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     

Nonlinear electronic circuit, Part II: synchronization in a chaotic MODEM scheme

In this work we present a thorough investigation of the effect of noise (internal or external) on the synchronization of a drive-response configuration system (unidirectional coupling between two identical systems). Moreover, since in every practical implementation of a communication system, the transmitter and receiver circuits (although identical) operate under slightly different conditions it is essential to consider the case of the mismatch between the parameters of the transmitter and the receiver. In our work we consider the non-autonomous 2nd order nonlinear oscillator system presented in [G. Mycolaitis, A. Tamasevicious, A. Cenys, A. Namajunas, K. Navionis, A. N. Anagnostopoulos, Globally synchronizable non-autonomous chaotic oscillator, in: Proc. of 7th International Workshop on Nonlinear Dynamics of Electronic Systems, Denmark, July 1999, pp. 277-280] which is particularly suitable for digital communications.Furthermore, we modified the previous chaotic communication system in order to exhibit enhanced security features. The enhancement in the security of the system is achieved by introducing a set of parameters used in the encoding and decoding of the message signal. We also introduce a time delay parameter in the dynamical system which on the one hand improves the chaotic behavior of the system and on the other hand, adds further security in the encoding-decoding scheme.     

HPLC Determination of Colistin in Human Urine Using Alkaline Mobile Phase Combined with Post-Column Derivatization: Validation Using Accuracy Profiles

In this study, the development, validation, and application of a new liquid chromatography post-column derivatization method for the determination of Colistin in human urine samples is demonstrated. Separation of Colistin was performed using a core–shell C₁₈ analytical column in an alkaline medium in order (i) to be compatible with the o-phthalaldehyde-based post-column derivatization reaction and (ii) to obtain better retention of the analyte. The Colistin derivative was detected spectrofluorometrically (λ_ext/λ_em = 340/460 nm) after post-column derivatization with o-phthalaldehyde and N-acetyl cysteine. The post-column derivatization parameters were optimized using the Box–Behnken experimental design, and the method was validated using the total error concept. The β-expectation tolerance intervals did not exceed the acceptance criteria of ±15%, meaning that 95% of future results would be included in the defined bias limits. The limit of detection of the method was adequate corresponding to 100 nmol·L⁻¹. The mean analytical bias (expressed as relative error) in the spiking levels was suitable, being in the range of −2.8 to +2.5% for both compounds with the percentage relative standard deviation lower than 3.4% in all cases. The proposed analytical method was satisfactorily applied to the analysis of the drug in human urine samples.     

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.     

The nonlinear current behaviour of a driven R–L-Varactor in the low frequency range

The nonlinear behaviour of an R–L-Varactor circuit, simulated by Multisim 7.0 at a driving frequency that is below the circuit resonance frequency, is reported and evaluated. A new high amplitude oscillation is observed and attributed to the emergence of a large diode junction capacitance. Increasing the driving signal amplitude, the circuit is led to a non-periodic mode of operation, producing trajectories of increasing chaotic content in a four-dimensional phase space. At specific amplitudes a two-dimensional tori was monitored, where trajectories are periodic, like in a two oscillator system with commensurate frequencies. Poincaré cross-sections, FFT spectra and correlation dimension calculations, suggest the quasi-periodicity route to chaos.     

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.     

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.