Faceting and commensurability in crystal structures of colloidal thin films

This Letter investigates the influence of finite size effects on the particle arrangement of thin film colloidal crystals. A rich variety of crystallographic faceting with large single domain microcrystallites is shown. Optical reflectance experiments together with scanning electron microscopy permit the identification of the crystal symmetry and the facet orientation, as well as the exact number of monolayers. When the cell thickness is not commensurable with a high symmetry layering, particles arrange themselves in a periodic distribution of (111)- and (100)-orientated face centered cubic (fcc) microcrystallites separated by planar defects. These structures can be described as a fcc ordering orientated along a vicinal surface, modified by a periodic distribution of fcc (111) stacking faults.     

Voltammetric Electronic Tongue Based on Carbon Paste Electrodes Modified with Biochar for Phenolic Compounds Stripping Detection

Biochar is a charcoal produced from the biomass pyrolysis process that presents a highly porous and functionalized surface. In the present work an array of carbon paste electrodes (CPE) made of different forms of carbon (graphite, carbon nanotubes and activated biochar) was evaluated in the development of an electronic tongue for discrimination and stripping voltammetric determination of catechol (CAT), 4‐ethylcatechol (4‐EC) and 4‐ethylguaiacol (4‐EG) phenolic compounds. Morphological characterization of carbon materials and electrodes surfaces was performed by scanning electron microscopy (SEM) and semi‐quantitative elemental composition by energy dispersive spectroscopy (EDS). Electrochemical Impedance Spectroscopy (EIS) measurements were used for electrochemical characterization of electrodes. Cyclic voltammetry measurements were performed for the phenolic compounds evaluated using different concentrations. Principal component analysis (PCA) was performed to evaluate the qualitative analysis. Quantitative data modeling was done using artificial neural networks (ANN). The proposed sensor array presented analytical potentiality allowing the distinction and determination of CAT, 4‐EC and 4‐EG by using chemometric processing. The method showed sensibility, reproducibility and a good linearity (R²>0.9940) for three compounds evaluated. Spontaneous preconcentration of three compounds was possible using all three sensors, which can allow the application of these as passive samplers for remote determinations of phenolic compounds in wine and food samples.     

Mean ergodicity and spectrum of the Cesàro operator on weighted $$c_0$$ spaces

A detailed investigation is made of the continuity, the compactness and the spectrum of the Cesàro operator \(\mathsf {C}\) acting on the weighted Banach sequence space \(c_0(w)\) for a bounded, strictly positive weight w. New features arise in the weighted setting (e.g. existence of eigenvalues, compactness, mean ergodicity) which are not present in the classical setting of \(c_0\).     

The Cesàro Operator in Growth Banach Spaces of Analytic Functions

The Cesàro operator C, when acting in the classical growth Banach spaces \({A^{-\gamma}}\) and \({A_0^{-\gamma}}\), for \({\gamma} > 0\), of analytic functions on \({\mathbb{D}}\), is investigated. Based on a detailed knowledge of their spectra (due to A. Aleman and A.-M. Persson) we are able to determine the norms of these operators precisely. It is then possible to characterize the mean ergodic and related properties of C acting in these spaces. In addition, we determine the largest Banach space of analytic functions on \({\mathbb{D}}\) which C maps into \({A^{-\gamma}}\) (resp. into \({A_0^{-\gamma}}\)); this optimal domain space always contains \({A^{-\gamma}}\) (resp. \({A_0^{-\gamma}}\)) as a proper subspace.     

Thermodynamic and transport properties of carbon dioxide from molecular simulation

Monte Carlo and molecular dynamics simulations have been used in order to test the ability of a three center intermolecular potential for carbon dioxide to reproduce literature experimental thermophysical values. In particular, both the shear viscosity under supercritical conditions and along the phase coexistence line, as well as the thermal conductivity under supercritical conditions, have been calculated. Together with the already reported excellent agreement for the phase coexistence densities, the authors find that the agreement with experimental values is, in general, good, except for the thermal conductivity at low density. Although extended versions of the model were employed, which include an explicit account of bending and vibrational degrees of freedom, a significant difference was still found with respect to the reported experimental value.     

Mean ergodicity of multiplication operators in weighted spaces of holomorphic functions

Multiplication operators in weighted Banach (and locally convex) spaces of functions holomorphic in the unit disc are well known. In this note we investigate the connection between power boundedness, mean ergodicity and uniform mean ergodicity of such operators. Received: 13 October 2008, Revised: 18 November 2008     

Topological Structure of the Set of Weighted Composition Operators on Weighted Bergman Spaces of Infinite Order

We consider the topological space of all weighted composition operators on weighted Bergman spaces of infinite order endowed with the operator norm. We show that the set of compact weighted composition operators is path connected. Furthermore, we find conditions to ensure that two weighted composition operators are in the same path connected component if the difference of them is compact. Moreover, we compare the topologies induced by L(H^∞) and L(H^∞_v) on the space of bounded composition operators and give a sufficient condition for a composition operator to be isolated.     

Analysis of polymer adsorption onto colloidal particles

The structure of the layer formed after polymer adsorption onto a spherical particle is numerically studied by means of the application of the Single-Chain Mean-Field theory. We have determined several overall layer properties including the monomer volume fraction profiles, the layer thickness, adsorbances related to loops and to tails, as well as the variation of the crossover distance between loops and tails for different particle radii and fixed polymer length. When the radius of the sphere is small enough to affect the loop layer, one enters a single-adsorbed-chain regime, characterized by a critical sphere radius. In this regime, structural changes in the adsorbed layer arise. For such small sphere, the loop layer is confined to a region whose thickness is of the order of the radius of the adsorbing sphere, and two long tails dominate the outer layer and the adsorbance due to tails dominates that due to loops. An analysis of the structure of the outer tail layer for this small sphere case is also presented.     

Model shape transitions of micelles: spheres to cylinders and disks

We present a microscopic analysis of shape transitions of micelles of model linear nonionic surfactants. In particular, symmetric H(4)T(4) and asymmetric H(3)T(6) surfactants have been chosen for the study. In a previous work, it has been observed that symmetric surfactants have a strong tendency to prefer spherical micelles over a wide range of chemical potentials, while asymmetric surfactants undergo shape transitions between a spherical micelle at low concentration to other forms, mainly finite cylindrical micelles. This study combines the application of a two-dimensional single-chain mean-field theory (SCMFT) with Monte Carlo (MC) simulations of exactly the same systems. On the one hand, the characteristics of the SCMFT make this method suitable for free energy calculations, especially for small surfactants, due to the incorporation of relevant microscopic details in the model. On the other hand, MC simulations permit us to obtain a complete picture of the statistical mechanical problem, for the purpose of validation of the mean-field calculations. Our results reveal that the spherical shape for the symmetric surfactant is stable over a large range of surfactant concentrations. However, the asymmetric surfactant undergoes a complex shape transition that we have followed by calculating the standard chemical potential as a function of the aggregation number. The results indicate that the system forms prolate spheroids prior to developing short capped cylinders that gradually grow in length, with some oscillations in the energy of formation. The most important result of our work is the evidence of a bifurcation where, together with the elongated objects, the system can develop oblate aggregates and finally a torus shape similar to a red blood cell.