The effect of synthesis conditions on the physicochemical properties of magnesium aluminate materials

Magnesium aluminate-based materials were prepared by applying different methods: (i) mechanochemical milling of the initial mixture of magnesium and aluminium nitrate powders (in appropriate stoichiometric amounts) followed by heat treatment at temperatures of 650 °C and 850 °C and (ii) melting of the mixture of nitrate precursors at 240 °C followed by thermal treatment at 650 °C, 750 °C and 850 °C. The effect of synthesis method on the structure and morphology of the obtained solids was studied by using various techniques such as: nitrogen adsorption-desorption isotherms, powder XRD, IR spectroscopy and SEM. It was shown that the mechanochemical milling performed before calcination procedure leads to obtaining of nanocrystalline magnesium aluminate spinel phase at lower temperature of 650 °C in comparison with the method using thermal treatment only (at 750 °C). The obtained nanomaterials exhibit mesoporous structure.     

Analysis of the fluorescence of mechanically processed defect-laden hexagonal boron nitride and the role of oxygen in catalyst deactivation

ABSTRACT

The use of hexagonal boron nitride (h-BN) as a non-metal heterogeneous catalyst has been a popular subject in research since the discovery of its catalytic properties in 2016. Previous work found that an activation step was necessary for producing an effective catalyst. Density functional theory (DFT) calculations indicate defect sites, such as nitrogen (V_N) and boron (V_B) vacancies, bind favourably to olefins, hydrogen, and oxygen. In particular, the visible fluorescence intensity of processed h-BN increased with the length of exposure to air. The fluorescence behaviour of dh-BN powders when exposed to air after exposure to species such as argon, propene, and carbon dioxide is presented. Density of state calculations for molecular and atomic oxygen bound to V_N and V_B show that this increase in fluorescence may be due to atomic oxygen binding to V_N. The fluorescence emission behaviour observed in dh-BN powders and its relationship to DOS of oxygen species bound to catalytically active defect sites provides a better understanding of potential deactivation modes for catalysts based on dh-BN.     

Superparamagnetic polyvinylpyrrolidone/chitosan/Fe3O4 electrospun nanofibers as effective U(VI) adsorbents

Magnetoactive electrospun fibrous membranes consisting of polyvinylpyrrolidone (PVP), chitosan (CS) and pre-fabricated, double-layer oleic acid-coated magnetite nanoparticles (OA.OA.Fe₃O₄) were fabricated and evaluated as new adsorbent materials for the removal and recovery of uranium (U(VI)) from aqueous solutions. The adsorption has been investigated by batch-type experiments and the solid material has been characterized by X-ray diffraction spectroscopy (XRD), Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy/energy dispersive X-ray analysis (TEM/EDX) and vibration sample magnetometry (VSM) measurements prior and after uranium adsorption. The experimental adsorption data were found to be well fitted with the Langmuir isotherm and the pseudo-second order kinetic model. The results indicate that PVP/CS/OA.OA.Fe₃O₄ fibrous adsorbents exhibit good adsorption properties towards U(VI) in aqueous solutions, achieving a q_max value of 0.77 mol kg⁻¹ (183.3 mg g⁻¹) at pH 6.0. The experiments regarding the regeneration and reuse of the magnetoactive adsorbents were carried out using Na₂CO₃, at pH ~11. After four cycles, the percentage relative adsorption remained stable (~100%) whereas the desorption percentage decreased from 31.9% to 21.0%. Generally, the presented results demonstrate that the incorporation of the Fe₃O₄ NPs has a positive effect on the adsorption efficiency of U(VI) from aquatic environments.     

Anti-Idiotype scFv Localizes an Autoepitope in the Globular Domain of C1q

We addressed the issue of C1q autoantigenicity by studying the structural features of the autoepitopes recognized by the polyclonal anti-C1q antibodies present in Lupus Nephritis (LN) sera. We used six fractions of anti-C1q as antigens and selected anti-idiotypic scFv antibodies from the phage library “Griffin.1”. The monoclonal scFv A1 was the most potent inhibitor of the recognition of C1q and its fragments ghA, ghB and ghC, comprising the globular domain gC1q, by the lupus autoantibodies. It was sequenced and in silico folded by molecular dynamics into a 3D structure. The generated 3D model of A1 elucidated CDR similarity to the apical region of gC1q, thus mapping indirectly for the first time a globular autoepitope of C1q. The V_H CDR2 of A1 mimicked the ghA sequence GSEAD suggested as a cross-epitope between anti-DNA and anti-C1q antibodies. Other potential inhibitors of the recognition of C1q by the LN autoantibodies among the selected recombinant antibodies were the monoclonal scFv F6, F9 and A12.     

Analyzing developmental processes on an individual level using nonstationary time series modeling.

Individuals change over time, often in complex ways. Generally, studies of change over time have combined individuals into groups for analysis, which is inappropriate in most, if not all, studies of development. The authors explain how to identify appropriate levels of analysis (individual vs. group) and demonstrate how to estimate changes in developmental processes over time using a multivariate nonstationary time series model. They apply this model to describe the changing relationships between a biological son and father and a stepson and stepfather at the individual level. The authors also explain how to use an extended Kalman filter with iteration and smoothing estimator to capture how dynamics change over time. Finally, they suggest further applications of the multivariate nonstationary time series model and detail the next steps in the development of statistical models used to analyze individual-level data. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Isotopic and Elemental Authenticity Markers: a Case Study on Cypriot Wines

This study monitors variations in isotopes and elements in relation to grape variety, environmental factors and provenance in order to address the wine authenticity issue. Inductively coupled plasma atomic emission spectroscopy (ICP-AES) assessed the wines’ elemental content. Site-specific nuclear isotope fractionation-nuclear magnetic resonance and isotope ratio mass spectrometry methodologies determined in authentic and commercial wines the distribution of the naturally occurring stable isotopes of the deuterium/hydrogen (D/H) ratios and carbon (¹³C/¹²C) in ethanol of wine and oxygen ratio (¹⁸O/¹⁶O) in wine water. Chemometrics delineated the elements and isotopes responsible for wine classification. Specifically, unsupervised principal component analysis (PCA) framed the importance of grape variety and provenance, while supervised analysis pinpointed the vineyard effect and highlighted the contribution of the vintage year. Validation steps ensured that the extracted models do not predict randomly and their results are reliable. In fact, the acquired results can be incorporated to the EU Wine Isotopic Databank database providing both a guide and a tool for eventual candidatures for denomination of origin and support both Cypriot wine and winemakers. In this context, this research contributes to authenticity assurance of wines and adds value to final products, while it helps controlling hazards arising from environmental changes.     

Empirical Characterization of Session–Based Workload and Reliability for Web Servers

The growing availability of Internet access has led to significant increase in the use of World Wide Web. If we are to design dependable Web–based systems that deal effectively with the increasing number of clients and highly variable workload, it is important to be able to describe the Web workload and errors accurately. In this paper we focus on the detailed empirical analysis of the session–based workload and reliability based on the data extracted from actual Web logs of eleven Web servers. First, we introduce and rigourously analyze several intra–session and inter–session metrics that collectively describe Web workload in terms of user sessions. Then, we analyze Web error characteristics and estimate the request–based and session–based reliability of Web servers. Finally, we identify the invariants of the Web workload and reliability that apply through all data sets considered. The results presented in this paper show that session–based workload and reliability are better indicators of the users perception of the Web quality than the request–based metrics.     

Photoluminescence decay rate of silicon nanoparticles modified with gold nanoislands

We investigated plasmon-assisted enhancement of emission from silicon nanoparticles (ncs-Si) embedded into porous SiO _x matrix in the 500- to 820-nm wavelength range. In the presence in the near-surface region of gold nanoisland film, ncs-Si exhibited up to twofold luminescence enhancement at emission frequencies that correspond to the plasmon resonance frequency of Au nanoparticles. Enhancement of the photoluminescence (PL) intensity was attributed to coupling with the localized surface plasmons (LSPs) excited in Au nanoparticles and to increase in the radiative decay rate of ncs-Si. It has been shown that spontaneous emission decay rate of ncs-Si modified by thin Au film over the wide emission spectral range was accelerated. The emission decay rate distribution was determined by fitting the experimental decay curves to the stretched exponential model. The observed increase of the PL decay rate distribution width for the Au-coated nc-Si-SiO _x sample in comparison with the uncoated one was explained by fluctuations in the surface-plasmon excitation rate.

PACS

78. 67. Bf; 78.55.-m     

Thermal conductivity of highly porous Si in the temperature range 4.2 to 20?K

We report on experimental results of the thermal conductivity k of highly porous Si in the temperature range 4.2 to 20 K, obtained using the direct current (dc) method combined with thermal finite element simulations. The reported results are the first in the literature for this temperature range. It was found that porous Si thermal conductivity at these temperatures shows a plateau-like temperature dependence similar to that obtained in glasses, with a constant k value as low as 0.04 W/m.K. This behavior is attributed to the presence of a majority of non-propagating vibrational modes, resulting from the nanoscale fractal structure of the material. By examining the fractal geometry of porous Si and its fractal dimensionality, which was smaller than two for the specific porous Si material used, we propose that a band of fractons (the localized vibrational excitations of a fractal lattice) is responsible for the observed plateau. The above results complement previous results by the authors in the temperature range 20 to 350 K. In this temperature range, a monotonic increase of k with temperature is observed, fitted with simplified classical models. The extremely low thermal conductivity of porous Si, especially at cryogenic temperatures, makes this material an excellent substrate for Si-integrated microcooling devices (micro-coldplate).

PACS

61.43.-j; 63.22.-m; 65.8.-g