Separation of organoselenium compounds and their electrochemical detection

A simplified procedure based on ion-exchange separation of selenourea (Se-U) and selenocystamine (Se-CM), which have very close half-wave potential when they are simultaneously analyzed by voltammetric techniques, has been developed and optimized. Thus, selenocystamine remains in the cation exchanger Purolite C 100 H, whereas selenourea is found in the effluent and is determined by square wave cathodic stripping voltammetry using Na₂CO₃ as electrolyte. Selenocystamine is then eluted from the cation exchanger using 4 M HCl and analyzed by square wave cathodic stripping voltammetry in the HCl solution. For each voltammetric determination the corresponding parameters were investigated and optimized; the obtained detection limits were 0.3 ng Se mL^–1 for Se-CM and 2 ng Se mL^–1 for Se-U. A flow sheet for the separation of inorganic (Se(IV) and Se(VI)) and organoselenium compounds (Se-U, Se-CM, (CH₃)₂Se₂, and (CH₃)₂Se) developed for their electrochemical detection is presented and it was successfully applied to a certified reference material, an environmental soil sample, and a urine sample.     

Composition-dependent photosensitivity in As-S glasses induced by bandgap light: structural origin by Raman scattering

Massive photoinduced short- and medium-range structural changes (photopolymerization) in As-S glasses are induced by near-bandgap light and studied by Raman scattering. Structural changes involve bond restructuring in sulfur-rich nanodomains of these nanoscale-phase-separated glasses. The spectral dependence of the photopolymerization effect demonstrates that various wavelengths can be used to optically change the structure of As-S glasses. The immense structural changes are relevant to recent findings about the role of bandgap light illumination for fabricating channel waveguides in noncrystalline arsenic sulfides.     

Antioxidant behaviour of 2′‐hydroxy‐chalcones: a study of their electrochemical properties

The electrochemical behaviour of 13 chalcone analogues was systematically studied by means of cyclic voltammetry and chronoamperometry at a glassy carbon (GC), gold and platinum working electrodes using two different supporting electrolyte/solvent combinations. It was found that chalcone analogues can be easily oxidized at both GC and gold working electrodes, but not at a platinum electrode. Principal component analysis was further employed to reveal similarities/dissimilarities between oxidation potentials, chronoamperometric signals and ability of the compounds to scavenge the reactive oxygen species H₂O₂. The study reveals the inverse proportional relationship between the scavenging ability of H₂O₂, expressed as IC₅₀, and chronoamperometric signal at 800 mV using gold as working electrode. Copyright © 2012 John Wiley & Sons, Ltd.     

Comparative hemodynamics in an aorta with bicuspid and trileaflet valves

Bicuspid aortic valve (BAV) is a congenital heart defect that has been associated with serious aortopathies, such as aortic stenosis, aortic regurgitation, infective endocarditis, aortic dissection, calcific aortic valve and dilatation of ascending aorta. There are two main hypotheses to explain the increase prevalence of aortopathies in patients with BAV: the genetic and the hemodynamic. In this study, we seek to investigate the possible role of hemodynamic factors as causes of BAV-associated aortopathy. We employ the curvilinear immersed boundary method coupled with an efficient thin-shell finite-element formulation for tissues to carry out fluid–structure interaction simulations of a healthy trileaflet aortic valve (TAV) and a BAV placed in the same anatomic aorta. The computed results reveal major differences between the TAV and BAV flow patterns. These include: the dynamics of the aortic valve vortex ring formation and break up; the large-scale flow patterns in the ascending aorta; the shear stress magnitude, directions, and dynamics on the heart valve surfaces. The computed results are in qualitative agreement with in vivo magnetic resonance imaging data and suggest that the linkages between BAV aortopathy and hemodynamics deserve further investigation.     

Detached eddy simulation of flow around two wall-mounted cubes in tandem

We investigate the performance of unsteady Reynolds-averaged Navier–Stokes (URANS) computation and various versions of detached eddy simulation (DES) in resolving coherent structures in turbulent flow around two cubes mounted in tandem on a flat plate at Reynolds number (Re) of 22,000 and for a thin incoming boundary layer. Calculations are carried out using four different coherent structure resolving turbulence models: (1) URANS with the Spalart–Allmaras model; (2) the standard DES [Spalart, P.R., Jou, W.H., Strelets, M., Allmaras, S.R., 1997. Comments on the feasibility of LES for wings, and on a hybrid RANS/LES approach. In: Liu, C., Liu, Z., (Eds.), Advances in DNS/LES. Greyden Press, Columbus, OH]; (3) the Delayed DES (DDES); and (4) the DES with a low-Re modification (DES-LR) [Spalart, P., Deck, S., Shur, M., Squires, K., Strelets, M., Travin, A., 2006. A new version of detached eddy simulation, resistant to ambiguous grid densities. Theor. Comput. Fluid Dyn. 20 (3), 181–195]. The grid sensitivity of the computed solutions is examined by carrying out simulations on two successively refined grids. The computed results for all cases are compared with the experimental measurements of Martinuzzi and Havel [Martinuzzi, R., Havel, B., 2000. Turbulent flow around two interfering surface-mounted cubic obstacles in tandem arrangement. ASME J. Fluids Eng. 122, 24–31] for two different cube spacings. All turbulence models reproduce essentially identical separation of the approach thin boundary layer and yield an unsteady horseshoe vortex system consisting of multiple vortices in the leading edge region of the upstream cube. Significant discrepancies between the URANS and all DES solutions are observed, however, in other regions of interest such as the shear layers emanating from the cubes, the inter-cube gap and the downstream wake. Regardless of the grid refinement, URANS fails to capture key features of the mean flow, including the second horseshoe vortex in the upstream junction and recirculating flow on the top surface of the downstream cube for the large cube spacing, and underestimates significantly turbulence statistics in most regions of the flow for both cases. On the coarse mesh, all three DES approaches appear to yield very similar results and fail to reproduce the second horseshoe vortex. The standard DES and DDES solutions obtained on the fine meshes are essentially identical and both suffer from premature switching to unresolved DNS, due to the mis-interpretation of grid refinement as wall proximity, which leads to spurious vortices in the inter-cube region. Numerical solutions show that the low-Re modification (DES-LR) is critical prerequisite in DES on the ambiguously fine – not fine enough for full LES – mesh to prevent excessive nonlinear drop of the subgrid eddy viscosity in low cell-Re regions like in the inter-obstacle gap. Mean flow quantities and turbulence statistics obtained with DES-LR on the fine mesh are in good overall agreement with the measurements in most regions of interest for both cases.     

Study of the lipophilicity of selenium species

In this work the lipophilicity of different selenium species occurring in environmental matrices and food, Se(IV), Se(VI), selenomethionine (Se-Met), selenocystamine (Se-CM), selenocystine (Se-Cyst), and dimethyl diselenide (CH₃)₂Se₂, was investigated in the octanol–water system, using the shaking flask method and detection with inductively coupled plasma–atomic emission spectrometry (ICP–AES), in order to assess their environmental fate and tendency to bioaccumulate. Polarography was also used for the electrochemically active Se species, Se(IV), Se-Cyst, Se-CM and (CH₃)₂Se₂, and the results were compared with those measured by ICP–AES. Furthermore, the influence of pH was studied by determining the logarithm of the distribution coefficient, log D, at three pH values, 5, 7, and 9, as was the impact of the marine environment on the lipophilicity profile of the six investigated Se species. The results were compared with those estimated approximately by use of PrologD software, based on the Ghose-Crippen log P (P: partition coefficient) calculation system, the only system which incorporates values—even though approximate—for the atom type of Se. Finally, from our experimental data an indicative value of the Se–Se fragment for log P prediction, for use in drug design, was estimated.     

Synthesis,Bioactivity, Pharmacokinetic and Biomimetic Properties of Multi-Substituted Coumarin Derivatives

A series of novel multi-substituted coumarin derivatives were synthesized, spectroscopically characterized, and evaluated for their antioxidant activity, soybean lipoxygenase (LOX) inhibitory ability, their influence on cell viability in immortalized human keratinocytes (HaCaT), and cytotoxicity in adenocarcinomic human alveolar basal epithelial cells (A549) and human melanoma (A375) cells, in vitro. Coumarin analogues 4a–4f, bearing a hydroxyl group at position 5 of the coumarin scaffold and halogen substituents at the 3-phenyl ring, were the most promising ABTS^•+ scavengers. 6,8-Dibromo-3-(4-hydroxyphenyl)-4-methyl-chromen-2-one (4k) and 6-bromo-3-(4,5-diacetyloxyphenyl)-4-methyl-chromen-2-one (3m) exhibited significant lipid peroxidation inhibitory activity (IC₅₀ 36.9 and 37.1 μM). In the DCF-DA assay, the 4′-fluoro-substituted compound 3f (100%), and the 6-bromo substituted compounds 3i (80.9%) and 4i (100%) presented the highest activity. The 3′-fluoro-substituted coumarins 3e and 4e, along with 3-(4-acetyloxyphenyl)-6,8-dibromo-4-methyl-chromen-2-one (3k), were the most potent lipoxygenase (LOX) inhibitors (IC₅₀ 11.4, 4.1, and 8.7 μM, respectively) while displaying remarkable hydroxyl radical scavenging ability, 85.2%, 100%, and 92.9%, respectively. In silico docking studies of compounds 4e and 3k, revealed that they present allosteric interactions with the enzyme. The majority of the analogues (100 μΜ) did not affect the cell viability of HaCaT cells, though several compounds presented over 60% cytotoxicity in A549 or A375 cells. Finally, the human oral absorption (%HOA) and plasma protein binding (%PPB) properties of the synthesized coumarins were also estimated using biomimetic chromatography, and all compounds presented high %HOA (>99%) and %PPB (60–97%) values.