Analysis of thermal phases in calcareous Iron Age pottery using FT-IR and Raman spectroscopy

The work deals with the FT-IR and micro-Raman spectroscopy study of the pseudo-amorphous and crystalline thermal phases in the composition of calcareous Iron Age pottery from the Galilee. The application of second-derivative and curve-fitting techniques improves the identification of the thermal phases in the composition of the pottery and makes it possible to analyze the pseudo-amorphous phases which are formed during the firing of the clayey raw material to pottery. This technique makes it possible to distinguish between meta-smectite and meta-kaolinite and to estimate the firing temperature of the pottery. The Micro-Raman spectroscopy is sensitive to the structural degree of ordering of the thermal phases and enables point analysis of peculiar components in the composition of the pottery. Based on the spectroscopic study, it is concluded that the calcareous pottery contained large amounts of microcrystalline-recarbonated calcite mixed with the meta-clay. The large amount of recarbonated calcite in the pottery material and the relatively low firing temperature indicates that instead of sintering the clay, lime technology was used for the cementation of the calcareous vessels. This process took place after the firing by recarbonation of the decomposed calcite which leads to cementation of the vessels with microcrystalline calcite.     

First Order Approximation of an Elliptic 3D Singular Perturbation Problem

A three-dimensional elliptic singular perturbation problem with discontinuous boundary values is considered. The solution of the problem is written in terms of a double integral. A saddle point analysis is used to obtain a first approximation, which is expressed in terms of a function that can be viewed as a generalization of the complementary error function.     

Antibacterial and antifungal LDPE films for active packaging

Active antimicrobial packaging is a promising form of active packaging that can kill or inhibit microorganism growth in order to maintain product quality and safety. One of the most common approaches is based on the release of volatile antimicrobial agents from the packaging material such as essential oils. Due to their highly volatile nature, the challenge is to preserve the essential oils during the high‐temperature melt processing of the polymer, while maintaining high antimicrobial activity for a desired shelf life. This study suggests a new approach in order to achieve this goal. Antimicrobial active films are developed based on low‐density polyethylene (LDPE), organo‐modified montmorillonite clays (MMT) and carvacrol (used as an essential oil model). In order to minimize carvacrol loss throughout the polymer compounding, a pre‐compounding step is developed in which clay/carvacrol hybrids are produced. The hybrids exhibit a significant increase in the d‐spacing of clay and enhanced thermal stability. The resulting LDPE/(clay/carvacrol) films exhibit superior and prolonged antibacterial activity against Escherichia coli and Listeria innocua, while polymer compounded with pure carvacrol loses the antibacterial properties within days. The films also present an excellent antifungal activity against Alternaria alternata, used as a model plant pathogenic fungus. Furthermore, infrared spectroscopy analysis of the LDPE/(clay/carvacrol) system displayed significantly higher carvacrol content in the film as well as a slower out‐diffusion of the carvacrol molecules in comparison to LDPE/carvacrol films. Thus, these new films have a high potential for antimicrobial food packaging applications due to their long‐lasting and broad‐spectrum antimicrobial efficacy. Copyright © 2014 John Wiley & Sons, Ltd.     

Protein delivery based on uncoated and chitosan-coated mesoporous silicon microparticles

Mesoporous silicon is a biocompatible, biodegradable material that is receiving increased attention for pharmaceutical applications due to its extensive specific surface. This feature enables to load a variety of drugs in mesoporous silicon devices by simple adsorption-based procedures. In this work, we have addressed the fabrication and characterization of two new mesoporous silicon devices prepared by electrochemistry and intended for protein delivery, namely: (i) mesoporous silicon microparticles and (ii) chitosan-coated mesoporous silicon microparticles. Both carriers were investigated for their capacity to load a therapeutic protein (insulin) and a model antigen (bovine serum albumin) by adsorption. Our results show that mesoporous silicon microparticles prepared by electrochemical methods present moderate affinity for insulin and high affinity for albumin. However, mesoporous silicon presents an extensive capacity to load both proteins, leading to systems were protein could represent the major mass fraction of the formulation. The possibility to form a chitosan coating on the microparticles surface was confirmed both qualitatively by atomic force microscopy and quantitatively by a colorimetric method. Mesoporous silicon microparticles with mean pore size of 35 nm released the loaded insulin quickly, but not instantaneously. This profile could be slowed to a certain extent by the chitosan coating modification. With their high protein loading, their capacity to provide a controlled release of insulin over a period of 60-90 min, and the potential mucoadhesive effect of the chitosan coating, these composite devices comprise several features that render them interesting candidates as transmucosal protein delivery systems.     

Application of complementary mass spectrometric techniques to the identification of ketoprofen phototransformation products

Ketoprofen (KP) is a nonsteroidal anti-inflammatory drug, which during UV irradiation rapidly transforms into benzophenone derivatives. Such transformation products may occur after topical application of KP, which is then exposed to sunlight resulting in a photo-allergic reaction. These reactions are mediated by the benzophenone moiety independently of the amount of allergen. The same reactions will also occur during wastewater or drinking water treatment albeit their effect in the aqueous environment is yet to be ascertained. In addition, only a few such transformation products have been recognised. To enable the detection and structural elucidation of the widest range of KP transformation products, this study applies complementary chromatographic and mass spectrometric techniques including gas chromatography coupled to single quadrupole or ion trap mass spectrometry and liquid chromatography hyphenated with quadrupole-time-of-flight mass spectrometry. Based on structural information gained in tandem and multiple MS experiments, and on highly accurate molecular mass measurements, chemical structures of 22 transformation products are proposed and used to construct an overall breakdown pathway. Among the identified transformation products all but two compounds retained the benzophenone moiety--a result, which raises important issues concerning the possible toxic synergistic effects of KP and its transformation products. These findings trigger further research into water treatment technologies that would limit their entrance into environmental or drinking waters.     

A straightforward synthetic entry to cleavamine-type indole alkaloids by a ring-closing metathesis-vinyl halide Heck cyclization strategy

An indole-templated ring-closing metathesis has been used to create the central nine-membered ring of the cleavamine-type alkaloids. A subsequent intramolecular vinyl halide Heck reaction upon the resulting azacyclononene ring completes the assembly of the strained 1-azabicyclo[6.3.1]dodecane framework of the alkaloids. The usefulness of the approach is illustrated with the synthesis of (±)-cleavamine and (±)-dihydrocleavamine.     

Characterization of porosity in a 19th century painting ground by synchrotron radiation X-ray tomography

The study of the early oeuvre of the Swiss painter Cuno Amiet (1868–1961) has revealed that, up to 1907, many of his grounds were hand applied and are mainly composed of chalk, bound in protein. These grounds are not only lean and absorbent, but also, as Synchrotron radiation X-ray microtomography has shown, porous. Our approach to the characterization of pore structure and quantity, their connectivity, and homogeneity is based on image segmentation and application of a clustering algorithm to high-resolution X-ray tomographic data. The issues associated with the segmentation of the different components of a ground sample based on X-ray imaging data are discussed. The approach applied to a sample taken from “Portrait of Max Leu” (1899) by Amiet revealed the presence of three sublayers within the ground with distinct porosity features, which had not been observed optically in cross-section. The upper and lower layers are highly porous with important connectivity and thus prone to water uptake/storage. The middle layer however shows low and nonconnected porosity at the resolution level of the X-ray tomography images, so that few direct water absorption paths through the entire sample exist. The potential of the method to characterize porosity and to understand moisture-related issues in paint layer degradation are discussed.     

Some New Results for McKean’s Graphs with Applications to Kac’s Equation

The main goal of the present paper is to sharpen some results about the error made when the Wild sums, used to represent the solution of the Kac analog of Boltzmann’s equation, are truncated at the n-th stage. More precisely, in Carlen, Carvalho and Gabetta (J. Funct. Anal. 220: 362–387 (2005)), one finds a bound for the above-mentioned error which depends on (an ^Λ+ε). On the one hand, it is shown that Λ, the least negative eigenvalue of the linearized collision operator, is the best possible exponent. On the other hand, ε is an extra strictly positive number and a a positive coefficient which depends on ε too. Thus, it is interesting to check whether ε can be removed from the above bound. According to the aforesaid reference, this problem is studied here by means of the probability distribution of the depth of a leaf in a McKean random tree. In fact, an accurate study of the probability generating function of such a depth leads to conclude that the above bound can be replaced with (a′ n ^Λ).     

The compound decision problem in the opponent case

The compound decision problem is considered under the assumption that Nature plays the role of an opponent. The empirical Bayes approach is a particular case of this approach. It is shown that in many instances sequential compound rules with good asymptotic properties for the fixed case have similar good properties in the opponent case.     

Central limit theorems for solutions of the Kac equation: speed of approach to equilibrium in weak metrics

This paper is part of our efforts to show how direct application of probabilistic methods, pertaining to central limit general theory, can enlighten us about the convergence to equilibrium of the solutions of the Kac equation. Here, we consider convergence with respect to the following metrics: Kolmogorov’s uniform metric; 1 and 2 Gini’s dissimilarity indices (widely known as 1 and 2 Wasserstein metrics); χ-weighted metrics. Our main results provide new bounds, or improvements on already well-known ones, for the corresponding distances between the solution of the Kac equation and the limiting Gaussian (Maxwellian) distribution. The study is conducted both under the necessary assumption that initial data have finite energy, without assuming existence of moments of order greater than 2, and under the condition that the (2 + δ)-moment of the initial distribution is finite for some δ > 0.