Human Biomonitoring of Selected Hazardous Compounds in Portugal: Part I—Lessons Learned on Polycyclic Aromatic Hydrocarbons,Metals, Metalloids,and Pesticides

Human biomonitoring (HBM) data provide information on total exposure regardless of the route and sources of exposure. HBM studies have been applied to quantify human exposure to contaminants and environmental/occupational pollutants by determining the parent compounds, their metabolites or even their reaction products in biological matrices. HBM studies performed among the Portuguese population are disperse and limited. To overcome this knowledge gap, this review gathers, for the first time, the published Portuguese HBM information concerning polycyclic aromatic hydrocarbons (PAHs), metals, metalloids, and pesticides concentrations detected in the urine, serum, milk, hair, and nails of different groups of the Portuguese population. This integrative insight of available HBM data allows the analysis of the main determinants and patterns of exposure of the Portuguese population to these selected hazardous compounds, as well as assessment of the potential health risks. Identification of the main difficulties and challenges of HBM through analysis of the enrolled studies was also an aim. Ultimately, this study aimed to support national and European policies promoting human health and summarizes the most important outcomes and lessons learned through the HBM studies carried out in Portugal.     

Human Biomonitoring of Selected Hazardous Compounds in Portugal: Part II—Lessons Learned on Mycotoxins

Human biomonitoring (HBM) data provide information on total exposure regardless of the route and sources of exposure. HBM studies have been applied to quantify human exposure to contaminants and environmental/occupational pollutants by means of determining the parent compounds, their metabolites, or even their reaction products in biological matrices. HBM studies performed among the Portuguese population are dispersed and limited. Thus, to overcome this knowledge gap, this work reviews the published Portuguese HBM information concerning mycotoxins detected in the urine, serum, milk, hair, and nails of different groups of the Portuguese population. This integrative approach to the available HBM data allows us to analyze the main determinants and patterns of exposure of the Portuguese population to the selected hazardous compounds, as well as to assess the potential health risks. We also aimed to identify the main difficulties and challenges of HBM through the analysis of the enrolled studies. Ultimately, this study aims to support national and European policies in promoting human health by summarizing the most important outcomes and lessons learned through the HBM studies carried out in Portugal.     

Amphiphiles as novel solvents for photochromics: stability and photophysical properties

Abstract

The photochromic compound 2,6-bis(2-hydroxybenzilidene)cyclohexanone (PC) has been dissolved in some selected liquid amphiphiles: dibutyl, tributyl, bis-2-ethylhexyl, tris-2-ethylhexyl phosphate and bis-2-ethylhexyl amine. The aim was to explore its photophysical properties when embedded in the novel chemical environment provided by the amphiphilic solvents. UV-Vis spectra revealed different features depending on the solvent thus highlighting specific solvent-solute interactions and different chemical environments. All the alkylphosphate-based systems were found to be unstable; slow (days) changes in the absorption features due to the slow change in populations of the various species present in solution. Interestingly, the dissolution of PC into bis-2-ethylhexyl amine leads to stable solutions most probably due to the basic character of the solvent stabilising as major specie chalcone forms. Fluorescence spectra suggested the equilibrium between two species with different absorption and fluorescence properties.     

Face counting on an Acyclic Birkhoff polytope

In this paper we present some algorithms allowing an exhaustive account on the number of edges and faces of the acyclic Birkhoff polytope.     

Borromean sheets assembled by self-supporting argentophilic interactions

An infinite two-dimensional Borromean coordination framework, stabilized by argentophilic interactions, was obtained by the reaction of a flexible ligand with AgBF4.     

A discrete metallocyclic complex that retains its solvent-templated channel structure on guest removal to yield a porous, gas sorbing material

A discrete rectangular metal-organic complex that stacks to form one-dimensional channels filled with acetonitrile solvent molecules is described. Removal of the solvent under relatively mild conditions proceeds via a single-crystal to single-crystal transformation that leaves the host lattice unaltered. These findings proffer a design strategy for porous materials based on the simple principle that rigid molecular rings cannot pack efficiently and would thus favor the inclusion of guest species whenever possible. Upon guest removal, an efficiently packed new phase can then only be achieved by means of bond cleavage. Thus, achieving crystal porosity by maintaining robust metal-ligand coordination bonds in such discrete cyclic systems directly parallels the strategy employed for MOFs.     

Reiter's condition (P2) and hypergroup representations

Let K be a hypergroup with Haar measure. We relate Reiter's condition $(P_2)$ to positive definite measures and associated representations, induced representations from a subgroup of K and convolution operators on $L_2(K)$. To cite this article: L. Pavel, C. R. Acad. Sci. Paris, Ser. I 341 (2005).     

On the continuum limit of a discrete inverse spectral problem on optimal finite difference grids

We consider finite difference approximations of solutions of inverse Sturm‐Liouville problems in bounded intervals. Using three‐point finite difference schemes, we discretize the equations on so‐called optimal grids constructed as follows: For a staggered grid with 2 k points, we ask that the finite difference operator (a k × k Jacobi matrix) and the Sturm‐Liouville differential operator share the k lowest eigenvalues and the values of the orthonormal eigenfunctions at one end of the interval. This requirement determines uniquely the entries in the Jacobi matrix, which are grid cell averages of the coefficients in the continuum problem. If these coefficients are known, we can find the grid, which we call optimal because it gives, by design, a finite difference operator with a prescribed spectral measure. We focus attention on the inverse problem, where neither the coefficients nor the grid are known. A key question in inversion is how to parametrize the coefficients, i.e., how to choose the grid. It is clear that, to be successful, this grid must be close to the optimal one, which is unknown. Fortunately, as we show here, the grid dependence on the unknown coefficients is weak, so the inversion can be done on a precomputed grid for an a priori guess of the unknown coefficients. This observation leads to a simple yet efficient inversion algorithm, which gives coefficients that converge pointwise to the true solution as the number k of data points tends to infinity. The cornerstone of our convergence proof is showing that optimal grids provide an implicit, natural regularization of the inverse problem, by giving reconstructions with uniformly bounded total variation. The analysis is based on a novel, explicit perturbation analysis of Lanczos recursions and on a discrete Gel'fand‐Levitan formulation. © 2005 Wiley Periodicals, Inc.     

Activity coefficients of water and sulfolane from the solid + liquid phase diagram

The solid + liquid phase diagram drawn from thermal analysis is presented. It exhibits a eutectic at x₂ = 0.303 and T = 262.2 K and precludes the existence of definite compounds between the two components. Mixed crystals are observed in the sulfolane-rich region. The activity coefficients of water, f_{x, 1}, and of sulfolane, f_{x, 2}, are calculated from the initial freezing points of water. Log f_{x, 1} and log f_{x, 2} show a steady dependence on volume composition, providing evidence for the supposition that strongly self-associated water and monomer sulfolane scarcely interact with one another, and that the thermodynamic properties of the mixtures should rather be related to steric factors.