Orbital picture of ionization and its breakdown in nanoarrays of quantum dots

We present exact numerical results indicating that ionization could be a useful tool to study electron correlations in artificial molecules and nanoarrays of metallic quantum dots. For nanorings consisting of Ag quantum dots of the type already fabricated, we demonstrate that the molecular orbital picture breaks down even for lowest energy ionization processes, in contrast to ordinary molecules. Our ionization results yield a transition point between localization and delocalization regimes in good agreement with various experimental data.     

Surface photovoltage spectroscopy and surface piezoelectric effect in GaAs

“Real” (111) surfaces of n-type GaAs were investigated employing surface photovoltage spectroscopy and the surface piezoelectric effect. Surface states at the energy position E_c ? E_t ? 0.72 eV were found on both the Ga and the As surfaces. Both types of surfaces exhibited a barrier of about 0.55 V. No variations in the surface barrier or the energy position of the surface states were observed in various ambients at atmospheric pressure (dry air, wet air, ammonia and ozone). However, the capture cross-section of the surface states for electrons, as determined from the surface piezoelectric effect transients (of the order of 10^?13 cm²), was found to be sensitive to the ambient. It decreased in wet air and increased in ozone. This effect was more pronounced on the As than on the Ga surfaces. Additional surface states were found to be present in the energy region of 0.9 to 1.0 eV, below the bottom of the conduction band. However, their exact energy positions could not be determined due to interference caused by the carrier trapping of the surface states at E_c ? E_t ? 0.72 eV.     

Fluctuation-driven molecular transport through an asymmetric membrane channel

Channel proteins that selectively conduct molecules across cell membranes often exhibit an asymmetric structure. By means of a stochastic model, we argue that channel asymmetry in the presence of nonequilibrium fluctuations, fueled by the cell's metabolism as observed recently, can dramatically influence the transport through such channels by a ratchetlike mechanism. For an aquaglyceroporin that conducts water and glycerol, we show that a previously determined asymmetric glycerol potential leads to enhanced inward transport of glycerol, but for unfavorably high glycerol concentrations also to enhanced outward transport that protects a cell against poisoning.     

Frequency‐dependent NMR relaxation of liquids confined inside porous media containing an increased amount of magnetic impurities

Frequency‐dependent NMR relaxation studies have been carried out on water (polar) and cyclohexane (nonpolar) molecules confined inside porous ceramics containing variable amounts of iron oxide (III). The porous ceramics were prepared by compression of powders mixed with iron oxide followed by thermal treatment. The pore size distribution was estimated using a technique based on diffusion in internal fields that exposed a narrow distribution of macropore sizes with an average pore dimension independent of iron oxide content. The relaxation dispersion curves were obtained at room temperature using a fast field cycling NMR instrument. They display an increase of the relaxation rate proportional to the iron oxide concentration. This behavior is more prominent at low Larmor frequencies and is independent of the polar character of the confined molecules. The results reported here can be fitted well with a relaxation model considering exchange between molecules in the close vicinity of the paramagnetic centers located in the surface and bulk‐like molecules inside the pores. This model allows the extraction of the transverse diffusional correlation time that can be related to the polar character of the confined molecules. Copyright © 2013 John Wiley & Sons, Ltd.     

Sequential optimality conditions for composed convex optimization problems

Using a general approach which provides sequential optimality conditions for a general convex optimization problem, we derive necessary and sufficient optimality conditions for composed convex optimization problems. Further, we give sequential characterizations for a subgradient of the precomposition of a K-increasing lower semicontinuous convex function with a K-convex and K-epi-closed (continuous) function, where K is a nonempty convex cone. We prove that several results from the literature dealing with sequential characterizations of subgradients are obtained as particular cases of our results. We also improve the above mentioned statements.     

Earth surface effects on active faults: An eigenvalue asymptotic analysis

We study in this paper an eigenvalue problem (of Steklov type), modeling slow slip events (such as silent earthquakes, or earthquake nucleation phases) occurring on geological faults. We focus here on a half space formulation with traction free boundary condition: this simulates the earth surface where displacements take place and can be picked up by GPS measurements. We construct an appropriate functional framework attached to a formulation suitable for the half space setting. We perform an asymptotic analysis of the solution with respect to the depth of the fault. Starting from an integral representation for the displacement field, we prove that the differences between the eigenvalues and eigenfunctions attached to the half space problem and those attached to the free space problem, is of the order of d^-2, where d is a depth parameter: intuitively, this was expected as this is also the order of decay of the derivative of the Green's function for our problem. We actually prove faster decay in case of symmetric faults. For all faults, we rigorously obtain a very useful asymptotic formula for the surface displacement, whose dominant part involves a so called seismic moment. We also provide results pertaining to the analysis of the multiplicity of the first eigenvalue in the line segment fault case. Finally we explain how we derived our numerical method for solving for dislocations on faults in the half plane. It involves integral equations combining regular and Hadamard's hypersingular integration kernels.     

The Effects of Different Superplasticizers and Water-to-Cement Ratios on the Hydration of Gray Cement Using T2-NMR

In the present work, we compare the influence introduced by the variation of water-to-cement ratio and the presence of different superplasticizers on the hydration process of gray cement using the low-field nuclear magnetic resonance relaxometry. The stages of hydration are identified and a relationship between the ettringite formation during hydration process and the transverse relaxation time is established. It is also demonstrated that the addition of small amounts of superplasticizer in the cement paste significantly expands the dormant period while the hardening period is reduced. On the other side, the increase in the water-to-cement ratio has little influence on the dormant period but can instead increase the porosity of the sample and consequently reduce its strength.     

Shape-preserving properties and asymptotic behaviour of the semigroup generated by the Black-Scholes operator

The paper is devoted to a careful analysis of the shape-preserving properties of the strongly continuous semigroup generated by a particular second-order differential operator, with particular emphasis on the preservation of higher order convexity and Lipschitz classes. In addition, the asymptotic behaviour of the semigroup is investigated as well. The operator considered is of interest, since it is a unidimensional Black-Scholes operator so that our results provide qualitative information on the solutions of classical problems in option pricing theory in Mathematical Finance. The paper is dedicated to Professor Luigi Albano on the occasion of his 70th birthday.     

A unique geometry of the active site of angiotensin-converting enzyme consistent with structure-activity studies

Summary Previous structure-activity studies of captopril and related active angiotensin-converting enzyme (ACE) inhibitors have led to the conclusion that the basic structural requirements for inhibition of ACE involve (a) a terminal carboxyl group; (b) an amido carbonyl group; and (c) different types of effective zinc (Zn) ligand functional groups. Such structural requirements common to a set of compounds acting at the same receptor have been used to define a pharmacophoric pattern of atoms or groups of atoms mutually oriented in space that is necessary for ACE inhibition from a stereochemical point of view. A unique pharmacophore model (within the resolution of approximately 0.15 Å) was observed using a method for systematic search of the conformational hyperspace available to the 28 structurally different molecules under study. The method does not assume a common molecular framework, and, therefore, allows comparison of different compounds that is independent of their absolute orientation.Consequently, by placing the carboxyl binding group, the binding site for amido carbonyl, and the Zn atom site in positions determined by ideal binding geometry with the inhibitors' functional groups, it was possible to clearly specify a geometry for the active site of ACE.