Lens alpha-crystallin and hypericin: a photophysical mechanism explains observed lens

Determining whether alpha-crystallin (the major lens protein) affects the photophysics of hypericin, a photosensitizing agent found in various plants, such as St. John's Wort, is important. Hypericin shows promise in cancer and human immunodeficiency virus therapy but may harm individuals taking St. John's Wort extracts (for mild to moderate depression). Hypericin causes hypericism, which is characterized by cellular damage in light-exposed areas. Ocular tissues are at risk for photosensitized damage; thus, we investigated the effects on hypericin photophysics by alpha-crystallin. We measured the transient absorption spectra and the 1270 nm luminescence of singlet (1Deltag) oxygen produced from hypericin in the presence of alpha-crystallin. alpha-Crystallin complexes hypericin, extending the lifetime of its triplet excited state; the Stern-Volmer slope is negative, but not linear, after a saturation curve. Damage to the lens protein by hypericin is known to occur via singlet oxygen, which oxidizes methionine, tryptophan and histidine residues. Binding to alpha-crystallin does not inhibit singlet oxygen formation by hypericin. alpha-Crystallin reacts with singlet oxygen with a rate constant of 1.3 x 10(8) M(-1) s(-1). Thus, we anticipate that hypericin will be an effective photosensitizer in the lens.     

Adsorption of block copolymers in nanoporous alumina

We have studied the adsorption of end-attaching block copolymer chains inside the cylindrical pores of nanoporous alumina. Highly asymmetric PS-PEO block copolymers, with a small PEO anchoring block and a long PS dangling block, were allowed to adsorb onto porous alumina substrates with an average pore diameter of ∼200 nm from toluene solution. The adsorption process was monitored using FTIR spectroscopy, whereas depth profile analysis was performed by means of XPS and Ar⁺ ion sputtering. It is found that the PS-PEO adsorption kinetics in porous alumina are ∼4 orders of magnitude slower than the corresponding case of a flat alumina substrate. It appears that chains adsorbed near the pore entrance early on tend to form a barrier for chains entering the pore at later times, thereby slowing down the adsorption process significantly. This effect is much more pronounced for large chains whose dimensions are comparable with the pore diameter. The equilibrium adsorbance value is also affected by chain size due to the additional entropic penalty associated with chain confinement, the adsorbance falling substantially when the chain dimensions become comparable with the pore diameter. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1676–1682, 2010     

Aspects of electromagnetic scattering in chiral media

In this work, we study two operators that arise in electromagnetic scattering in chiral media. We first consider electromagnetic scattering by a chiral dielectric with a perfectly conducting core. We define a chiral Calderon‐type surface operator in order to solve the direct electromagnetic scattering problem. For this operator, we state coercivity and prove compactness properties. In order to prove existence and uniqueness of the problem, we define some other operators that are also related to the chiral Calderon‐type operator, and we state some of their properties that they and their linear combinations satisfy. Then we sketch how to use these operators in order to prove the existence of the solution of the direct scattering problem. Furthermore, we focus on the electromagnetic scattering problem by a perfect conductor in a chiral environment. For this problem, we study the chiral far‐field operator that is defined on a unit sphere and contains the far‐field data, and we state and prove some of its properties that are preliminaries properties for solving the inverse scattering problem. Copyright © 2016 John Wiley & Sons, Ltd.     

Effect of reactant size on discrete stochastic chemical kinetics

This paper is aimed at understanding what happens to the propensity functions (rates) of bimolecular chemical reactions when the volume occupied by the reactant molecules is not negligible compared to the containing volume of the system. For simplicity our analysis focuses on a one-dimensional gas of N hard-rod molecules, each of length l. Assuming these molecules are distributed randomly and uniformly inside the real interval [0,L] in a nonoverlapping way, and that they have Maxwellian distributed velocities, the authors derive an expression for the probability that two rods will collide in the next infinitesimal time dt. This probability controls the rate of any chemical reaction whose occurrence is initiated by such a collision. The result turns out to be a simple generalization of the well-known result for the point molecule case l=0: the system volume L in the formula for the propensity function in the point molecule case gets replaced by the "free volume" L-Nl. They confirm the result in a series of one-dimensional molecular dynamics simulations. Some possible wider implications of this result are discussed.     

Polymer Dynamics in Polyurethane/clay Nanocomposites Studied by Dielectric and Thermal Techniques

Differential scanning calorimetry (DSC), broadband dielectric relaxation spectroscopy (DRS), and thermally stimulated depolarization current (TSDC) techniques were employed to investigate glass transition and polymer dynamics in nanocomposites of polyurethane (PU) and organically modified montmorillonite (MMT) (weight fraction 0%–15%) prepared by solution casting. The PU matrix was obtained from oligo(oxytetramethylene glycol) of molar mass 1000 g/mol, 4,4′-diphenylmethane diisocyanate and 1,1-dimethylhydrazine as chain extender. Wide-angle X-ray scattering confirmed the formation of partly exfoliated structures at low MMT content. DSC, DRS, and TSDC show, in agreement with each other, that a fraction of polymer makes no contribution to the glass transition and to the corresponding α relaxation, whereas the rest exhibits similar glass transition dynamics as the pure matrix. This fraction of immobilized polymer reaches a maximum at about 5 wt% MMT. Effects of MMT on the microphase-separated structure of PU are negligible, as indicated by the study of glass transition and interfacial dielectric polarization/relaxation. No effects of MMT on the local, secondary γ and β relaxations were observed. Mechanical properties show a maximum improvement at about 5 wt% MMT, in good correlation with morphology and dynamics.     

Effects of CNT inclusions on structure and dielectric properties of PVDF/CNT nanocomposites

ABSTRACT

The effects of multiwall carbon nanotube (CNT) inclusions on the crystalline structure of poly(vinylidene fluoride) (PVDF), and on the dielectric properties of PVDF/CNT nanocomposites (NCs), prepared by melt mixing, were investigated by employing X-ray diffraction, differential scanning calorimetry, and dielectric spectroscopy techniques. Our results imply that, in the NCs, the formation of β-phase crystals depends on specific compression treatment in the melt and fast cooling. Dielectric measurements on NCs, with CNT concentrations below the electrical percolation threshold, reveal that the dielectric strength of the two relaxation processes in the amorphous phase and dielectric permittivity, ?′, measured within the broad temperature range from ?150 °C to 60 °C, increase strongly with increasing CNT concentration. This enhancement of amorphous PVDF polarizability has been attributed to the increase of the local electric field, due to local polarization generated at the surface of conductive inclusions/CNT clusters.     

Stability of long transversely-isotropic elastic cylindrical shells under bending

The present paper investigates buckling of cylindrical shells of transversely-isotropic elastic material subjected to bending, considering the nonlinear prebuckling ovalized configuration. A large-strain hypoelastic model is developed to simulate the anisotropic material behavior. The model is incorporated in a finite-element formulation that uses a special-purpose “tube element”. For comparison purposes, a hyperelastic model is also employed. Using an eigenvalue analysis, bifurcation on the prebuckling ovalization path to a uniform wrinkling state is detected. Subsequently, the postbuckling equilibrium path is traced through a continuation arc-length algorithm. The effects of anisotropy on the bifurcation moment, the corresponding curvature and the critical wavelength are examined, for a wide range of radius-to-thickness ratio values. The calculated values of bifurcation moment and curvature are also compared with analytical predictions, based on a heuristic argument. Finally, numerical results for the imperfection sensitivity of bent cylinders are obtained, which show good comparison with previously reported asymptotic expressions.     

A Techno-Economic Study on the Outside Plant Cost of Current and Next-Generation Fiber-to-the-X Deployments

Abstract

A techno-economic study on the outside plant costs of fiber-to-the-X infrastructures is presented in this article. Standardized passive optical network and active optical network technologies, implemented in fiber-to-the-home architectures, are presented/compared in terms of costs. Future architectures based on passive optical networks are investigated, their outside plant infrastructure, and corresponding costs are reviewed. Cost comparisons of fiber-to-the-X infrastructures reveal significant differences. Besides fiber-to-the-node being the less costly, it is shown that the cost of high splitting ratio passive optical network fiber-to-the-home infrastructures is not increasing linearly with the splitting ratio. The highest splitting ratio is not always the one with the largest savings percentage. Referring to current and future fiber-to-the-home access network architectures/technologies, the flexibility of wavelength division multiplexing/time division multiplexing passive optical networks is estimated to reach a 40% reduction in outside plant cost compared with the home run architecture.