Wet chemical synthesis and a combined X-ray and Mössbauer study of the formation of FeSb2 nanoparticles

Understanding how solids form is a challenging task, and few strategies allow for elucidation of reaction pathways that are useful for designing the synthesis of solids. Here, we report a powerful solution-mediated approach for formation of nanocrystals of the thermoelectrically promising FeSb(2) that uses activated metal nanoparticles as precursors. The small particle size of the reactants ensures minimum diffusion paths, low activation barriers, and low reaction temperatures, thereby eliminating solid-solid diffusion as the rate-limiting step in conventional bulk-scale solid-state synthesis. A time- and temperature-dependent study of formation of nanoparticular FeSb(2) by X-ray powder diffraction and iron-57 M?ssbauer spectroscopy showed the incipient formation of the binary phase in the temperature range of 200-250 °C.     

Aerodynamic and aeroacoustic analysis of a pulsating internal flow by a multidomain weak collocation spectral method

A numerical methodology is presented for the coupled aerodynamic and aeroacoustic analysis of time dependent laminar viscous flows in general two-dimensional geometries. The overall procedure is constituted firstly by the solution of the incompressible Navier-Stokes equations and secondly by the solution of a linear evolution equation of second order in space and time which originates from Lighthill's acoustic analogy. A semi-implicit projection method is utilized for the time integration of the incompressible Navier-Stokes system, while a choice between a second order implicit Newmark scheme and a fourth order explicit Runge-Kutta-Nyström method is offered for the temporal discretization of the wave equation. The multidomain weak Legendre collocation spectral method on quadrilateral subdomain topologies is employed for the spatial approximation of both the fluid dynamic and the acoustic problems. A specific pulsating internal flow inside a plane constricted channel is selected as a representative application for the assessment of the capabilities of the proposed discrete algorithm. Numerous results are presented and discussed, so as to thoroughly demonstrate the behavior of the numerical procedure.     

Exact parametric analytic solutions of the elastica ODEs for bars including effects of the transverse deformation

We succeed in constructing exact parametric analytic solutions for the non-linear ordinary differential equations governing the elastica response of a cantilever due to a generalized end loading by taking into account the effects of transverse deformation. Application to the case of the eccentric buckling of a cantilever by taking into account the above influences is developed.     

State diagrams of arabinoxylan-water binaries

Since Arabinoxylans are natural polysaccharides that seem promising candidates as cryostabilizers, the state diagram (i.e. the representation in the temperature-composition plan of the macroscopic phases) of their aqueous solutions seemed worth determining.

Two lots of purified water extractable arabinoxylans (WEA) of different molecular mass (56 and 410 kDa labeled as LMW-AX and HMW-AX, respectively) were used to prepare aqueous solutions of various composition. These were cooled below their freezing point and annealed for 2 h at a suitable temperature before a DSC 5°C min⁻¹ heating run aimed at determining their primary glass transition temperature, T_g′, and the onset of ice fusion. Once the corresponding composition, C_g′, was assessed, the main curves of the corresponding state diagram were drawn.

As expected, the T_g′ value drawn for HMW-AX was higher (−17°C) than for LMW-AX (−35°C). The C_g′ was instead found close to 75% w/w for both HMW-AX and LMW-AX. The fictitiousness of this coincidence could be easily recognized by expressing the solute concentration in molar fraction, X: it was then possible to verify that, as expected, X_g′ for LMW-AX was one order of magnitude larger than for HLW-AX.     

Effect of Ca2+/Sr2+ substitution on the electronic structure of the oxygen-evolving complex of photosystem II: a combined multifrequency EPR, 55Mn-ENDOR, and DFT study of the S2 state

The electronic structures of the native Mn(4)O(x)Ca cluster and the biosynthetically substituted Mn(4)O(x)Sr cluster of the oxygen evolving complex (OEC) of photosystem II (PSII) core complexes isolated from Thermosynechococcus elongatus, poised in the S(2) state, were studied by X- and Q-band CW-EPR and by pulsed Q-band (55)Mn-ENDOR spectroscopy. Both wild type and tyrosine D less mutants grown photoautotrophically in either CaCl(2) or SrCl(2) containing media were measured. The obtained CW-EPR spectra of the S(2) state displayed the characteristic, clearly noticeable differences in the hyperfine pattern of the multiline EPR signal [Boussac et al. J. Biol. Chem.2004, 279, 22809-22819]. In sharp contrast, the manganese ((55)Mn) ENDOR spectra of the Ca and Sr forms of the OEC were remarkably similar. Multifrequency simulations of the X- and Q-band CW-EPR and (55)Mn-pulsed ENDOR spectra using the Spin Hamiltonian formalism were performed to investigate this surprising result. It is shown that (i) all four manganese ions contribute to the (55)Mn-ENDOR spectra; (ii) only small changes are seen in the fitted isotropic hyperfine values for the Ca(2+) and Sr(2+) containing OEC, suggesting that there is no change in the overall spin distribution (electronic coupling scheme) upon Ca(2+)/Sr(2+) substitution; (iii) the changes in the CW-EPR hyperfine pattern can be explained by a small decrease in the anisotropy of at least two hyperfine tensors. It is proposed that modifications at the Ca(2+) site may modulate the fine structure tensor of the Mn(III) ion. DFT calculations support the above conclusions. Our data analysis also provides strong support for the notion that in the S(2) state the coordination of the Mn(III) ion is square-pyramidal (5-coordinate) or octahedral (6-coordinate) with tetragonal elongation. In addition, it is shown that only one of the currently published OEC models, the Siegbahn structure [Siegbahn, P. E. M. Acc. Chem. Res.2009, 42, 1871-1880, Pantazis, D. A. et al. Phys. Chem. Chem. Phys.2009, 11, 6788-6798], is consistent with all data presented here. These results provide important information for the structure of the OEC and the water-splitting mechanism. In particular, the 5-coordinate Mn(III) is a potential site for substrate 'water' (H(2)O, OH(-)) binding. Its location within the cuboidal structural unit, as opposed to the external 'dangler' position, may have important consequences for the mechanism of O-O bond formation.     

GC-MS and HPLC methods for peroxynitrite (ONOO- and O15NOO-) analysis: a study on stability, decomposition to nitrite and nitrate, laboratory synthesis, and formation of peroxynitrite from S-nitrosoglutathione (GSNO) and KO2

Nitric oxide (˙NO) and superoxide (O(2)(-)˙) are ubiquitous in nature. Their reaction product peroxynitrite (ONOO(-)) and notably its conjugated peroxynitrous acid (ONOOH) are highly unstable in aqueous phase. ONOO(-)/ONOOH (referred to as peroxynitrite) isomerize and decompose to NO(3)(-), NO(2)(-) and O(2). Here, we report for the first time GC-MS and HPLC methods for the analysis of peroxynitrite in aqueous solution. For GC-MS analysis peroxynitrite in alkaline solution was derivatized to a pentafluorobenzyl derivative using pentafluorobenzyl bromide. O(15)NOO(-) was synthesized from H(2)O(2) and (15)NO(2)(-) and used as internal standard. HPLC analysis was performed on stationary phases consisting of Nucleosil? 100-5C(18)AB or Nucleodur? C(18) Gravity. The mobile phase consisted of a 10 mM aqueous solution of tetrabutylammonium hydrogen sulfate and had a pH value of 11.5. UV absorbance detection at 300 nm was used. HPLC allows simultaneous analysis of ONOO(-), NO(2)(-) and NO(3)(-). The GC-MS and HPLC methods were used to study stability, synthesis, formation from S-[(15)N]nitrosoglutathione (GS(15)NO) and KO(2), and isomerization/decomposition of peroxynitrite to NO(2)(-) and NO(3)(-) in aqueous buffer.     

Hydrothermal Synthesis of Siderite and Application as Catalyst in the Electro-Fenton Oxidation of p-Benzoquinone

A weak aspect of the electro-Fenton (EF) oxidation of contaminants is the dependence of the Fenton reaction on acidic pH values. Therefore, the rationale of this work was to develop a novel catalyst capable of promoting the EF oxidation process at near-neutral and basic pH values. In this framework, rhombohedral FeCO₃ was synthesized hydrothermally and used as a catalyst in the EF oxidation of p-benzoquinone (BQ). The catalyst was characterized using various surface and spectroscopic methods. Moreover, the effects of applied current (100–500 mA), time (1–9 h), catalyst dosage (0.25–1.00 g L⁻¹), and initial concentration of BQ (0.50–1.00 mM) on the total organic carbon removal efficiency were determined. The results indicated that a 400 mA current was sufficient for a 95% total organic carbon removal and that the increase in catalyst dosage had a positive effect on the mineralization of BQ. It was determined that at pH 3, FeCO₃ behaved like a homogeneous catalyst by releasing Fe³⁺ ions; whereas, at the pH range of 5–7, it shifted to a homogeneous/heterogeneous catalyst. At pH 9, it worked solely as a heterogeneous catalyst due to the decrease of Fe ions passing into the solution. Finally, the spent catalyst did not undergo structural deformations after the EF treatment at higher pH values and could be regenerated and used several times     

Pták function and symmetry

We investigate subadditivity of Pták function as a sufficient and necessary condition for symmetry in the class of involutive spectrally bounded algebras. Among others it is proved an analogue of Raikov's criterion for complete lmc^*-algebras in which the hermitian elements have finite spectral radius.     

Vapor liquid equilibrium modeling of alkane systems with Equations of State: “Simplicity versus complexity”

Two types of Equations of State (EoS), which are characterized here as “simple” and “complex” EoS, are evaluated in this study. The “simple” type involves two versions of the Peng–Robinson (PR) EoS: the traditional one that utilizes the experimental critical properties and the acentric factor and the other, referred to as PR-fitted (PR-f), where these parameters are determined by fitting pure compound vapor pressure and saturated liquid volume data. As “complex” EoS in this study are characterized the EoS derived from statistical mechanics considerations and involve the Sanchez–Lacombe (SL) EoS and two versions of the Statistical Associating Fluid Theory (SAFT) EoS, the original and the Perturbed-Chain SAFT (PC-SAFT).

The evaluation of these two types of EoS is carried out with respect to their performance in the prediction and correlation of vapor liquid equilibria in binary and multicomponent mixtures of methane or ethane with alkanes of various degree of asymmetry. It is concluded that for this kind of systems complexity offers no significant advantages over simplicity. Furthermore, the results obtained with the PR-f EoS, especially those for multicomponent systems that are encountered in practice, even with the use of zero binary interaction parameters, indicate that this EoS may become a powerful tool for reservoir fluid phase equilibria modeling.