María Teresa Casas

Hybrid polythiophene–clay exfoliated nanocomposites for ultracapacitor devices

Exfoliated nanocomposites of poly(3,4-ethylenedioxythiophene) (PEDOT) and montmorillonite (MMT) have been prepared by in situ anodic polymerization, concentrations of clay ranging from 5% w/w to 50% w/w being included in the aqueous polymerization medium. The morphology, electrical conductivity, adherence, thermal stability, charge storage, specific capacitance, electrostability, doping level and band gap have been determined for the different PEDOT–MMT nanocomposites and compared with those of pristine PEDOT. Many of these properties have been found to depend on both the concentration of clay and the thickness (micrometric or nanometric) of the generated films. Types I and II ultracapacitors have been fabricated using nanometric and micrometric films of PEDOT and PEDOT–MMT. The properties of such devices have been characterized and compared with those reported in the literature for ultracapacitors fabricated using nanocomposites of PEDOT and other inorganic materials. Both nanometric and micrometric type II ultracapacitors, which correspond to an asymmetric configuration of PEDOT and PEDOT–MMT films, have been found to present the better properties (e.g. the specific capacitance for nanometric and micrometric devices is 429 and 116 F g−1, respectively), evidencing the favorable effect of the clay. Finally, the effects of the electrochemical degradation on the ultracapacitors have been rationalized using electrochemical impedance spectroscopy.

Structural data on the packing of poly(ester amide)s derived from glycine, hexanediol, and odd‐numbered dicarboxylic acids

The crystalline structure of a series of Poly(ester amide)s derived from glycine, hexanediol, and odd-numbered dicarboxylic acids has been studied using transmission electron microscopy and X-ray diffraction. Polymers crystallize in an orthorhombic lattice with parameters a = 4.80 A, b = 22.68 A, and c in the 45–55 A interval, depending on the number of methylenes of the chemical repeat unit. The structure of the glutaric derivative can be interpreted as a singular packing of six hydrogen-bonded sheets. Amide and ester interactions between neighboring layers favor two different sheet arrangements that give rise to the observed superstructure.

Polylactide nanofibers loaded with vitamin B6 and polyphenols as bioactive platform for tissue engineering

AbstractElectrospun polylactide nanofibers loaded with different antioxidants (i.e. vitamin B6 in pyridoxine and pyridoxal form, p-coumaric acid and caffeic acid) are prepared from N,N-dimethylformamide/dimethylsulfoxide solutions. Morphology, structure and crystallinity of the nanofibers are evaluated by transmission electron microscope (TEM), scanning electron microscope (SEM), X-ray diffraction and differential scanning calorimetry (DSC) techniques. Fibers are highly amorphous but able to crystallize easily due to the high molecular orientation induced by the electrospinning process. The drug molecules are incorporated into the polymeric matrix or formed isolated crystals. A fast release of loaded drug occurs within the first 8 h in hydrophobic medium; but, a slow and sustained release during several days occurs in a hydrophilic medium. Cell attachment on the loaded scaffolds was unaffected by the incorporation of the antioxidants. In contrast, cell proliferation increases with high antioxidative activity against free radicals responsible for cell damage. These new electrospun scaffolds provide high protection of cells against oxidative stress and resulting in innovative 3D fibrous platforms for tissue growth and proliferation.

Micro-molding with ultrasonic vibration energy: New method to disperse nanoclays in polymer matrices

Ultrasound technology was proved as an efficient processing technique to obtain micro-molded specimens of polylactide (PLA) and polybutylene succinate (PBS), which were selected as examples of biodegradable polyesters widely employed in commodity and specialty applications. Operational parameters such as amplitude, molding force and processing time were successfully optimized to prepare samples with a decrease in the number average molecular weight lower than 6%. Ultrasonic waves also seemed an ideal energy source to provide effective disaggregation of clay silicate layers, and therefore exfoliated nanocomposites. X-ray diffraction patterns of nanocomposites prepared by direct micro-molding of PLA or PBS powder mixtures with natural montmorillonite or different organo-modified clays showed the disappearance of the 001 silicate reflection for specimens having up to 6 wt.% clay content. All electron micrographs revealed relatively homogeneous dispersion and sheet nanostructures oriented in the direction of the melt flow. Incorporation of clay particles during processing had practically no influence on PLA characteristics but enhanced PBS degradation when an organo-modifier was employed. This was in agreement with thermal stability data deduced from thermogravimetric analysis. Cold crystallization experiments directly performed on micro-molded PLA specimens pointed to a complex influence of clay particles reflected by the increase or decrease of the overall non-isothermal crystallization rate when compared to the neat polymer. In all cases, the addition of clay led to a clear decrease in the Avrami exponent.

Structure of poly(hexamethylene sebacate)

Abstract The crystalline structure of poly(hexamethylene sebacate) has been studied using transmission electron microscopy and X-ray diffraction. Molecular chains adopt a slightly distorted all-trans conformation and pack in a Monoclinic unit cell with space group P121/n1. The unit cell contains two chain segments, with a chain setting angle similar to that reported for polyethylene. Similar results were obtained from energy calculations that took into account both van der Waals and electrostatic interactions. Sectorized lamellar crystals were observed by decoration with polyethylene. Different folds involving methylene or ester groups exist at the lamellar surface depending of the growth sector.

Detection of Dopamine Using Chemically Synthesized Multilayered Hollow Microspheres

Microspheres made of alternating layers of two different conducting polymers, poly(3,4-ethylenedioxythiophene) and poly(N-methylpyrrole), have been found to be sensitive to dopamine (DA) oxidation, presenting a very well-defined and linear response in the range of DA concentrations from 0.5 to 2 mM. The novelty of the present study is the use of doped multilayered hollow microspheres, which are prepared by successive oxidative chemical polymerizations in FeCl3 aqueous solution. The multilayered microspheres were characterized by FTIR and UV-visible spectroscopies, scanning and transmission electron microscopies, and atomic force microscopy. The UV-visible bands confirm that the multilayered system is not well doped with FeCl4(-) counterions. Therefore, the doping level was increased by further oxidation with LiClO4 before DA electrochemical detection. Despite that the range of concentration detection was limited from 0.5 mM to 2 mM, doped hollow multilayered microspheres show a very good anodic peak current response compared to single-layer films fabricated with an individual conducting polymer and activated by gold nanoparticles.

DNA adsorbed on hydroxyapatite surfaces

Hydroxyapatite (HAp) particles with very different surface charges and compositions (i.e. different Ca/P and CO3 2-/PO4 3- ratios) have been obtained by varying the experimental conditions used during the chemical precipitation process. The DNA adsorption capacity and protection imparted against the attack of nucleases of HAp particles have been proved to depend on the surface charge while the buffering capacity is affected by the chemical composition. On the basis of both the surface charge and the crystallinity, the predominant planes at the surfaces of HAp particles have been identified. Atomistic molecular dynamics simulations of surfaces constructed with these planes (i.e. (001) and the two terminations of (010)) with the adsorbed B-DNA double helix have been performed to get microscopic understanding of the influence of the mineral in the biomolecule structure and the interaction energies. The results indicate that the DNA secondary structure is perfectly preserved on the (001) surface, this stability being accompanied by an attractive binding energy. In contrast, the (010) surface with PO4 3-, OH- and Ca2+ ions in the termination induces significant local and global deformations in the double helix, repulsive OH-(HAp)PO4 3- (DNA) interactions provoking the desorption of the biomolecule. Finally, although the termination of the (010) surface with PO4 3- and Ca2+ ions also deforms the double helix, it forms very strong attractive interactions with the biomolecule. These binding characteristics are in excellent agreement with the DNA adsorption and protection abilities experimentally determined for the HAp samples. Finally, the surface charge has been found less decisive than the chemical composition in the efficacy of the transfection process.

Synergistic Approach to Elucidate the Incorporation of Magnesium Ions into Hydroxyapatite

Although the content of Mg(2+) in hard tissues is very low (typically ≤1.5 wt %), its incorporation into synthetic hydroxyapatite (HAp) particles and its role in the minerals properties are still subject of intensive debate. A combined experimental-computational approach is used to answer many of the open questions. Mg(2+) -enriched HAp particles are prepared using different synthetic approaches and considering different concentrations of Mg(2+) in the reaction medium. The composition, morphology and structure of the resulting particles are investigated using X-ray photoelectron spectroscopy, energy dispersive X-ray spectroscopy, scanning and transmission electron microscopies, FTIR, and wide-angle X-ray diffraction. After this scrutiny, the role of the Mg(2+) in the first nucleation stages, before HAp formation, is investigated using atomistic molecular dynamics simulations. Saturated solutions are simulated with and without the presence of DNA, which has been recently used as a soft template in the biomineralization process. This synergistic investigation provides a complete picture of how Mg(2+) ions affect the mineralization from the first stages onwards.

Controlling the Morphology of Poly(N-cyanoethylpyrrole)

The morphology of poly(N-cyanoethylpyrrole) has been controlled through the polymerization process. This polymer has been prepared by anodic polymerization, chemical oxidative polymerization in emulsion medium, and layer-by-layer templating polymerization. Anodic polymerization using LiClO4 as supporting electrolyte provides compact films, in which the oxidation degree is controlled through the thickness, useful for the microdetection of dopamine. Chemical polymerization using FeCl3 as oxidant agent results in very well-defined microspheres with porous internal structure, which may be useful in molecular loading and transport processes. Finally, the layer-by-layer templating technique produces core-shell particles of controlled size and thickness. Moreover, these core-shell particles can be easily converted in hollow microspheres by removing the template.

Preparation of micro-molded exfoliated clay nanocomposites by means of ultrasonic technology

Ultrasound micro-molding technology has been tested as a new method to get polymer/clay nanocomposites. Biodegradable polylactide (PLA) and poly (nona-methylene azelate) (PE99) have been used as polymer matrices, whereas different silicate clays have been assayed. The new technology is able to get specimens without evidences of degradation during processing. Only the use of organo-modified clays could give rise to a slight molecular weight decrease when the poly (alkylene dicarboxylate) sample was considered. Ultrasonic micro-molding has revealed effective to get directly nanocomposites with the final form required for a selected application, a homogeneous clay distribution up to a load of 6 wt-% and more interestingly exfoliated structures without being necessary the use of a compatibilizer agent between the organic polymer and the inorganic silicate clay. Transmission electron micrographs and X-ray diffraction profiles revealed exfoliated structure when N757, C20A, C25A, and N848 clays were employed.Crystallization behavior of exfoliated PLA nanocomposites was highly peculiar since clay particles had an antinucleating effect that decreased the overall crystallization rate respect to the neat polymer. In addition, the incorporation of layers into growing spherulites increased the crystal growth rate. A typical crystallization effect was on the contrary observed for nanocomposites derived from the poly (alkylene dicarboxylate) sample.