Cyclic oligomers content in anionic poly (ϵ-caprolactam)

The influence of initiator and activator concentrations on the anionic polymerization of ϵ-caprolactam and, in particular, on the methanol – extractable fraction of the final polymer has been widely studied. Due to the increasing interest of this polymerization in the field of reaction injection molding (RIM) technology, a thorough investigation has been also carried out to find the best experimental conditions for this reaction in the mold. The effect of postpolymerization annealing on the overall amount of low-molecular mass substances, among which cyclic oligomers, has been evaluated. Thermal properties as well as crystallinity of the resultant materials have been examined. A comparison with literature data is given; the suggested correlation between the amount of the oligomeric fraction and the molecular arrangement of the polymer in the solid state is discussed.     

High performance electrochemical sensor based on modified screen-printed electrodes with cost-effective dispersion of nanostructured carbon black

A novel sensor based on a screen-printed electrode (SPE) modified with a stable dispersion of commercially available carbon black (CB) N220 was developed. This probe showed significantly enhanced electrochemical activity relative to a bare SPE when tested with ferricyanide, epinephrine, norepinephrine, benzoquinone and NADH. When challenged in amperometric batch mode with NADH, the response was stable and revealed a linear dependence up to 2·10^?4 mol L^?1 with a detection limit of 3·10^?7 mol L^?1. The analytical performance, coupled with the low cost of the CB nanomaterial, suggests that this sensor holds promise for electrochemical applications.     

The MAST FV/FE scheme for the simulation of two-dimensional thermohaline processes in variable-density saturated porous media

A novel methodology for the simulation of 2D thermohaline double diffusive processes, driven by heterogeneous temperature and concentration fields in variable-density saturated porous media, is presented. The stream function is used to describe the flow field and it is defined in terms of mass flux. The partial differential equations governing system is given by the mass conservation equation of the fluid phase written in terms of the mass-based stream function, as well as by the advection–diffusion transport equations of the contaminant concentration and of the heat. The unknown variables are the stream function, the contaminant concentration and the temperature. The governing equations system is solved using a fractional time step procedure, splitting the convective components from the diffusive ones. In the case of existing scalar potential of the flow field, the convective components are solved using a finite volume marching in space and time (MAST) procedure; this solves a sequence of small systems of ordinary differential equations, one for each computational cell, according to the decreasing value of the scalar potential. In the case of variable-density groundwater transport problem, where a scalar potential of the flow field does not exist, a second MAST procedure has to be applied to solve again the ODEs according to the increasing value of a new function, called approximated potential. The diffusive components are solved using a standard Galerkin finite element method. The numerical scheme is validated using literature tests.     

Subtracted shifted Raman spectroscopy of organic dyes and lakes

Resonance Raman spectroscopy has been utilized to identify vegetal and animal dyes and lakes. These compounds have been used by artists since antiquity, and their identification has important implications in art history and conservation. The resonance condition is useful when working with real ancient objects so as to enhance the Raman scattering of chromophores with respect to the strong signal of the matrix, such as the textile or parchment over which the colorant is supported. The strong fluorescence that generally characterizes the resonance Raman spectra was eliminated by using subtracted shifted Raman spectroscopy (SSRS). A systematic study on reference organic dyes was primarily carried out to evaluate the suitability of the method and to estimate the strengths and limitations of the spectrum reconstruction process. The method was then applied to the noninvasive identification of madder on ancient dyed silk textiles such as an altar table cloth and a manutergium attributed to the Egyptian artistic textile production of the 10th–11th Century A.D. Copyright © 2009 John Wiley & Sons, Ltd.     

Bleaching of red lake paints in encaustic mummy portraits

The present paper reports on the study of the development of whitish opacity in pink paints in encaustic mummy portraits. Non-invasive measurements carried out on two encaustic portraits belonging to the Ny Carlsberg Glyptotek, Copenhagen, by reflectance FTIR and UV–vis fluorescence have shown that the areas prone to the bleaching phenomenon had been painted with melted beeswax and an anthraquinone vegetal lake mixed with calcium sulphate hemihydrate and dihydrate. The hypothesis that the bleaching disease was neither related to a degradation of the dyes nor to an alteration of the wax but rather to a dehydration–hydration reaction of the CaSO₄–H₂O system, has been corroborated by the analyses of two microsamples from the bleached areas and ascertained by accelerated ageing experiments on encaustic models.     

Kinetic control of the direction of inclusion of nitroxide radicals into cyclodextrins

N-benzyl-tert-butyl nitroxide derivatives substituted at the aromatic ring form host-guest inclusion complexes with β-and γ-cyclodextrin. They were employed as probes to assess substituent effects on the geometry of the complex and on the kinetics of this complexation by combining EPR and (1)H NMR data.     

Molecular Fluorescence Imaging Spectroscopy for Mapping Low Concentrations of Red Lake Pigments: Van Gogh's Painting The Olive Orchard

Vincent van Gogh used fugitive red lake pigments that have faded in some paintings. Mapping their distribution is key to understanding how his paintings have changed with time. While red lake pigments can be identified from microsamples, in situ identification and mapping remain challenging. This paper explores the ability of molecular fluorescence imaging spectroscopy to identify and, more importantly, map residual non-degraded red lakes. The high sensitivity of this method enabled identification of the emission spectra of eosin (tetrabromine fluorescein) lake mixed with lead or zinc white at lower concentrations than elemental X-ray fluorescence (XRF) spectroscopy used on account of bromine. The molecular fluorescence mapping of residual eosin and two carmine red lakes in van Gogh's The Olive Orchard is demonstrated and compared with XRF imaging spectroscopy. The red lakes are consistent with the composition of paint tubes known to have been used by van Gogh.     

On Hyers-Ulam stability for a class of functional equations

Summary In this paper we prove some stability theorems for functional equations of the formg[F(x, y)]=H[g(x), g(y), x, y]. As special cases we obtain well known results for Cauchy and Jensen equations and for functional equations in a single variable. Work supported by M.U.R.S.T. Research funds (60%).     

The bidimensional interproximation problem and mixed splines

Interproximation methods for surfaces can be used to construct a smooth surface interpolating some data points and passing through specified regions. In this paper we study the use of mixed splines, that is smoothing splines with additional interpolation constraints, to solve the interproximation problem for surfaces in the case of scattered data. The solution is obtained by solving a linear system whose structure can be improved by using “bell-shaped” thin plate splines.     

Low-energy electron diffraction,Auger electron spectroscopy,and thermal desorption studies of chemisorbed CO and O2 on the (111) and stepped [6(111) × (100)] iridium surfaces

The adsorption of CO, O₂, and H₂O was studied on both the (111) and [6(111) × (100)] crystal faces of iridium. The techniques used were LEED, AES, and thermal desorption. Marked differences were found in surface structures and heats of adsorption on these crystal faces. Oxygen is adsorbed in a single bonding state on the (111) face. On the stepped iridium surface an additional bonding state with a higher heat of adsorption was detected which can be attributed to oxygen adsorbed at steps. On both (111) and stepped iridium crystal faces the adsorption of oxygen at room temperature produced a (2 × 1) surface structure. Two surface structures were found for CO adsorbed on Ir(111); a (√3 × √3)R30° at an exposure of 1.5–2.5 L and a (2√3 × 2√3)R30° at higher coverage. No indication for ordering of adsorbed CO was found on the Ir(S)-[6(111) × (100)] surface. No significant differences in thermal desorption spectra of CO were found on these two faces. H₂O is not adsorbed at 300 K on either iridium crystal face. The reaction of CO with O₂ was studied on Ir(111) and the results are discussed. The influence of steps on the adsorption behaviour of CO and O₂ on iridium and the correlation with the results found previously on the same platinum crystal faces are discussed.