Polyelectrolyte stars in planar confinement

We employ monomer-resolved molecular dynamics simulations and theoretical considerations to analyze the conformations of multiarm polyelectrolyte stars close to planar, uncharged walls. We identify three mechanisms that contribute to the emergence of a repulsive star-wall force, namely, the confinement of the counterions that are trapped in the star interior, the increase in electrostatic energy due to confinement as well as a novel mechanism arising from the compression of the stiff polyelectrolyte rods approaching the wall. The latter is not present in the case of interaction between two polyelectrolyte stars and is a direct consequence of the impenetrable character of the planar wall.     

The mechanism of the protonation of metal (hydr)oxides in aqueous solutions studied for various interfacial/surface ionization models and physicochemical parameters: a critical review and a novel approach

The mechanism of the protonation of solid metal (hydr)oxides in aqueous media was investigated using simulation and experimental work. It was found that the apparent acidity/basicity of each kind of surface sites of metal (hydr)oxides in aqueous suspensions is strongly influenced by the overall surface charge of the (hydr)oxide and thus by the electrical potential smeared out at the interfacial region. Depending on its sign this increases or decreases the hydrogen ion concentration on the surface, thus promoting or hindering protonation. This is manifested by the shifts of the protonation peaks of the various kinds of sites with respect to the -pK values of the corresponding intrinsic protonation constants and the appearance of an extra peak in the d[H+cons,surf]/dpH vs. pH curves. Potentiometric titrations experiments performed for four technologically important oxides showed that the proposed protonation mechanism describes indeed the protonation of polycrystalline (hydr)oxides in aqueous media.     

Targeting of sebocytes by aminolevulinic acid-dependent photosensitization

Photodynamic therapy using 5-aminolevulinic acid-induced protoporphyrin IX has been developed as a very useful therapeutic modality. Recently, several authors have reported on the efficacy of this procedure for acne. This approach is based on the fact that 5-aminolevulinic acid-induced protoporphyrin IX has strong selectivity for sebaceous glands. We used the immortalized human sebaceous gland cell line SZ95 to investigate cellular mechanisms of photodynamic therapy using 5-aminolevulinic acid-induced protoporphyrin IX. Quantification of induced protoporphyrin IX production showed dependence on the applied 5-aminolevulinic acid dose. When SZ95 sebocytes were differentiated by arachidonic acid treatment, there was no difference between them and the control cells with respect to both the amount of 5-aminolevulinic acid-induced protoporphyrin IX and the phototoxic effects. We altered protoporphyrin IX formation rates by growing cells scattered as single cells in the culture dishes. Single cells produced significantly lower protoporphyrin IX levels than those grown with intercellular contacts. Intracellular localization of protoporphyrin IX was imaged using confocal laser scanning microscopy. The differentiation-specific lipid droplets were virtually excluded from protoporphyrin IX fluorescence. In addition to weak mitochondrial and strong membrane fluorescence, distinctive spots with strong fluorescence were observed. These did not colocalize with fluorescent probes for mitochondria, lysosomes or the Golgi apparati.     

A Multi-Scale Approach to Model Two-Phase Flow in Heterogeneous Porous Media

The immiscible displacement of a wetting fluid by a non-wetting one in heterogeneous porous media is modeled using a multi-scale network-type analysis: (1) The pressure-controlled immiscible displacement of water by oil in pore-and-throat networks (1st length scale ~ 1?mm) is simulated as a capillary-driven process. (2) The pressure-controlled immiscible displacement in uncorrelated cubic lattices (2nd length scale ~ 1?cm) is simulated as a site percolation process governed by capillary and gravity forces. At this scale, each node represents a network of the previous scale. (3) The rate-controlled immiscible displacement of water by oil in cubic networks (3rd length scale ~ 10?cm), where each node represents a lattice of the previous scale, is simulated by accounting for capillary, gravity, and viscous forces. The multi-scale approach along with the information concerning the pore structure properties of the porous medium can be employed to determine the transient responses of the pressure drop and axial distribution of water saturation, and estimate the effective (up-scaled) relative permeability functions. The method is demonstrated with application to data of highly heterogeneous soils.     

Linear and nonlinear optical susceptibilities in a laterally coupled quantum-dot–quantum-ring system

Linear and nonlinear optical susceptibilities in a laterally coupled quantum-dot–quantum-ring system have been theoretically studied. In general, we find that the structure parameters of the coupled system significantly affect the optical susceptibilities. The enhancement of the coupling effects between the dot and ring is found to increase considerably the optical susceptibilities and redshift drastically the transition energies. Comparing to the linear susceptibility, the nonlinear optical susceptibility is found to be more sensitive to the variation of the structure parameters. A comprehensive analysis of the electron probability density movement with respect to the modification of the structure parameters is provided, which offers a unique perspective of the ground-state localization.     

Raman spectroscopic characterization of novel carbon‐bonded filter compositions for steel melt filtration

In this work, Raman scattering results on novel carbon‐bonded filter compositions are presented. Such filters are already used for steel melt filtration; however, the potential of this carbon‐bonded Al₂O₃–C system regarding material characteristics and filtration efficiency has not been fully understood yet. In order to investigate thermally induced structural changes of the filter compositions, micro‐Raman spectroscopy was applied. Analyzing the position, intensity, and full width at half maximum of G and D peaks in the Raman spectra, it could be determined that the carbon appears in graphitic form and the graphitic cluster size was estimated. We found an increase of the lateral cluster size L_a with increasing coking temperature. Copyright © 2013 John Wiley & Sons, Ltd.     

Multiplicative intrinsic component optimization (MICO) for MRI bias field estimation and tissue segmentation

This paper proposes a new energy minimization method called multiplicative intrinsic component optimization (MICO) for joint bias field estimation and segmentation of magnetic resonance (MR) images. The proposed method takes full advantage of the decomposition of MR images into two multiplicative components, namely, the true image that characterizes a physical property of the tissues and the bias field that accounts for the intensity inhomogeneity, and their respective spatial properties. Bias field estimation and tissue segmentation are simultaneously achieved by an energy minimization process aimed to optimize the estimates of the two multiplicative components of an MR image. The bias field is iteratively optimized by using efficient matrix computations, which are verified to be numerically stable by matrix analysis. More importantly, the energy in our formulation is convex in each of its variables, which leads to the robustness of the proposed energy minimization algorithm. The MICO formulation can be naturally extended to 3D/4D tissue segmentation with spatial/sptatiotemporal regularization. Quantitative evaluations and comparisons with some popular softwares have demonstrated superior performance of MICO in terms of robustness and accuracy.     

Ferromagnetic interactions in a 1D alternating linear chain of π-stacked 1,3-diphenyl-7-(thien-2-yl)-1,4-dihydro-1,2,4-benzotriazin-4-yl radicals

X-ray studies show that 1,3-diphenyl-7-(thien-2-yl)-1,4-dihydro-1,2,4-benzotriazin-4-yl (6) adopts a distorted, slipped π-stacked structure of centrosymmetric dimers with alternate short and long interplanar distances (3.48 and 3.52 ?). Cyclic voltammograms of 7-(thien-2-yl)benzotriazin-4-yl 6 show two fully reversible waves that correspond to the -1/0 and 0/+1 processes. EPR and DFT studies on radical 6 indicate that the spin density is mainly delocalized over the triazinyl fragment. Magnetic susceptibility measurements show that radical 6 obeys Curie-Weiss behavior in the 5-300 K region with C=0.378 emu K mol(-1) and θ=+4.72 K, which is consistent with ferromagnetic interactions between S=1/2 radicals. Fitting the magnetic susceptibility revealed the behavior is consistent with an alternating ferromagnetic chain (g=2.0071, J(1) =+7.12 cm(-1), J(2) =+1.28 cm(-1)).     

A photosynthetic biosensor with enhanced electron transfer generation realized by laser printing technology

One of the limits of current electrochemical biosensors is a lack of methods providing stable and highly efficient junctions between biomaterial and solid-state devices. This paper shows how laser-induced forward transfer (LIFT) can enable efficient electron transfer from photosynthetic biomaterial immobilized on screen-printed electrodes (SPE). The ideal pattern, in terms of photocurrent signal of thylakoid droplets giving a stable response signal with a current intensity of approximately 335 ± 13 nA for a thylakoid mass of 28 ± 4 ng, was selected. It is shown that the efficiency of energy production of a photosynthetic system can be strongly enhanced by the LIFT process, as demonstrated by use of the technique to construct an efficient and sensitive photosynthesis-based biosensor for detecting herbicides at nanomolar concentrations.