Simple technique for the simultaneous determination of solvent diffusion coefficient in polymer by Quantum Resistive Sensors and FT‐IR spectroscopy

A simple, quick and novel method for the determination of diffusion properties through polymer films, based on Quantum Resistive Sensors made of Conductive Polymer nanoComposites is presented. The integral time lag method is employed for the calculation of diffusion coefficient, and the results are compared simultaneously with that of Fourier transform infrared spectroscopy and sorption method. Two model polymers, a semi‐crystalline poly(lactic acid) and an amorphous poly(isobutylene‐co‐isoprene), are used to validate the study. A good correlation is established between the diffusion coefficient values derived from all techniques demonstrating the interest of such reliable, simple and cheap nanosensors for the quick determination (several minutes) of diffusion properties in polymer films. Our first results suggest that this technique is meaningful for the determination of barrier properties in nanocomposite membranes filled with platelets of graphene or clay. Copyright © 2013 John Wiley & Sons, Ltd.     

Insight into industrial PLA aging process by complementary use of rheology,HPLC, and MALDI

Nowadays, there is a growing availability of biodegradable industrial materials intended to food contact applications whose service life behavior needs to be further investigated. This article is focused on the degradation of two materials based on polylactic acid. The correlation between the rate of degradation and the amount of trapped degradation products was investigated applying three characterization techniques in parallel, namely rheology, high‐performance liquid chromatography (HPLC), and matrix‐assisted laser desorption/ionization (MALDI). The rate of degradation was studied through the evaluation of their rheological properties and calculation of the number of average molecular weights, and weight‐average molecular weights. Water‐soluble oligomers and lactic acid were quantified by HPLC‐ultraviolet. Changes in cyclic and linear oligomers were monitored by MALDI‐time‐of‐flight mass spectrometry. Specimens of 4‐mm thickness of each biopolymer were subjected to hydrolysis in deionized water up to 6 months at two temperatures, simulating service conditions of food packaging. The diminution in viscosity and consequently in molecular weight distribution (20–60%) showed the degradation of the molecular structure of both polylactic acids. The chain scission was followed through the increasing values of lactic acid and hydrolyzed oligomers (twofold to eightfold), and the predominant signal of the linear oligomers over the cyclic ones with aging. Rheology, HPLC, and MALDI showed to be complementary tools to better understand the changes in the molecular structure. The obtained results showed the necessity of adding suitable stabilizers for each particular food packaging application. Copyright © 2013 John Wiley & Sons, Ltd.     

A Simple Method for Producing Pure (+) trans-1,2-Epoxylimonene

In this paper we report a simple methodology for obtaining (+) trans - 1,2 - epoxylimonene (1b) in high purity (>99% HRGC) and reasonable quantity. The mixture of 1a and 1b in CH₂Cl₂ is stirred with 1M NaHSO₃ in water. Under these conditions 1a is completely destroyed, while 1b is only partially destroyed.     

Simulation of mesogenic diruthenium tetracarboxylates: Development of a force field for coordination polymers of the MMX type

A classical molecular mechanics force field, able to simulate coordination polymers (CP) based on ruthenium carboxylates (Ru₂(O₂CR_eq)₄L_ax) (eq = equatorial group containing aliphatic chains, L_ax= axial ligand), has been developed. New parameters extracted from experimental data and quantum calculations on short aliphatic chains model systems were included in the generalized AMBER force field. The proposed parametrization was evaluated using model systems with known structure, containing either short or long aliphatic chains; experimental results were reproduced satisfactorily. This modified force field, although in a preliminary stage, could then be applied to long chain liquid crystalline compounds. The resulting atomistic simulations allowed assessing the relative influence of the factors determining the CP conformation, determinant for the physical properties of these materials. © 2013 Wiley Periodicals, Inc.     

An ALE finite element method for a coupled Stefan problem and Navier–Stokes equations with free capillary surface

In this article, an ALE finite element method to simulate the partial melting of a workpiece of metal is presented. The model includes the heat transport in both the solid and liquid part, fluid flow in the liquid phase by the Navier–Stokes equations, tracking of the melt interface solid/liquid by the Stefan condition, treatment of the capillary boundary accounting for surface tension effects and a radiative boundary condition. We show that an accurate treatment of the moving boundaries is crucial to resolve their respective influences on the flow field and thus on the overall energy transport correctly. This is achieved by a mesh‐moving method, which explicitly tracks the phase boundary and makes it possible to use a sharp interface model without singularities in the boundary conditions at the triple junction. A numerical example describing the welding of a thin‐steel wire end by a laser, where all aforementioned effects have to be taken into account, proves the effectiveness of the approach.Copyright © 2012 John Wiley & Sons, Ltd.     

Classical and quantum effects in spatially modulated optical parametric oscillators

We study the effects of transverse spatial modulations in a multimode degenerate optical parametric oscillator. Intracavity photonic crystals allow us to tune the instability threshold and improve entanglement above threshold. Here we compare such results with the case in which the modulation is in the injected field profile.     

Synthesis of 6-Ami NO-5-Nitro-4-Thi Oxopyri Mi Dines

The synthesis of 6-ami no-5-nitro-4-thioxo-pyrimidines starting from the C-adducts of nitro-keteneaminals and acyl isothiocyanates is described.     

Synthesis and characterization of new galactosylated-based N2O-donors tridentate ligands

The synthesis and characterization of three novel N₂O-donor ligands containing the group 4-[1-β-d-2,3,4,6-tetra-O-acetyl-galactosyl)]benzaldehyde are presented. The insertion of this group was designed to increase the absorption of the prodrug in tumor cells, and is part of an ongoing work in our group with tridentate ligands to develop potential cobalt(III) prodrugs. The synthetic route described here allowed the isolation of pure ligands with yields ranged 81–89%. Finally, compounds were characterized by IR, NMR and HRMS (ESI⁺).