Exploring the role of lignin structure in molecular dynamics of lignin/bio-derived thermoplastic elastomer polyurethane blends.

The relaxation behavior of two lignins (Alcell organosolv, OSL, and hydroxypropyl modified Kraft, ML) and bio-based thermoplastic polyurethane (TPU) blends have been studied by Differential Scanning Calorimetry (DSC), Dynamic-Mechanical Analysis (DMA) and Dielectric Relaxation Spectroscopy (DRS). The effect of blending on the glass and local relaxation processes as a function of composition, frequency, and temperature has been assessed. The dielectric spectra were resolved into dipolar relaxations as well as conductive processes for differing blend compositions. Characteristic relaxation times, activation energies and dielectric relaxation strengths of lignin/xTPU blends were also investigated. It was found that blending suppresses the α-relaxation process of the blends compared to virgin TPU. On the other hand, while the position of the ß-relaxation was not influenced by blending, a reduction of the activation energies, Ea, of this process was observed in the lignin/xTPU blends. Finally, changes are observed in the conductivity behavior of both blends, with conductivity processes more favorable for the OSL/xTPU blends.

Molecular dynamics of carrageenan composites reinforced with Cloisite Na+ montmorillonite nanoclay.

Nanocomposites comprising biodegradable carrageenan and glycerol (KCg) as the host polymer, with different contents of natural montmorillonite (MMT) as filler, were prepared by a solution casting process. Different techniques have been used to determine the interaction/behavior among the different components of the samples such as Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), Transmission electron microscope (TEM) and, mainly, Dielectric relaxation spectroscopy (DRS). FTIR indicates hydrogen interaction between carrageenan matrix and silicate that is confirmed by the XRD data indicating some kind of carrageenan intercalation between the MMT layers. A rather homogenous distribution of MMT into KCg matrix were observed using transmission electron microscopy. The MMT effect on the molecular mobility at the glass transition was studied by dielectric relaxation spectroscopy. The MMT addition resulted in a slower relaxation and a wider distribution of the relaxation times. The fragility index, m, increased upon MMT incorporation, which may be attributed to a reduction in mobility chains, due to the MMT confinement of the KCg network. In addition, the apparent activation energy associated with the relaxation dynamics of the chains at Tg increased with the MMT content. The modified films developed in this paper could be used to prepare biodegradable and edible packaging films and films for biomedical applications with improved mechanical and good dielectric response.

Monitoring molecular dynamics of bacterial cellulose composites reinforced with graphene oxide by carboxymethyl cellulose addition.

Broadband Dielectric Relaxation Spectroscopy was performed to study the molecular dynamics of dried Bacterial Cellulose/Carboxymethyl Cellulose-Graphene Oxide (BC/CMC-GO) composites as a function of the concentration of CMC in the culture media. At low temperature the dielectric spectra are dominated by a dipolar process labelled as a ß-relaxation, whereas electrode polarization and the contribution of dc-conductivity dominate the spectra at high temperatures and low frequency. The CMC concentration affects the morphological structure of cellulose and subsequently alters its physical properties. X-ray diffractometry measurements show that increasing the concentration of CMC promotes a decrease of the Iα/Iß ratio. This structural change in BC, that involves a variation in inter- and intramolecular interactions (hydrogen-bonding interactions), affects steeply their molecular dynamics. So, an increase of CMC concentration produces a significantly decrease of the ß-relaxation strength and an increase of the dc-conductivity.

Interconversion algorithm between mechanical and dielectric relaxation measurements for acetate of cis- and trans-2-phenyl-5-hydroxymethyl-1,3-dioxane.

The dielectric and mechanical spectroscopies of acetate of cis- and trans-2-phenyl-5-hydroxymethyl-1,3-dioxane are reported in the frequency domain from 10(-2) to 10(6)Hz. This ester has been selected in this study for its predominant α relaxation with regard to the ß relaxation, which can be neglected. This study consists of determining an interconversion algorithm between dielectric and mechanical measurements, given by using a relation between rotational and translational complex viscosities. These important viscosities were obtained from measures of the dielectric complex permittivity and by dynamic mechanical analysis, respectively. The definitions of rotational and translational viscosities were evaluated by means of fractional calculus, by using the fit parameters of the Havriliak-Negami empirical model obtained in the dielectric and mechanical characterization of the α relaxation. This interconversion algorithm is a generalization of the break of the Stokes-Einstein-Debye relationship. It uses a power law with an exponent defined as the shape factor, which modifies the translational viscosity. Two others factors are introduced for the interconversion, a shift factor, which displaces the translational viscosity in the frequency domain, and a scale factor, which makes equal values of the two viscosities. In this paper, the shape factor has been identified as the relation between the slopes of the moduli of the complex viscosities at higher frequency. This is interpreted as the degree of kinetic coupling between the molecular rotation and translational movements. Alternatively, another interconversion algorithm has been expressed by means of dielectric and mechanical moduli.

Contributions of dipolar relaxation processes and ionic transport to the response of liquids to electrical perturbation fields.

The objective of this work was to study the influence of small variations in the chemical structure on the molecular dynamics of liquids using as models bis(cyclohexylmethyl) 2-methyl- and dicyclohexyl 2-methylsuccinate. The dielectric behavior of the low molecular weight liquids was studied over a wide range of frequencies and temperatures. The results show that the temperature dependence of the dielectric strengths, relaxation times, and shape parameters of the secondary and glass-liquid relaxations are very sensitive to the slight differences in the structures of the liquids. Significant changes take place in the dielectric strength of the ß relaxation in the glass liquid transition. Moreover, the temperature dependence of the ß relaxation exhibits Arrhenius behavior in the glassy state and departs from this behavior in the liquid state. Special attention is paid to the temperature dependence of low-frequency relaxations produced by the motion of a macrodipole arising from charges located near the liquid-electrode boundaries.

Instability of incompressible cylinder rubber tubes under radial electric fields.

The possibility of instability of cylindrical tubes of elastomers is analyzed taking into account Mooney-Rivlin (M. Mooney, J. Appl. Phys. 11, 582 (1940)) and Ogden (R.W. Ogden, Proc. R. Soc. London, Ser. A 326, 565 (1972)) models. In some aspects this paper is the elasto-electric counterpart of a previous paper by Bustamante, Dorfmann and Ogden (R. Bustamante, A. Dorfmann, R.W. Ogden, J. Engn. Math. 59, 139 (2007)). However in the present case the appearance of instability is checked. The results indicate that models more complex than the Mooney-Rivlin model are necessary to predict instability zones showing minimum critical points.

Effect of an electric field on the bifurcation of a biaxially stretched incompressible slab rubber.

This paper describes the effect of an electrical field on the bifurcation phenomenon that appears in a biaxially stretched slab of Mooney-Rivlin material (M. Mooney, J. Appl. Phys. 11, 582 (1940)) subjected to equal dead loads. The main conclusion of the analysis is that the stretch ratio at which the bifurcation phenomenon appears crucially depends on the configuration of the system rubber slab-electrodes. The theoretical foundations of the present study are based on a recent formulation on this subject carried out by Dorfmann and Ogden (A. Dorfmann, R.W. Ogden, Acta Mech. 174, 167 (2005); J. Elasticity 82, 99 (2006)).

Interconversion of mechanical and dielectrical relaxation measurements for dicyclohexylmethyl-2-methyl succinate.

A comparison between results of dielectrical relaxation and dynamic mechanical spectroscopies is carried out for the alpha-relaxation of the ester dicyclohexyl methyl-2-methyl succinate (DCMMS). The results for the dielectric permittivity and the shear modulus measurements are presented according to the empirical Havriliak-Negami (HN) equation. By using the time-temperature principle a master curve in each case was obtained for several temperatures. The comparative analysis presented here is based on the assumption of a relationship between rotational and shear viscosities. The former one is associated to the dielectrical relaxation, whereas the latter is associated to mechanical relaxation. Both viscosities are not necessarily equal in general, and we assume that the difference between them is an important factor to appropriately compare the dielectrical and mechanical results.

HLA polymorphism in the Murcia population (Spain): in the cradle of the archaeologic Iberians.

Human leukocyte antigen (HLA) study in Murcian individuals was performed in order to provide information of their historical origins and relationships with other Iberian and Mediterranean populations. HLA class I and class II alleles were determined in 173 unrelated Caucasoid donors from Murcia Region in the Southeast of Spain by serologic and DNA based polymerase chain reaction (PCR) typing. Class I antigen and class II allele frequencies of our series were not very different to those found in Spaniards. The analysis of extended haplotypes showed that the three haplotypes most frequent in our population were respectively, A29-B44-Cwb-DRB1*0701-DRB4*0101-DQA1*0201-DQB1*0202, A1-B8-Cw7-DRB1*0301-DRB3*0101-DQA1*0501-DQB1*0201 and A30-B18-Cw5-DRB1*0301-DRB3*0101-DQA1*0501-DQB1*0201. They were followed by A26-B38-Cwb-DRB1*1301-DRB3*0202-DQA1*0103-DQB1*0603, which could point to an ancestral relationship between Murcian and Portuguese Iberian populations, and by A2-B7-Cw7-DRB1*1501-DRB5*0101-DQA1*0102-DQB1*0602 also present in all Iberian Peninsula populations. Allelic frequencies, populations distance dendrogram and correspondence analysis were used to study the relationships between Murcian and other populations. The closest relation was observed with Spaniards and Portuguese, followed in decreasing order by French, Italians, Algerians, Germans, Catalans, Basques, Cretans, Sardinians, and Greeks. Thus, Murcian population seems to belong to the European genetic pool, revealing a lesser genetic distance with the North Africans and the rest of populations from the Iberian Peninsula.

Analysis of the phenotypic distribution of HLA class I and class II in atopic and non-atopic asthma patients.

In several studies the HLA system has been implicated in the development of asthma, but the importance of the associations between HLA genes and asthma remains unclear. The aim of this study was to determine the HLA class I and II phenotypic frequencies in a population of asthmatics, and to analyse the relationship between these phenotypes and any type of asthma. We typed HLA class I and II antigens in a series of 189 asthmatic individuals (102 atopic and 87 non-atopic), and in a control population of 150 unrelated healthy Caucasoid donors. When the HLA phenotypic frequencies were compared, no statistical differences were found. Therefore, no definitive HLA association could be established with atopic or non-atopic asthma in the studied population. Abbreviations AA, atopic asthma; FEV1, forced expiratory volume in 1 s; NAA, non-atopic asthma; PCR, polymerase chain reaction; SSOP, sequence-specific oligonucleotide probes; SPT, skin prick test.

[The liver and AIDS]. / Hígado y SIDA.

Hepatic disorders in AIDS are very common, although the injuries observed are usually non-specific. This is the reason why the real usefulness of hepatic biopsy in this patients is being currently discussed. In this work, such aspect and the hepatic injuries observed in patients with AIDS are discussed. Current indications for hepatic biopsy are summarized, as well as its later manipulation in order to obtain maximum profitability of it.