Clara M. Gómez

Nanocomposites of bacterial cellulose/hydroxyapatite for biomedical applications

In the present work, a nanocomposite material formed by bacterial cellulose (BC) networks and calcium-deficient hydroxyapatite (HAp) powders was synthesized and characterized. The HAp nanoparticles were previously prepared by a wet chemical precipitation method, starting from aqueous solutions of calcium nitrate and di-ammonium phosphate salts. Energy-dispersive spectroscopy reveals that the prepared HAp corresponds to calcium-deficient hydroxyapatite. BC-HAp nanocomposites were prepared by introducing carboxymethylcellulose (CMC) into the bacteria culture media. HAp nanoparticles were then introduced and remained suspended in the culture medium during the formation of cellulose nanofibrils. The maximum gel thickness was obtained after 21 days of bacteria cultivation. X-ray diffractograms showed the difference of crystallinity among the materials involved in the formation of nanocomposites. The inorganic and organic bonds that corresponded to hydroxyapatite and bacterial cellulose respectively, were depicted by attenuated total reflectance Fourier transform infrared spectra. Scanning electron microscopy and atomic force microscopy measurements confirmed the formation of networks and fibres with smaller diameter corresponding to BC synthesized in the presence of CMC. Image analysis was also used to assess the orientation distributions and Feret diameters for networks of BC and BC-CMC. Thermogravimetric analysis showed that the amount of the mineral phase is 23.7% of the total weight of the nanocomposite. Moreover, HEK cells were cultivated and the biocompatibility of the materials and the cell viability was demonstrated.

Blends of poly(methyl methacrylate) with epoxy resin and an aliphatic amine hardener

Abstract Miscibility, phase separation and curing behaviour have been studied in blends of poly(methyl methacrylate) (PMMA) with diglycidyl ether of bisphenol A (DGEBA) resin and 4,4′-diamino-3,3′-dimethyldicyclohexyl-methane (3DCM) hardener. Quasi-binary mixtures of PMMA with the resin monomer show complete miscibility over the whole composition range, at all temperatures studied (−25 to 200°C). However, PMMA is much less miscible with the hardener, and cast films show two Tg values. Several techniques have been used to monitor phase separation and curing characteristics in PMMA blends, including viscometry, size exclusion chromatography, turbidity and optical microscopy. The morphologies and the thermal and dynamic mechanical properties of the cured blends, including non-stoichiometric compositions, are related to these observations.

Viscometric study on the compatibility of polymer-polymer mixtures in solution

Abstract The viscosity behaviour of mixtures formed by two uncharged polymers in dilute solution has been studied at 25°C. The ternary systems assayed, and denoted solvent (1)/ polymer (2)/ polymer (3), have in common the poly(ether sulphone) (PES) as polymer 2, and poly(vinylidene fluoride) (PVDF), poly(methyl methacrylate) (PMMA) or poly(styrene) (PS) as polymer 3. The intrinsic viscosity and the viscometric interaction parameters have been experimentally measured for the binary (solvent/polymer) as well as for the ternary systems, and also theoretically evaluated for the latter. The estimation of the compatibility degree of the above polymer pairs have been done by means of three criteria: (i) the sign of Δbm, according to the traditional formalism developed by Krigbaum and Wall; (ii) the sign of a new defined Δb′m; and (iii) the sign of Δ[η]m. The two last criteria are proposed in this work and are based on treating the viscosity interaction parameter and the intrinsic viscosity as excess properties by similarity with those of real solutions. Both methods provide compatibility predictions in agreement with those made with the traditional one but they are much more simple in handling the calculations. Finally, the observed compatibility behaviour follows the order: (PES+PMMA)≫(PES+PVDF)>(PES+PS), in dimethylformamide as solvent, at least in the assayed composition range.

Review on Polymers for Thermoelectric Applications

In this review, we report the state-of-the-art of polymers in thermoelectricity. Classically, a number of inorganic compounds have been considered as the best thermoelectric materials. Since the prediction of the improvement of the figure of merit by means of electronic confinement in 1993, it has been improved by a factor of 3–4. In the mean time, organic materials, in particular intrinsically conducting polymers, had been considered as competitors of classical thermoelectrics, since their figure of merit has been improved several orders of magnitude in the last few years. We review here the evolution of the figure of merit or the power factor during the last years, and the best candidates to compete with inorganic materials. We also outline the best polymers to substitute classical thermoelectric materials and the advantages they present in comparison with inorganic systems.

Phase separation from solutions of poly(ether sulfone) in epoxy resins

Abstract Cloud-point measurements were made on quasi-binary mixtures of diglycidyl ether of bisphenol A (DGEBA) epoxy resin with poly(ether sulfone) (PES). The relative molecular masses of both resin and polymer were varied, and temperature-dependent Flory-Huggins interaction parameters were estimated on the assumption that both components are monodisperse. The data were used to calculate lower critical solution temperatures (LCST) and compositions, and to construct coexistence curves. The evolution of two-phase morphology during curing of epoxy-PES blends containing 4,4′-diaminodiphenylmethane (DDM) hardener is related to these results.

Enhanced thermoelectric performance of PEDOT with different counter-ions optimized by chemical reduction

This work reports on the synthesis of the intrinsically conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) doped with several counter-ions, ClO4, PF6 and bis(trifluoromethylsulfonyl)imide (BTFMSI), by electro-polymerization and its thermoelectric properties. We show that, depending on the counter-ion size, the thermoelectric efficiency of PEDOT can be increased up to two orders of magnitude. A further chemical reduction with hydrazine optimizes the power factor (PF). By changing the counter-ions, we were able to increase the electrical conductivity (σ) of PEDOT by a factor of three, while the Seebeck coefficient remains at the same order of magnitude in the three polymers. The best thermoelectric efficiency has been observed in PEDOT:BTFMSI. From the measurement of the Seebeck coefficient and σ, a PF of 147 μW m−1 K−2 has been deduced, while the measured thermal conductivity is κ = 0.19 W m−1 K−1, resulting in a ZT ∼ 0.22 at room temperature, one of the highest values reported in the literature for polymers. The increase in σ with the change of the counter-ion is mainly due to the stretching of the polymer chains. In this work, we provide a chemical route to further improve ZT in polymers and demonstrate a method of synthesis based on the electro-polymerization on gold. After removing the gold layer, a very thin semiconducting polymer film can be isolated.

Chitosan microspheres in PLG films as devices for cytarabine release.

Cytarabine was included in chitosan microspheres and several of these microspheres were embedded in a poly(lactide-co-glycolide) (PLG) film to constitute a comatrix system, to develop a prolonged release form. Chitosan microspheres, in the range of 92+/-65 microm, having good spherical geometry and a smooth surface incorporating cytarabine, were prepared. The cytarabine amount included in chitosan microspheres was 43.7 microg of ara-C per milligram microsphere. The incorporation efficiency of the cytarabine in microspheres was 70.6%. Total cytarabine release from microspheres in vitro was detected at 48 h. Inclusion of cytarabine-loaded microspheres in poly(lactide-co-glycolide) film initiated a slower release of the drug and, in this way, the maximum of cytarabine released (80%) took place in vitro at 94.5 h. Comatrices, with 8.7 mg of cytarabine, signifying a dose of 34.5 microg/kg, were subcutaneously implanted in the back of rats. Maximum plasma cytarabine concentration was 18.5+/-1.5 microg/ml, 48 h after the device implantation and the drug was detected in plasma for 13 days. The histological studies show a slow degradative process. After 6 months of implantation, most of the microspheres of the matrix seemed to be intact, the comatrix appeared surrounded by conjunctive tissue and small blood vessels and nerve packets were detected in the periphery of the implant.

Laser treatments on skin enhancing and controlling transdermal delivery of 5-fluorouracil.

Laser ablation of stratum corneum (SC) enhances transdermal delivery of hydrophilic drugs. The influence of the infrared (IR) (λ = 1,064 nm), visible (λ = 532 nm), and ultraviolet (UV) (λ = 355 nm) radiations of a Nd:YAG laser on transdermal delivery of 5‐Fluorouracil (5‐Fu) across skin was studied in vitro.

Processing and Mechanical Properties of Natural Fiber Reinforced Thermoplastic Starch Biocomposites

Natural fiber reinforced starch polymers are processed by compression molding. Potato, sweet potato, and corn starch are used as matrices. Three types of natural fibers, namely sisal, jute, and cabuya, are used in concentrations varying from 2.5 to 12.5% w/w in the composites. Different plasticizers are used for the starch polymers, such as water and glycerol. Mechanical properties are assessed by tensile and impact tests. In both cases, improved mechanical properties are obtained at increasing fiber contents. Tensile strength appears to be markedly improved with the addition of 10% by weight of sisal fibers, while the best results for impact strength are obtained for cabuya fibers.

Enhancement of laser properties of pyrromethene 567 dye incorporated into new organic–inorganic hybrid materials

Abstract The incorporation of pyrromethene 567 dye into newly synthesized organic–inorganic hybrid materials, laser photostabilities were demonstrated, which are, to the best of our knowledge, the highest achieved to date for both inorganic and hybrid matrices doped with pyrromethene dyes. These results evidence that, in order to reach the necessary photostability for a solid-state dye laser being competitive with liquid dye lasers, hybrid matrices combine advantageous properties of inorganic materials, such as a high thermal dissipation capability, without losing the benefits of organic polymers.