A high selective and sensitive liquid chromatography–tandem mass spectrometry method for quantization of BPA urinary levels in children

A selective and highly sensitive liquid chromatography–tandem mass spectrometry method has been developed and validated for determination of Bisphenol A (BPA) in human urine using labeled d₆-BPA as internal standard. BPA was purified from human urine by affinity chromatography on solid extraction AFFINIMIP® Bisphenol A cartridges, based on molecularly imprinted polymers. After purification, the samples were analyzed on a Phenomenex Kinetex 100?×?4.6 mm, 2.6 μm particle PFP reversed-phase HPLC column, coupled to a triple quadrupole mass spectrometer by an electrospray ion source. Analyses were performed in the multiple reaction monitoring mode and negative ionization; the product ions at 133.2 and 212.1?m/z for BPA and at 138.2 and 215.0?m/z for d₆-BPA were monitored to assess unambiguous identification. The linearity of the detector response was verified in human urine over the concentration range 0.100–200 ng/mL. The detection limit was calculated as 0.03 ng/mL and the limit of quantification of the method is 0.10 ng/mL. This LC/ESI-MS/MS method was in-house validated evaluating specificity, trueness, within-day and between-days precision. The mean recoveries of BPA from spiked urine samples were higher than 94 % and good reproducibility (relative standard deviations?≤?8.1 %) was observed. The developed method was applied to a pilot study involving 105 children, aged from 6 to 14 years (16 normal weight and 89 obese children), from the Regione Campania (Southern Italy). The aim of this study was to determine the concentrations of BPA in urine of children and possible correlations with childhood obesity.     

Silver‐capped silicon nanopillar platforms for adsorption studies of folic acid using surface enhanced Raman spectroscopy and density functional theory

The study of the interactions of folic acid (FA) with surface enhanced Raman scattering substrates is relevant for understanding its adsorption mechanism and for fabricating analytical devices for detection of malignant cells over‐expressing folate receptors. This paper presents a study of the adsorption of FA on silver‐capped silicon nanopillar substrates employing surface enhanced Raman scattering spectroscopy and density functional theory calculations. The experimentally observed vibrations from free FA and FA bound to the Ag surface display different vibrational spectra indicating chemical interaction of the molecule with the metal surface. Density functional theory calculations show that the Ag–FA interaction is primarily through the nitrogen from the pteridine ring anchoring to the Ag metal surface. To investigate the Ag–FA binding behavior further, the adsorption isotherm of FA on the silver‐capped silicon nanopillar surface is estimated. The results show a positive cooperative Ag–FA binding mechanism. That is, adsorbed FA increases the affinity of new incoming FA molecules. Copyright © 2015 John Wiley & Sons, Ltd.     

Convexity considerations and spatial behavior for the harmonic vibrations in thermoelastic plates

In this paper we study the spatial behavior of the steady-state solutions for the approach of thin thermoelastic plates developed by Lagnese and Lions [J.E. Lagnese, J.-L. Lions, Modelling, Analysis and Control of Thin Plates, Collection RMA, vol. 6, Masson, Paris, 1988]. The model leads to a coupled complex system of partial differential equations, one of fourth order in terms of the amplitude of the vertical deflection and the other of second-order in terms of the amplitude of temperature field. Coupling in an appropriate way the two equations in an integral identity we are able to identify some cross-sectional line integral measures associated with the amplitudes of the vertical deflection and temperature vibrations, provided that the exciting frequency is less than a certain critical frequency. Furthermore, we are able to establish a second-order differential inequality whose integration furnishes a Saint-Venant type decay estimate for a bounded strip and an alternative of Phragmén-Lindelöf type for a semi-infinite strip. The critical frequency is individuated by means of the use of some Wirtinger and Knowles inequalities.     

On the description of the environment polarization response to electronic transitions

This paper addresses the issue of accurately describing the structures and properties of electronically excited systems embedded in an environment, through multiscale approaches combining quantum-mechanical (QM) and polarizable classical representations of the system and environment, respectively. Such approaches represent an efficient strategy and allow to effectively study the excited states of molecular systems in the condensed phase, still maintaining the computational efficiency and the physical reliability of the ground-state calculations. The most important theoretical and computational aspects of the coupling between the QM system and the polarizable environment are presented and discussed. Even if these approaches already reached an evident degree of maturity, they can still be subject to further development, in order to achieve their full potential. This perspective presents an overview of the state of the art of these strategies, showing the fields of applicability and indicating the current limitations, which need to be overcome in future developments.     

On the use of uniaxial tests on the sclera to understand the difference between emmetropic and highly myopic eyes

This study aims at assessing the differences between highly myopic eyes and emmetropic eyes in the biomechanical response to ex vivo uniaxial tests of the human sclera. Scleral strips were collected from two enucleated eyes with markedly different axial length (AXL) of 24 and 31 mm, respectively. Static stress measurements under uniaxial loading were carried out with a Zwicki-Line testing machine, specially designed for low load mechanical testing applications. Although all uniaxial stress–strain curves showed an exponential response typical of biological viscoelastic materials loaded within the physiological strain range, the qualitative behavior was ostensibly different between the two eyes. With respect to the 24 mm AXL eye, the 31 mm AXL eye mm showed a lower stiffness at physiological strains and a more evident stiffening at larger strains. It was concluded that the myopic eye is more compliant at low strains and stiffer at strains larger than the physiological ones. An interpretation of this behaviour is that the higher percentage of small diameter collagen in myopic sclera delays the process of fiber recruitment and shifts the tissue stiffening to higher strains.     

Algorithms for vector field generation in mass consistent models

Diagnostic models in meteorology are based on the fulfillment of some time independent physical constraints as, for instance, mass conservation. A successful method to generate an adjusted wind field, based on mass conservation equation, was proposed by Sasaki and leads to the solution of an elliptic problem for the multiplier. Here we study the problem of generating an adjusted wind field from given horizontal initial velocity data, by two ways. The first one is based on orthogonal projection in Hilbert spaces and leads to the same elliptic problem but with natural boundary conditions for the multiplier. We derive from this approach the so called E–algorithm. An innovative alternative proposal is obtained from a second approach where we consider the saddle–point formulation of the problem—avoiding boundary conditions for the multiplier— and solving this problem by iterative conjugate gradient methods. This leads to an algorithm that we call the CG–algorithm, which is inspired from Glowinsk's approach to solve Stokes–like problems in computational fluid dynamics. Finally, the introduction of new boundary conditions for the multiplier in the elliptic problem generates better adjusted fields than those obtained with the original boundary conditions. © 2009 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq 2010     

On Saint-Venant's principle for a linear poroelastic material in plane strain

In this paper we consider the state of plane strain in an elastic material with voids occupying a rectangular strip. Such a strip is maintained in equilibrium under self-equilibrated traction and equilibrated force applied on one of the edges, while the other three edges are traction-free and subjected to zero volumetric fraction or zero equilibrated force. Our aim is to derive some explicit spatial estimates describing how some appropriate measures of a specific Airy stress function and volume fraction evolve with respect to the distance to the loaded edge. The both cases of homogeneous and inhomogeneous poroelastic materials are considered. The results of the present paper prove how the spatial-decay rate varies with the constitutive profile.     

Enthalpy Relaxation of Polymers: On the Possible Role of Liquid‐Crystalline Order

Isothermal physical ageing experiments were performed by differential scanning calorimetry to probe the enthalpy relaxation in a methacrylate copolymer carrying azobenzene mesogenic side groups. Further evidence of the ability of the configurational entropy model developed by Gomez Ribelles in describing the structural relaxation mechanism of polymers is provided. The trend of the equilibrium structural relaxation time was also determined as a function of the reduced temperature T_g/T. The comparison of the aging dynamics of the copolymer with those of previous analogous copolymers containing different amounts of azobenzene counits allowed us to highlight effects of the liquid‐crystalline nematic order on the properties of structural relaxation.

     

Synthesis of novel pyrimidine nucleoside analogues

Two new tetrazolopyrimidinedeoxynucleosides were synthesized and their physico-chemical data are described. Results of preliminary analyses of their biological properties are also reported.