-XPS), extended X-ray absorption fine structure (EXAFS), and X-ray absorption near edge structure (XANES) unde...

Understanding nanoparticle catalysis requires novel approaches in which adjoining crystal orientations can be studied under the same reactive conditions. Here we use a curved palladium crystal and near-ambient pressure X-ray photoemission spectroscopy to characterize chemical species during the catalytic oxidation of CO in a whole set of surfaces vicinal to the (111) direction simultaneously. By stabilizing the reaction at fixed temperatures around the ignition point, we observe a strong variation of the catalytic activity across the curved surface. Such spatial modulation of the reaction stage is straightforwardly mapped through the photoemission signal from active oxygen species and poisoning CO, which are shown to coexist in a transient regime that depends on the vicinal angle. Line-shape analysis and direct comparison with ultrahigh vacuum experiments help identifying and quantifying all such surface species, allowing us to reveal the presence of surface oxides during reaction ignition and cooling-off., We acknowledge financial support from the Spanish Ministry of Economy (Grants MAT-2012-38567-C02-02, MAT-2016-78293-C6, MAT-2017-88374-P) and Basque Government (Grant IT-1255-19).

The reaction of dirhodium tetrakis(3,4,5-trialkoxy)benzoates Rh2(B3OCn)4 (n = 10, 14, and 18) with three different dinitrogenated axial ligands (Lax), namely tetrazine (tz), phenazine (phz), and 4,4′-bipyridine (bpy), gave rise to three homologous series of mesogenic coordination polymers, [Rh2(B3OCn)4]Lax. All of them exhibited thermotropic columnar mesophases that were of the hexagonal type for tz and phz and rectangular for bpy. The lighter n = 10 homologs of the three series are liquid crystals (LC) at room temperature. Their mesomorphic properties have been compared with those of the previously studied Lax = pyrazine series. Models for the supramolecular organization of the three polymeric series in their Col LC phases are proposed on the basis of their structural parameters, as measured by XRD and SAXS. The differences are interpreted in terms of different coordination features of the axial ligands. Fil: Rossi, Leonardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina Fil: Huck Iriart, Cristián. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de San Martín. Escuela de Ciencia y Tecnología; Argentina Fil: Castro, Maria Ana. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina Fil: Cukiernik, Fabio Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina

The encapsulation of fluorescent dyes inside silica nanoparticles is advantageous to improve their quality as probes. Inside the particle, the fluorophore is protected from the external conditions and its main emission parameters remains unchanged even in the presence of quenchers. On the other hand, the amine-functionalized nanoparticle surface enables a wide range of applications, as amino groups could be easily linked with different biomolecules for targeting purposes. This kind of nanoparticle is regularly synthesized by methods that employ templates, additional nanoparticle formation or multiple pathway process. However, a one-step synthesis will be an efficient approach in this sort of bifunctional hybrid nanoparticles. A co-condensation sol-gel synthesis of hybrid fluorescent silica nanoparticle where developed. The chemical and morphological characterization of the particles where investigated by DRIFTS, XPS, SEM and SAXS. The nanoparticle fluorescent properties were also assessed by excitation-emission matrices and time resolved experiments. We have developed a one-pot synthesis method that enables the simultaneous incorporation of functionalities, the fluorescent molecule and the amino group, by controlling co-condensation process. An exhaustive characterization allows the definition of the spatial distribution of the fluorescent probe, fluorescein isothiocyanate, inside the particle and reactive amino groups on the surface of the nanoparticle with diameter about 100 nm., Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas

Flocculation process was studied in emulsions formulated with 10wt.% sunflower oil, 2, 5 or 7.5wt.% NaCas, and with or without addition of sucrose (0, 5, 10, 15, 20 or 30wt.%). Two different processing conditions were used to prepare emulsions: ultraturrax homogenization or further homogenization by ultrasound. Emulsions with droplets with diameters above (coarse) or below (fine) 1μm were obtained. Emulsions were analyzed for droplet size distribution by static light scattering (SLS), stability by Turbiscan, and structure by confocal laser scanning microscopy (CLSM) and small angle X-ray scattering (SAXS). SAXS data were fitted by a theoretical model that considered a system composed of poly dispersed spheres with repulsive interaction and presence of aggregates. Flocculation behavior was caused by the self-assembly properties of NaCas, but the process was more closely related to interfacial protein content than micelles concentration in the aqueous phase. The results indicated that casein aggregation was strongly affected by disaccharide addition, hydrophobic interaction of the emulsion droplets, and interactions among interfacial protein molecules. The structural changes detected in the protein micelles in different environments allowed understanding the macroscopic physical behavior observed in concentrated NaCas emulsions.

The aim of the present work was to investigate the effect of aqueous phase composition on the stability of emulsions formulated with 10 wt% sunflower oil as fat phase. Aqueous phase was formulated with 0.5, 2, or 5 wt% sodium caseinate, or sodium caseinate with the addition of two different hydrocolloids, xanthan gum or locust bean gum, both at 0.3 or 0.5 wt% level or sodium caseinate or with addition of 20 wt% sucrose. Emulsions were processed by Ultra-Turrax and then further homogenized by ultrasound. Creaming and flocculation kinetics were quantified by analyzing the samples with a Turbiscan MA 2000. Emulsions were also analyzed for particle size distribution, microstructure, viscosity, and dynamic surface properties. The most stable systems of all selected in the present work were the 0.3 or 0.5 wt% XG or 0.5 wt% LBG/ 0.5 wt% NaCas coarse emulsion and the 20 wt% sucrose/5 wt% NaCas fine emulsion. Surprisingly, coarse emulsions with the lower concentration of NaCas, which had greater D4,3, were more stable than fine emulsions when the aqueous phase contained XG or LBG. In these conditions, the overall effect was less negative bulk interactions between hydrocolloids and sodium caseinate, which led to stability. Sugar interacted in a positive way, both in bulk and at the interface sites, producing more stable systems for small-droplet high-protein-concentration emulsions. This study shows the relevance of components interactions in micro- structure and stability of caseinate emulsions. Fil: Huck Iriart, Cristián. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires; Argentina Fil: Pizones Ruiz Henestrosa, Víctor Manuel. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina Fil: Candal, Roberto Jorge. Universidad Nacional de San Martín; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina Fil: Herrera, Maria Lidia. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina

The physicochemical properties of emulsions play an important role in food systems as they directly contribute to texture, sensory and nutritional properties of foods. Sodium caseinate (NaCas) is a well-used ingredient because of its good solubility and emulsifying properties and its stability during heating. One of most significant aspects of any food emulsion is its stability. Among the methods used to study emulsion stability it may be mentioned visual observation, ultrasound profiling, microscopy, droplet size distribution, small deformation rheometry, measurement of surface concentration to characterize adsorbed protein at the interface, nuclear magnetic resonance, confocal microscopy, diffusing wave spectroscopy, and turbiscan. They have advantages and disadvantages and provide different insights into the destabilization mechanisms. Related to stability, the aspects more deeply investigated were the amount of NaCas used to prepare the emulsion, and specially the oil-to-protein ratio, the mobility of oil droplets and the interactions among emulsion components at the interface. It is known that the amount of protein required to stabilize oil-in-water emulsions depends, not only on the structure of protein at the interface, and the average diameters of the emulsion droplets, but also on the type of oils and the composition of the aqueous phase. Several authors have investigated the effect of a thickening agent or of a surface active molecule. Factors such as pH, temperature, and processing conditions during emulsion preparation are also very relevant to stability. There is a general agreement among authors that the most stable systems are obtained for conditions that produce size reduction of the droplets, an increase in viscosity of the continuous phase and structural changes in emulsions such as gelation. All these conditions decrease the molecular mobility and slow down phase separation. © 2011 Elsevier B.V. Fil: Huck Iriart, Cristián. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina Fil: Álvarez Cerimedo, María Soledad. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina Fil: Candal, Roberto Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad Nacional de San Martín. Escuela de Ciencia y Tecnología; Argentina Fil: Herrera, Maria Lidia. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina

Many food products such as ice cream, yoghurt, and mayonnaise are some examples of emulsion-based food. The physicochemical properties of emulsions play an important role in food systems as they directly contribute to texture, sensory and nutritional properties of food. One of the main properties is stability which refers to the ability of an emulsion to resist physical changes over time. The aim of the present work was to analyze the effect of processing conditions and composition on sodium caseinate (NaCas) emulsions stability. The main destabilization mechanisms were identified and quantified. The relationship between them and the factors that influence them were also investigated. Emulsions stabilized with NaCas were prepared using an ultrasound liquid processor or a high pressure homogenizer. Stability of emulsions was followed by a Turbiscan (TMA 2000) which allows the optical characterization of any type of dispersion. The physical evolution of this process is followed without disturbing the original system and with good accuracy and reproducibility. To further describe systems, droplet size distribution was analyzed with light scattering equipment. The main mechanism of destabilization in a given formulation depended on different factors such as NaCas concentration, droplet size or processing conditions. The rate of destabilization was markedly lower with addition of sugar or a hydrocolloid to the aqueous phase. Xanthan (XG) and locust bean (LBG) gums produced an increase in viscosity of the continuous phase and structural changes in emulsions such as gelation. Sugars interacted with the protein decreasing particle size and increasing emulsion stability. The stability of caseinate emulsions was strongly affected not only by the oil-to-protein ratio but also by processing conditions and composition of aqueous phase. The structure of the protein and the interactions protein–sugar or the presence of a hydrocolloid played a key role in creaming and flocculation processes of these emulsions.

Stability of emulsions formulated with 10wt.% oil (concentrated fish oil, CFO, sunflower oil, SFO, or olive oil, OO), sodium caseinate concentrations varying from 0.5 to 5wt.%, giving oil-to-protein ratios of 20-2, and 0, 20, 30 or 40wt.% aqueous trehalose solution was studied by Turbiscan. Particle size distribution, microstructure, and small angle X-ray scattering (SAXS) patterns were also obtained. The main mechanism of destabilization in a given formulation strongly depended on oil-to-protein ratio. As evidenced by the BS-profile changes with time, emulsions formulated with 0.5 and 1wt.% NaCas destabilized mainly by creaming while for the 2wt.% NaCas concentration, both creaming and flocculation mechanisms, were involved. The main destabilization mechanism for the 3, 4 or 5wt.% NaCas emulsions was flocculation. Stability of emulsions was also affected by the content of trehalose in the aqueous phase. Trehalose diminished the volume-weighted mean diameter (D4,3) and greatly improved stability. Fil: Álvarez Cerimedo, María Soledad. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina Fil: Huck Iriart, Cristián. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina Fil: Candal, Roberto Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad Nacional de San Martín. Escuela de Ciencia y Tecnología; Argentina Fil: Herrera, Maria Lidia. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina

The effect of addition of a highly hydrophobic emulsifier, the palmitic sucrose ester P-170, on isothermal crystallization behavior of a high-melting fraction of milk fat (HMF) and its mixtures with 20% or 40% sunflower oil (SFO), both in bulk and in emulsion systems, were studied by nuclear magnetic resonance (NMR) and by time-resolved in situ small-angle synchrotron X-ray scattering (SAXS). NMR studies showed that the effect of P-170 on the overall isothermal crystallization kinetics in bulk phase could be either acceleration or delay. The effect was strongly dependent on supercooling. For HMF, P-170 retarded crystallization at temperatures above 29.0 ± 0.2°C, while below that temperature, it accelerated the process. For the blends of HMF with 20% or 40% SFO, the temperature at which the behavior changed was 27.0 ± 0.2 or 26.0 ± 0.2°C, respectively. In emulsion systems, however, the effect was always acceleration for all temperatures selected. With the aid of SAXS, it was possible to study early stage of crystallization during real time and therefore to improve our understanding of the mechanism of P-170 action. The different effects caused by P-170, as described by SFC curves, were strongly related to the effects of P-170 on fat polymorphism, specially to the value of the time interval of coexistence of the α and β′ forms. These events took place at the very beginning of crystallization and thus could not be described by the traditional X-ray techniques used in previous studies of similar systems. Fil: Huck Iriart, Cristián. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Industrias; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Candal, Roberto Jorge. Universidad Nacional de San Martín. Escuela de Ciencia y Tecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina Fil: Herrera, Maria Lidia. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Industrias; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina

This investigation aims at studying-by in situ grazing-incidence small-angle x-ray scattering-the process of growth of hexagonal CoSi2 nanoplatelets endotaxially buried in a Si(001) wafer. The early formation of spherical Co nanoparticles with bimodal size distribution in the deposited silica thin film during a pretreatment at 500 °C and their subsequent growth at 700 °C were also characterized. Isothermal annealing at 700 °C promotes a drastic reduction in the number of the smallest Co nanoparticles and a continuous decrease in their volume fraction in the silica thin film. At the same time, Co atoms diffuse across the SiO2/Si(001) interface into the silicon wafer, react with Si, and build up thin hexagonal CoSi2 nanoplatelets, all of them with their main surfaces parallel to Si{111} crystallographic planes. The observed progressive growths in thickness and lateral size of the hexagonal CoSi2 nanoplatelets occur at the expense of the dissolution of the small Co nanoparticles that are formed during the pretreatment at 500 °C and become unstable at the annealing temperature (700 °C). The kinetics of growth of the volume fraction of hexagonal platelets is well described by the classical Avrami equation., Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas

The effect of the addition of sucrose and xanthan gum, protein concentration, and processing method on the stability and destabilization mechanism type of emulsions formulated with two commercial whey protein concentrate powders was described and quantified following system changes with a Turbiscan TMA 2000, a light scattering equipment and a confocal laser scanning microscope. Two different processing methods that gave particle sizes with different orders of magnitude were compared: homogenization by ULTRA-TURRAX (UT) and by ultrasound (US). The addition of sucrose to the aqueous phase of emulsions significantly diminished volume-weighted mean diameter (D 4,3 ) and improved stability. When the aqueous phase contained xanthan gum, the main destabilization mechanism for UT emulsions changed from creaming to flocculation. For US emulsions, although some aggregation was detected by confocal laser scanning microscopy, it was not great enough to modify the backscattering average (BS av ) in the middle zone of the tube (20?50 mm). At low protein concentrations, the profiles corresponded to destabilization of small aggregates. In those conditions, creaming was markedly enhanced as evident from creaming rate values. Independently of aqueous phase composition, US emulsions stabilized by protein concentrations higher than 5 wt% were stable, indicating that whey proteins were good emulsion stabilizers at pH close to 7. This study shows the relevance of protein type on stability and describes for the first time a behavior for whey proteins different from the one reported for caseins in literature. Fil: Huck Iriart, Cristián. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina Fil: Rincón Cardona, Jaime A.. Universidad Nacional de San Martín. Instituto de Investigación E Ingeniería Ambiental; Argentina Fil: Herrera, Maria Lidia. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina