Preparation and Characterization of Conductive Polymer Blends of Polypyrrole and Poly(ethylene oxide).

Conductive polymer blends of polypyrrole (PPy) and poly(ethylene oxide) (PEO) were obtained in the form of films and fibers, respectively by solvent casting and electrospinning. Different amounts of PPy were introduced in the blends in order to study the effect of the conductive polymer on the properties of the final material and in particular to elucidate the influence of the different morphology on conductivity. The structure and morphology of PPy/PEO blends were characterized by wide angle X-ray diffraction (WAXD) and small angle X-ray scattering (SAXS), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were used to understand the influence of different PPy content on thermal behavior and stability, electrospun fibrous mats were examined by scanning electron microscopy (SEM). The conductivity of the films and fibrous mats was measured and correlation with morphology was highlighted.

Polyvinyl alcohol electrospun nanofibers containing Ag nanoparticles used as sensors for the detection of biogenic amines.

Polyvinyl alcohol (PVA) electrospun nanofibers containing Ag nanoparticles (NPs) have been deposited on glass substrates. The aim of the work was to test the feasibility of this approach for the detection of biogenic amines by using either the Ag localized surface plasmon resonance quenching caused by the adsorption of amines on Ag NPs or by detecting the amines by surface enhanced Raman spectroscopy (SERS) after adsorption, from the gas phase, on the metal NPs. Two different approaches have been adopted. In the first one an ethanol/water solution containing AgNO3 was used directly in the electrospinning apparatus. In this way, a simple heat treatment of the nanofibers mat was sufficient to obtain the formation of Ag NPs inside the nanofibers and a partial cross-link of PVA. In the second procedure, the Ag NPs were deposited on PVA nanofibers by using the supersonic cluster beam deposition method, so that a beam of pure Ag NPs of controlled size was obtained. Exposure of the PVA mat to the beam produced a uniform distribution of the NPs on the nanofibers surface. Ethylendiamine vapors and volatile amines released from fresh shrimp meat were chemisorbed on the nanofibers mats. A SERS spectrum characterized by a diagnostic Ag-N stretching vibration at 230 cm(-1) was obtained. The results allow to compare the two different approaches in the detection of ammines.

Energetics of oxo- and thio-dipeptide formation via amino acid condensation: a systematic computational analysis.

Oxo-dipeptides and thio-dipeptides are built via condensation between couples of amino acids and amino thioacids, the latter with the carbonyl oxygen replaced by an sp(2) sulfur. We explored via in silico methods (PBE0/6-31G(d,p) and PBE0/6-311G(d,p)) all the possible combinations and built 800 dipeptides, whose structures were fully optimized. Maps of condensation energies are presented to highlight optimal partners leading to stable dipeptides and critical situations for which lower stability or instability is predicted in terms of Gibbs reaction free energies. To validate the feasibility of our computational investigation, we synthesized and compared the stabilities of two thionated dimers, namely -Gly[Ψ(CSNH)]Gly- and -Phe[Ψ(CSNH)]Phe-, characterized by diverging physico-chemical properties. To the best of our knowledge, this is the first systematic analysis reported for dipeptides built from natural amino acids as well as for their corresponding thio-analogs.

Structure-property relationships in heterophasic thermoplastic elastomers filled with montmorillonite.

Polypropylene (PP)/ethylene-propylene rubber (EPR)/Montmorillonite ternary nanocomposites with a phase separated morphology were studied in this work. Wide angle X-ray diffraction (WAXD), small angle X-ray scattering (SAXS), atomic force microscopy (AFM), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) were used to investigate the samples. One of the aim of this work was to separate the effects of rubber and clay content on the structure, morphology and mechanical properties of the samples. The presence of clay favored the formation of gamma phase and disrupted the lamellar framework. Clay had moreover a major role in shaping the phase separated morphology of the samples. Atomic Force Microscopy showed that the shear exerted by the clay layers was key for inducing a shish kebab morphology in the polymer matrix. Rubber content decreased the degree of crystallinity at a crystalline cell level and induced the formation of a double population of lamellar stacks. The mechanical properties of the samples primarily depended on rubber content, and they were secondarily tuned by the effect of clay. This synergistic effect allowed to obtain composites with increased stiffness, ductility and toughness, oppositely to what is frequently found.

A direct SAXS approach for the determination of specific surface area of clay in polymer-layered silicate nanocomposites.

The interfacial area between the matrix and the filler is a key parameter which shapes the performance of polymer-based composites and nanocomposites, even though it is difficult to quantify. A very easy SAXS method, based on the Porod equation, is proposed for measuring the specific surface area of nanofillers embedded in a polymer matrix. In order to assess its reliability, this approach was applied to natural rubber- or styrene butadiene-based samples containing different types of montmorillonite clay. A wide range of specific surfaces was detected. SAXS data were compared to complementary X-ray diffraction and TEM information, obtaining a good agreement. Interpretation of the tensile properties by theoretical models and comparison with the literature corroborated the validity of the specific surface area measurement. The possibility to quantify this feature of composites allows the rational design of such materials to be improved.

Crystallization of a (1-butene)-ethylene copolymer in phase I directly from the melt in nanocomposites with montmorillonite.

Nanocomposites based on a copolymer of 1-butene and ethylene filled with montmorillonite (Cloisite 15A) were studied, obtaining for the first time crystallization from the melt directly into phase I. The polymorphism of the polymer and the dispersion of the filler in the matrix were investigated. The effect of the compatibilizer (PB-g-MA) on these properties was also singled out. The dramatic increase in the rate of the II --> I phase transition due to montmorillonite was attributed to the alteration in the phase stability diagram of the matrix, due to the introduction of defects and to induction of local pressure on the crystalline domains.