Endogenous Nanoparticles Strain Perovskite Host Lattice Providing Oxygen Capacity and Driving Oxygen Exchange and CH4 Conversion to Syngas

Particles dispersed on the surface of oxide supports have enabled a wealth of applications in electrocatalysis, photocatalysis, and heterogeneous catalysis. Dispersing nanoparticles within the bulk of oxides is, however, synthetically much more challenging and therefore less explored, but could open new dimensions to control material properties analogous to substitutional doping of ions in crystal lattices. Here we demonstrate such a concept allowing extensive, controlled growth of metallic nanoparticles, at nanoscale proximity, within a perovskite oxide lattice as well as on its surface. By employing operando techniques, we show that in the emergent nanostructure, the endogenous nanoparticles and the perovskite lattice become reciprocally strained and seamlessly connected, enabling enhanced oxygen exchange. Additionally, even deeply embedded nanoparticles can reversibly exchange oxygen with a methane stream, driving its redox conversion to syngas with remarkable selectivity and long term cyclability while surface particles are present. These results not only exemplify the means to create extensive, self‐strained nanoarchitectures with enhanced oxygen transport and storage capabilities, but also demonstrate that deeply submerged, redox‐active nanoparticles could be entirely accessible to reaction environments, driving redox transformations and thus offering intriguing new alternatives to design materials underpinning several energy conversion technologies.     

Molecular dynamics simulation of brushes formed by star polyelectrolytes under theta solvent conditions

Using molecular dynamics simulations, we have studied polyelectrolyte brushes formed by partially or fully charged star polymers tethered on a planar surface under theta solvent conditions. The diagram of states for salt‐free solutions differs in the location of osmotic regime (OB) compared with the respective diagram reported by Borisov and Zhulina. In contrast, simulation results dictate that the OB regime appears for values of the ratio F /α ^?1/2 l_B ^?1 much larger than unity, which is the threshold of counterion localization, with F denoting the branch functionality, α the charged units fraction and l_B the Bjerrum length. The simulation results support that the brush height scaling laws H ～ α ² l_B F ^1.049S ³s ^?1 and H ～ α^0.302 F ^0.23S for the charged Pincus Brush (PB) and osmotic (OB) regimes, respectively, where S is the spacer length and s is the grafted area per star chain. The respective theoretical scaling laws are H ～ α ² l_B F ^1.88S ³s ^?1 and H ～ α ^1/2 F ^0.44S . © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55 , 1110–1117     

Magnetic neutron-electron scattering; use of thef-sum rule to assess the effect of electron correlations,lattice interaction and magnetic field

We have calculated thef-sum rule for magnetic neutron scattering off electrons. Correlations alter the cross-section significantly at intermediate scattering vectors. Field induced effects are most significant at small scattering vectors, and the sum rule diverges in the limit of zero scattering vector. This feature is attributed to the field induced coupling of neutrons to the lowest energy Landau level and the collective density oscillation (hybrid mode). Our interpretation is based on an RPA calculation of the response function for neutron scattering from a magnetized plasma. The contribution to the cross-section from the electron-phonon interaction is also assessed, and it is found to increase with decreasing scattering vector.     

Quadrature Methods for Bayesian Optimal Design of Experiments With Nonnormal Prior Distributions

Many optimal experimental designs depend on one or more unknown model parameters. In such cases, it is common to use Bayesian optimal design procedures to seek designs that perform well over an entire prior distribution of the unknown model parameter(s). Generally, Bayesian optimal design procedures are viewed as computationally intensive. This is because they require numerical integration techniques to approximate the Bayesian optimality criterion at hand. The most common numerical integration technique involves pseudo Monte Carlo draws from the prior distribution(s). For a good approximation of the Bayesian optimality criterion, a large number of pseudo Monte Carlo draws is required. This results in long computation times. As an alternative to the pseudo Monte Carlo approach, we propose using computationally efficient Gaussian quadrature techniques. Since, for normal prior distributions, suitable quadrature techniques have already been used in the context of optimal experimental design, we focus on quadrature techniques for nonnormal prior distributions. Such prior distributions are appropriate for variance components, correlation coefficients, and any other parameters that are strictly positive or have upper and lower bounds. In this article, we demonstrate the added value of the quadrature techniques we advocate by means of the Bayesian D-optimality criterion in the context of split-plot experiments, but we want to stress that the techniques can be applied to other optimality criteria and other types of experimental designs as well. Supplementary materials for this article are available online.     

Urea porphyrins as simple receptors for sugars

Urea-functionalized porphyrins with amino acid substituents bind sugar derivatives strongly in non-polar solution.     

Optimization and development of a high‐performance liquid chromatography method for the simultaneous determination of vitamin E and carotenoids in tomato fruits

A simple and reliable high‐performance liquid chromatography method was developed and validated for the simultaneous determination of lipophilic antioxidants in tomato fruits using C₃₀ column operated at 15°C and a gradient mobile phase based on acetonitrile/methanol/dichloromethane in a total run time of 30 min. Diode array and fluorescence detectors were used respectively for the detection of carotenoids (lutein, zeaxanthin, cryptoxanthin, lycopene, and β‐carotene) and vitamin E analogs (α‐, β‐, γ‐, and δ‐tocopherols, and tocotrienols). The best extraction yield of analytes in tomato fruits was achieved by employing ethyl acetate/hexane (1:1, v/v) after several treatments with various solvents. In addition, low extraction yields were obtained for carotenoids compared to tocopherols by adopting solid‐phase extraction as a second clean‐up step. The method was validated on the basis of recovery, precision, linearity, and limit of detection and quantification using spiked tomato samples. The method was applied to cherry and medium‐sized tomato fruits. Lycopene was found to be present in largest amount in tomato pulp, followed by β‐carotene and lutein. Due to its simplicity, rapidity, and efficiency, the method is suitable for routine analysis of lipophilic antioxidants in tomato fruits, and may also be applied to other vegetables of similar phytochemical profiles.     

Oxidation of Some Aliphatic Aldehydes in a Liquid-Liquid Interfacial System

In the present study the oxidation by chromic acid of some long-chain aliphatic aldehydes is investigated in a liquid-liquid interfacial system. For comparison the same oxidation was performed with the aldehydes dispersed in water. Higher yields were obtained in interfacial experiments as compared to the ones obtained when the aldehydes were dispersed in water. These results are rationalized by the fact that in the interfacial experiments reactants and products are exposed for short periods of time to the oxidative action of chromic acid, being in a way protected in the organic phase. Concerning the crucial problem of the reaction site i.e. where actually the oxidation occurs in interfacial experiments, it seems, based on kinetics and activation parameter determination as well as by modification of the interface with surfactants, that the oxidation occurs at the liquid-liquid interface and to a lesser extent in the aqueous phase. However, futher work is under way for the complete elucidation of the interfacial process.     

Heavy sterile neutrinos and supernova explosions

We consider sterile neutrinos with rest masses 0.2 GeV and with vacuum flavor mixing angles θ²>10⁻⁸ for mixing with τ-neutrinos, or 10⁻⁸<θ²<10⁻⁷ for mixing with muon neutrinos. Such sterile neutrinos could augment core collapse supernova shock energies by enhancing energy transport from the core to the vicinity of the shock front. The decay of these neutrinos could produce a flux of very energetic active neutrinos, detectable by future neutrino observations from galactic supernova. The relevant range of sterile neutrino masses and mixing angles can be probed in future laboratory experiments.     

Proteins and enzymatic activities in Erbaluce grape berries with different response to the withering process

During the off-vine natural withering process of Erbaluce (white) grapes to obtain “Erbaluce Caluso” Passito wine, some berries change in color from green-yellow to blue. This phenomenon appears at different extents in different years and might be related to several parameters, such as temperature and humidity during withering, grape composition and Botrytis cinerea loading. To better understand the mechanism involved in color variation, the metabolic changes corresponding to this event were studied.     

Design,Synthesis and Antiparasitic Evaluation of Click Phospholipids

A library of seventeen novel ether phospholipid analogues, containing 5-membered heterocyclic rings (1,2,3-triazolyl, isoxazolyl, 1,3,4-oxadiazolyl and 1,2,4-oxadiazolyl) in the lipid portion were designed and synthesized aiming to identify optimised miltefosine analogues. The compounds were evaluated for their in vitro antiparasitic activity against Leishmania infantum and Leishmania donovani intracellular amastigotes, against Trypanosoma brucei brucei and against different developmental stages of Trypanosoma cruzi. The nature of the substituents of the heterocyclic ring (tail) and the oligomethylene spacer between the head group and the heterocyclic ring was found to affect the activity and toxicity of these compounds leading to a significantly improved understanding of their structure–activity relationships. The early ADMET profile of the new derivatives did not reveal major liabilities for the potent compounds. The 1,2,3-triazole derivative 27 substituted by a decyl tail, an undecyl spacer and a choline head group exhibited broad spectrum antiparasitic activity. It possessed low micromolar activity against the intracellular amastigotes of two L. infantum strains and T. cruzi Y strain epimastigotes, intracellular amastigotes and trypomastigotes, while its cytotoxicity concentration (CC₅₀) against THP-1 macrophages ranged between 50 and 100 μM. Altogether, our work paves the way for the development of improved ether phospholipid derivatives to control neglected tropical diseases.