Compatible blends of thermoplastic starch and hydrolyzed ethylene-vinyl acetate copolymers

Ethylene-vinyl acetate copolymer (EVA) with 19% of vinyl acetate and its derivatives modified by hydrolysis of 50 and 100% of the initial vinyl acetate groups were used to produce blends with thermoplastic starch (TPS) plasticized with 30 wt% glycerol. The blends were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy. X-ray diffraction, water absorption, stress-strain mechanical tests, dynamic mechanical analysis and thermogravimetric analysis. In contrast to the blends with unmodified EVA. those made with hydrolyzed EVA were compatible, as demonstrated by the brittle fracture surface analysis and the results of thermal and mechanical tests. The mechanical characteristics and water absorption of the TPS were improved even with a small addition (2.5 wt%) of hydrolyzed EVA. The glass transition temperature rose with the degree of hydrolysis of EVA by 40 and 50 degrees, for the EVA with 50 and 100% hydrolysis, respectively. The addition of hydrolyzed EVA proved to be an interesting approach to improving TPS properties, even when very small quantities were used, such as 2.5 wt%. (C) 2012 Elsevier Ltd. All rights reserved.

Laminated Tubular-channel Ferroelectret Systems from Low-density Polyethylene Films and from Fluoroethylene-propylene Copolymer Films - A Comparison

A template-based lamination technique for the manufacture of ferroelectrets from uniform electret films was recently reported. In the present work, this technique is used to prepare similar ferroelectret structures from low-density polyethylene (LDPE) films and from fluoro-ethylene-propylene (FEP) copolymer films. A comparative analysis of the pressure-, temperature-, and frequency-dependent piezoelectric properties has been performed on the two ferroelectret systems. It is observed that the FEP ferroelectrets exhibit better piezoelectric responses and are thermally more stable. The difference between the piezoelectric d(33) coefficients of the two ferroelectret systems is partially explained here by their different elastic moduli. The anti-resonance peaks of both structures have been investigated by means of dielectric resonance spectroscopy and electroacoustic sound-pressure measurements. A difference of more than 10 kHz is observed between the anti-resonance frequencies of the two ferroelectret systems.

Clay-containing block copolymer nanocomposites with aligned morphology prepared by extrusion

Clay-containing nanocomposites of polystyrene-b-poly(ethylene-co-butylene)-b-polystyrene (SEBS) copolymers having cylindrical domains were obtained by melt extrusion using a tape die. One type of sample (SEBS-MA) had maleic anhydride attached to the middle block. Two types of organoclays were added, namely Cloisite 20A and Cloisite 30B. Small angle X-ray scattering and transmission electron microscopy (TEM) analyses showed that the addition of 20A clay to SEBS and SEBS-MA resulted in nanocomposites with intercalated and partially exfoliated structures, respectively. The addition of 30B clay to SEBS and SEBS-MA promoted the formation of composites containing relatively large micron-sized and partially exfoliated clay particles, respectively. Our TEM analysis revealed that clay particles embedded in SEBS are preferably in contact with the polystyrene cylindrical domains, while in SEBS-MA they are in contact with the maleated matrix. The extrusion processing promoted alignment of the axes of the polystyrene cylinders along the extrusion direction in all samples, and the basal planes of the clay particles were mostly parallel to the main external surfaces of the extruded tapes. © 2013 Society of Chemical Industry.

The impact of the alkali cation on the mechanism of the electro-oxidation of ethylene glycol on Pt

By means of in situ IR spectroscopy we investigate the effect of dissolved alkali cations on the electro-oxidation of ethylene glycol on platinum in alkaline media. The results revealed that the increase in the oxidation currents (Li(+) < Na(+) < K(+)) is reflected in the increase in the ratio between carbonate and oxalate produced.

Plasmid DNA partitioning and separation using poly(ethylene glycol)/poly(acrylate)/salt aqueous two-phase systems

Phase diagrams of poly(ethylene glycol)/polyacrylate/Na2SO4 systems have been investigated with respect to polymer size and pH. Plasmid DNA from Escherichia coil can depending on pH and polymer molecular weight be directed to a poly(ethylene glycol) or to a polyacrylate-rich phase in an aqueous two-phase system formed by these polymers. Bovine serum albumin (BSA) and E. coil homogenate proteins can be directed opposite to the plasmid partitioning in these systems. Two bioseparation processes have been developed where in the final step the pDNA is partitioned to a salt-rich phase giving a total process yield of 60-70%. In one of them the pDNA is partitioned between the polyacrylate and PEG-phases in order to remove proteins. In a more simplified process the plasmid is partitioned to a PEG-phase and back-extracted into a Na2SO4-rich phase. The novel polyacrylate/PEG system allows a strong change of the partitioning between the phases with relatively small changes in composition or pH. (C) 2012 Elsevier B.V. All rights reserved.

Langmuir and Langmuir-Blodgett films of a quinoline-fluorene based copolymer

The fabrication of Langmuir-Blodgett (LB) films of synthetic polymers allows the control of molecular architecture in order to optimize physical properties. In this paper, the surface chemistry of a quinoline-fluorene based copolymer spread on the air-water interface is investigated. Surface pressure-area isotherms as well as Polarization-Modulation Infrared Reflection-Absorption Spectroscopy (PM-IRRAS) were employed to characterize the films, which could be transferred to solid supports by the LB technique. Atomic force microscopy as well as UV-Vis and fluorescence spectroscopies have shown a regular deposition of the polymers, and the luminescence properties could be controlled with the number of layers deposited on the solid support. As a result, the photoluminescence of the LB films was considerably higher than that observed for the spin coated film, and the maximum emission peak was shifted to higher energies, which is attributed to the molecular-level interactions within the layer-ordered structure of the LB film. The luminescence response would possibly be tuned to approach the highest level, which allows the films to be employed in future applications in efficient optical devices such as organic light-emitting diodes (OLEDs). (C) 2011 Elsevier B.V. All rights reserved.

Photophysical properties of a fluorene-bipyridine copolymer and its complexes with europium

The synthesis and structural characterization of a europium complexed fluorene-bipyridine copolymer are described. A level of ion insertion of 80% in molar basis was achieved, and theoretical calculations showed that it required a twist of 179 degrees (49 kJ) between the pyridine units. Spectroscopy data showed that no electronic coupling between the main backbone and the complexation sites had occurred, but these hindered the interchain aggregation observed in the non complexed polymer. Preliminary electroluminescence studies showed that the EL and PL spectra are consistent, and that the ion had a trapping effect in the charge transport. (C) 2011 Elsevier B.V. All rights reserved.

Surfactant-assisted intercalation of high molecular weight poly(ethylene oxide) into vanadyl phosphate di-hydrate

A high molecular weight poly(ethylene oxide)/layered vanadyl phosphate di-hydrate intercalation compound was synthesized via the surfactant-assisted approach. Results confirmed that surfactant molecules were replaced with the polymer, while the lamellar structure of the matrix was retained, and that the material presents high specific surface area. In addition, intercalation produced a more thermally stable polymer as evidenced by thermal analysis. (C) 2011 Elsevier Ltd. All rights reserved.

Partitioning and extraction of collagenase from Penicillium aurantiogriseum in poly(ethylene glycol)/phosphate aqueous two-phase system

Purification of collagenase produced by Penicillium aurantiogriseum URM4622 was carried using a PEG/phosphate aqueous two-phase system (ATPS). A 2(3)-full experimental design was used to investigate the influence of PEG molar mass, PEG concentration and phosphate concentration on the selected responses, namely partition coefficient, activity yield and purification factor. The ATPS was composed of PEG (molar mass of 550, 1500 and 4000 g/mol) at concentrations of 15.0, 17.5 and 20.0% (w/w) and phosphate at concentrations of 12.5, 15.0 and 17.5% (w/w). The best results of one-step extraction of collagenase from the fermentation broth (partition coefficient of 1.01, activity yield of 242% and purification factor of 23.5) were obtained at pH 6.0 using 20.0% (w/w) PEG 550 and 17.5% (w/w) phosphate. The results of this preliminary study demonstrate that the selected ATPS is satisfactorily selective for the extraction of such a collagenase. (C) 2012 Elsevier B.V. All rights reserved.

Formation and Characterization of Oriented Micro-and Nanofibers Containing Poly (ethylene oxide) and Pectin

Formation of oriented or aligned micro- and nanofibers using biocompatible materials opens the possibility to obtain engineered tissues that can be used in medicine, environmental engineering, security and defense, among other applications. Pectin, a heteropolysaccharide, is a promising material to be incorporated into the fibers because, besides being biocompatible, this material is also biodegradable and bioactive. In this work, the formation of oriented fibers using solutions containing pectin and polyethylene oxide (biocompatible polymers), and chloroform (as the solvent) is investigated. The injection of solution into an intense electric field defined between two parallel electrodes was used to obtain oriented fibers. This novel approach is a modification of the conventional electrospinning process. The presence of pectin in the fibers was confirmed by FTIR analysis. Fibers with diameters of hundreds of nanometers and several centimeters long can be collected. The incorporation of pectin leads to a higher variation of the diameter of the fibers, and a trend to larger fiber diameters. This behavior can be related to the presence of pectin clusters in the fibers. (C) 2012 The Electrochemical Society. [DOI: 10.1149/2.057203jes] All rights reserved.

Compatibilization of polypropylene/poly(3-hydroxybutyrate) blends

Blending polypropylene (PP) with biodegradable poly(3-hydroxybutyrate) (PHB) can be a nice alternative to minimize the disposal problem of PP and the intrinsic brittleness that restricts PHB applications. However, to achieve acceptable engineering properties, the blend needs to be compatibilized because of the immiscibility between PP and PHB. In this work, PP/PHB blends were prepared with different types of copolymers as possible compatibilizers: poly(propylene-g-maleic anhydride) (PPMAH), poly (ethylene-co-methyl acrylate) [P(EMA)], poly(ethylene-co-glycidyl methacrylate) [P(EGMA)], and poly(ethylene-co-methyl acrylate-co-glycidyl methacrylate) [P(EMAGMA)]. The effect of each copolymer on the morphology and mechanical properties of the blends was investigated. The results show that the compatibilizers efficiency decreased in this order: P(EMAGMA) > P(EMA) > P(EGMA) > PP-MAH; we explained this by taking into consideration the affinity degree of the compatibilizers with the PP matrix, the compatibilizers properties, and their ability to provide physical and/or reactive compatibilization with PHB. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci 123: 3511-3519, 2012

Tailored norbornene-based copolymer with systematic variation of norbornadiene as a crosslinker obtained via ROMP with alternative amine Ru catalysts

Copolymers of norbornene (NBE) with norbomadiene (NBD) were obtained via ROMP with [RuCl2(PPh3)(2)(L)] type complexes as initiators (1 for L = piperidine and 2 for L = 3,5-Me(2)piperidine). The reactions were performed using a fixed quantity of NBE (5000 equivalents/[Ru]) for different concentrations of NBD (500, 1000, 1500 and 2000 equivalents/ [Ru]) in CHCl3, initiated with ethyl diazoacetate at room temperature. The presence of NBD in the NBE chains was characterized by H-1 and C-13 NMR. Whereas the copolymer microstructure was influenced neither by the NBD quantity nor by the initiator type, the N-n and PDI values were improved when increasing the NBD quantity in the medium. When raising the NBD amount, DMA results indicated increased cross-linking with increasing T-g and E ' storage modulus, as well as the fact that SEM micrographs indicated decreased pore sizes in the porous isolated copolymers. (C) 2011 Elsevier Ltd. All rights reserved.

Photophysical and photovoltaic properties of a PPV type copolymer containing alternated fluorene and thiophene units

The synthesis and photophysical characterization of a PPV-type copolymer containing a fluorene derivative alternated with thiophene units is presented: poly(9,9'-dioctylfluorene-thiophene) (LAPPS29). Photophysical studies demonstrated that in the solid state only preformed ground state aggregates are responsible for exciton formation. These aggregates are formed with a wide range of size distribution. The emission from isolated segments is quenched either by resonant energy transfer, or by migration processes. Also, the main photovoltaic parameters are discussed in connection with the photophysical behavior.

Hofmeister effects on the colloidal stability of poly(ethylene glycol)-decorated nanoparticles

The colloidal stability of poly(ethylene glycol)-decorated poly(methyl methacrylate), PMMA/Tween-20, particles was investigated by means of phase separation measurements, in the presence of sodium fluoride (NaF), sodium chloride, sodium bromide, sodium nitrate, or sodium thiocyanate (NaSCN) at 1.0 mol L-1. Following Hofmeister's series, the dispersions of PMMA/Tween-20 destabilized faster in the presence of NaF than with NaSCN. After the phase separation, the systems were homogenized and except for the dispersions in NaF, re-dispersed particles took longer to destabilize, indicating that anions adsorbed on the particles, creating a new surface. Except for F- ions, the adsorption of anions on the polar outmost shell was evidenced by means of tensiometry and small-angle X-ray scattering measurements. Fluoride ions induced the dehydration of the polar shell, without affecting the polar shell electron density, and the formation of very large aggregates. A model was proposed to explain the colloidal behavior in the presence of Hofmeister ions.

Antimicrobial effectiveness of silver nanoparticles co-stabilized by the bioactive copolymer pluronic F68

Abstract Background Silver nanoparticles (AgNps) have attracted much interest in biomedical engineering, since they have excellent antimicrobial properties. Therefore, AgNps have often been considered for incorporation into medical products for skin pathologies to reduce the risk of contamination. This study aims at evaluating the antimicrobial effectiveness of AgNps stabilized by pluronic™ F68 associated with other polymers such as polyvinyl alcohol (PVA) and polyvinylpyrrolidone (PVP). Methods AgNps antimicrobial activity was evaluated using the minimum inhibitory concentration (MIC) method. The action spectrum was evaluated for different polymers associated with pluronic™ F68 against the gram negative bacteria P. aeuroginosa and E. coli and the gram positive bacteria S. Aureus. Results AgNps stabilized with PVP or PVA and co-stabilized with pluronic™ F68 are effective against E. coli and P. aeruginosa microorganisms, with MIC values as low as 0.78% of the concentration of the original AgNps dispersion. The antimicrobial action against S. aureus is poor, with MIC values not lower than 25%. Conclusions AgNps stabilized by different polymeric systems have shown improved antimicrobial activity against gram-negative microorganisms in comparison to unstabilized AgNps. Co-stabilization with the bioactive copolymer pluronic™ F68 has further enhanced the antimicrobial effectiveness against both microorganisms. A poor effectiveness has been found against the gram-positive S. aureus microorganism. Future assays are being delineated targeting possible therapeutic applications.