Development of films based on blends of gelatin and poly(vinyl alcohol) cross linked with glutaraldehyde

Both gelatin and poly(vinyl alcohol) (PVA) can be cross linked with glutaraldehyde (GLU). In the case of gelatin, the GLU reacts with each e-NH2 functional group of adjacent lysine residues, while for PVA, the GLU reacts with two adjacent hydroxyl groups, forming acetal bridges. Thus it can be considered possible to cross link adjacent macromolecules of gelatin and PVA using GLU. In this context, the aims of this work were the development of biodegradable films based on blends of gelatin and poly(vinyl alcohol) cross linked with GLU, and the characterization of some of their main physical and functional properties. All the films were produced from film-forming solutions (FFS) containing 2 g macromolecules (PVA + gelatin)/100 g FFS, 25 g glycerol/100 g macromolecules, and 4 g GLU (25% solution)/100 g FFS. The FFS were prepared with two concentrations of PVA (20 or 50 g PVA/100 g macromolecules) and two reaction temperatures: 90 or 55 degrees C, applied for 30 min. The films were obtained after drying (30 degrees C/24 h) and conditioning at 25 degrees C and 58% of relative humidity for 7 days, and were then characterized. The results for the color parameters, mechanical properties, phase transitions and infrared spectra showed that some chemical modifications occurred, principally for the gelatin. However, in general, all the characteristics of the films were either typical of films based on blends of these macromolecules without cross linking, or slightly higher. A greater improvement in the properties of this material was probably not observed due to the crystallinity of the PVA, which has a melting point above 90 degrees C. The presence of microcrystals in the polymer chain probably reduced macromolecular mobility, hindering the reaction. Thus more research is necessary to produce biodegradable films with improved properties. (C) 2011 Elsevier Ltd. All rights reserved.

Study of some physical properties of biodegradable films based on blends of gelatin and poly(vinyl alcohol) using a response-surface methodology

The aim of this work was to study the effect of the hydrolysis degree (HD) and the concentration (C(PVA)) Of two types of poly(vinyl alcohol) (PVA) and of the type (glycerol and sorbitol) and the concentration (C(P)) of plasticizers on some physical properties of biodegradable films based on blends of gelatin and PVA Using a response-surface methodology. The films were prepared with a film forming solutions (FFS) with 2 g of macromolecules (gelatin+PVA)/100 g de FFS. The responses analyzed were the mechanical properties, the solubility, the moisture Content. the color difference and the opacity. The linear model was statistically significant and predictive for puncture force and deformation. elongation at break, solubility in water, Moisture content and opacity. The CPVA affected strongly the elongation at break of the films. The interaction of the HD and the C(P) affected this property. Moreover. the puncture force was affected slightly by the C(PVA). Concerning the Solubility in water, the reduction of the HD increased it and this effect was greater for high CPVA Values. In general. the most important effect observed in the physical properties of the films was that of the plasticizer type and concentration. The PVA hydrolysis degree and concentration have an important effect only for the elongation at break, puncture deformation and solubility in water. (C) 2008 Elsevier B.V. All rights reserved.

Thermomechanical properties of biodegradable films based on blends of gelatin and poly(vinyl alcohol)

The aim of this work was to study the effect of the poly(vinyl alcohol) (PVA) concentration on the thermal and viscoelastic properties of films based on blends of gelatin and PVA using differential scanning calorimetry (DSC) and dynamic-mechanical analysis (DMA). One glass transition was observed between 43 and 49 degrees C on the DSC curves obtained in the first scanning of the blended films, followed by fusion of the crystalline portion between 116 and 134 degrees C. However, the DMA results showed that only the films with 10% PVA had a single peak in the tan 5 spectrum. However, when the PVA concentration was increased the dynamic mechanical spectra showed two peaks on the tan 6 curves, indicating two T(g)s. Despite this phase separation behavior the Gordon and Taylor model was successfully applied to correlate T, as a function of film composition, thus determining k = 7.47. In the DMA frequency tests, the DMA spectra showed that the storage modulus values decreased with increasing temperature. The master curves for the PVA-gelatin films were obtained applying the TTS principle (T(r) = 100 degrees C). The WLF model was thus applied allowing for the determination of the constants C(1) and C(2). The values of these constants increased with increasing PVA concentrations in the blend: C(1) = 49-66 and C(2) = 463-480. These values were used to calculate the fractional free volume of the films at the T(g) and the thermal expansion coefficient of the films above the T(g). (c) 2007 Elsevier Ltd. All rights reserved.

Production of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) P(3HB-co-3HV) with a broad range of 3HV content at high yields by Burkholderia sacchari IPT 189

The biosynthesis of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) from sucrose and propionic acid by Burkholderia sacchari IPT 189 was studied using a two-stage bioreactor process. In the first stage, this bacterium was cultivated in a balanced culture medium until sucrose exhaustion. In the second stage, a solution containing sucrose and propionic acid as carbon source was fed to the bioreactor at various sucrose/propionic acid (s/p) ratios at a constant specific flow rate. Copolymers with 3HV content ranging from 40 down to 6.5 (mol%) were obtained with 3HV yield from propionic acid (Y-3HV/prop) increasing from 1.10 to 1.34 g g(-1). Copolymer productivity of 1 g l(-1) h(-1) was obtained with polymer biomass content rising up to 60% by increasing a specific flow rate at a constant s/p ratio. Increasing values of 3HV content were obtained by varying the s/p ratios. A simulation of production costs considering Y-3HV/prop obtained in the present work indicated that a reduction of up to 73% can be reached, approximating US$ 1.00 per kg which is closer to the value to produce P3HB from sucrose (US$ 0.75 per kg).

Application of abrupt cut-off models in the analysis of the capacitance spectra of conjugated polymer devices

In this paper, a detailed study of the capacitance spectra obtained from Au/doped-polyaniline/Al structures in the frequency domain (0.05 Hz-10 MHz), and at different temperatures (150-340 K) is carried out. The capacitance spectra behavior in semiconductors can be appropriately described by using abrupt cut-off models, since they assume that the electronic gap states that can follow the ac modulation have response times varying rapidly with a certain abscissa, which is dependent on both temperature and frequency. Two models based on the abrupt cut-off concept, formerly developed to describe inorganic semiconductor devices, have been used to analyze the capacitance spectra of devices based on doped polyaniline (PANI), which is a well-known polymeric semiconductor with innumerous potential technological applications. The application of these models allowed the determination of significant parameters, such as Debye length (approximate to 20 nm), position of bulk Fermi level (approximate to 320 meV) and associated density of states (approximate to 2x10(18) eV(-1) cm(-3)), width of the space charge region (approximate to 70 nm), built-in potential (approximate to 780 meV), and the gap states` distribution.

3D Cell-Migration Studies using Two-Photon Engineered Polymer Scaffolds

We use two-photon polymerization to fabricate 3D scaffolds with precise control over pore size and shape for studying cell migration in 3D. These scaffolds allow movement of cells in all directions. The fabrication, imaging, and quantitative analysis method developed here can be used to do systematic cell studies in 3D.

Magnetic resonance and conductivity study of gelatin-based proton conductor polymer electrolytes

This work report results from proton nuclear magnetic resonance (NMR), continuous-wave (CW-EPR) and pulsed electron paramagnetic resonance (P-EPR) and complex impedance spectroscopy of gelatin-based polymer gel electrolytes containing acetic acid. cross-linked with formaldehyde and plasticized with glycerol. Ionic conductivity of 2 x 10(-5) S/cm was obtained at room temperature for samples prepared with 33 wt% of acetic acid. Proton ((1)H) line shapes and spin-lattice relaxation times were measured as a function of temperature. The NMR results show that the proton mobility is dependent on acetic acid content in the plasticized polymer gel electrolytes. The CW-EPR spectra, which were carried out in samples doped with copper perchlorate, indicate the presence of the paramagnetic Cu(2+) ions in axially distorted sites. The P-EPR technique, known as electron spin echo envelope modulation (ESEEM), was employed to show the involvement of both, hydrogen and nitrogen atoms, in the copper complexation of the gel electrolyte. (C) 2009 Elsevier Ltd. All rights reserved.

Elastomeric Composites Based on Ethylene-Propylene-Diene Monomer Rubber and Conducting Polymer-Modified Carbon Black

Thermally stable elastomeric composites based on ethylene-propylene-diene monomer (EPDM) and conducting polymer-modified carbon black (CPMCB) additives were produced by casting and crosslinked by compression molding. CPMCB represent a novel thermally stable conductive compound made via ""in situ"" deposition of intrinsically conducting polymers (ICP) such as polyaniline or polypyrrole on carbon black particles. Thermogravimetric analysis showed that the composites are thermally stable with no appreciable degradation at ca. 300 degrees C. Incorporating CPMCB has been found to be advantageous to the processing of composites, as the presence of ICP lead to a better distribution of the filler within the rubber matrix, as confirmed by morphological analysis. These materials have a percolation threshold range of 5-10 phr depending on the formulation and electrical dc conductivity values in the range of 1 x 10(-3) to 1 x 10(-2) S cm(-1) above the percolation threshold. A less pronounced reinforcing effect was observed in composites produced with ICP-modified additives in relation to those produced only with carbon black. The results obtained in this study show the feasibility of this method for producing stable, electrically conducting composites with elastomeric characteristics. POLYM. COMPOS., 30:897-906, 2009. (C) 2008 Society of Plastics Engineers

NMR and conductivity study of gelatin-based polymer electrolytes

Nuclear Magnetic Resonance spectroscopy (NMR) and complex impedance spectroscopy have been used to study gelatin-based polymer electrolytes plasticized with glycerol and containing lithium perchlorate. The studied samples were prepared with salt concentration of 7.9 wt% and 10.3 wt%. Ionic conductivity of about 10(-5) S/cm was obtained at room temperature for both samples. Lithium (Li-7) and proton (H-1) lineshapes and spin-lattice relaxation times were measured as a function of temperature. The Li-7 NMR relaxation results indicate that the ionic mobility in this system is comparable to those found in other plasticized polymer electrolytes.

Dressing liposomal particles with chitosan and poly(vinylic alcohol) for oral vaccine delivery

Liposomes have been used as adjuvants since 1974. One major limitation for the use of liposomes in oral vaccines is the lipid structure instability caused by enzyme activities. Our aim was to combine liposomes that could encapsulate antigens (i.e., Dtxd, diphtheria toxoid) with chitosan, which protects the particles and promotes mucoadhesibility. We employed physical techniques to understand the process by which liposomes (SPC: Cho, 3: 1) can be sandwiched with chitosan (Chi) and stabilized by PVA (poly-vinylic alcohol), which are biodegradable, biocompatible polymers. Round, smooth-surfaced particles of REVs-Chi (reversed-phase vesicles sandwiched by Chi) stabilized by PVA were obtained. The REVs encapsulation efficiencies (Dtxd was used as the antigen) were directly dependent on the Chi and PVA present in the formulation. Chi adsorption on the REVs surface was accompanied by an increase of zeta-potential. In contrast, PVA adsorption on the REVs-Chi surface was accompanied by a decrease of zeta-potential. The presence of Dtxd increased the Chi surface-adsorption efficiency. The PVA affinity by mucine was 2,000 times higher than that observed with Chi alone and did not depend on the molecule being in solution or adsorbed on the liposomal surface. The liberation of encapsulated Dtxd was retarded by encapsulation within REVs-Chi-PVA. These results lead us to conclude that these new, stabilized particles were able to be adsorbed by intestinal surfaces, resisted degradation, and controlled antigen release. Therefore, REVs-Chi-PVA particles can be used as an oral delivery adjuvant.

Block Copolymers Containing (R)-3-Hydroxybutyrate and Isosorbide Succinate or (S)-Lactic Acid Mers

A new aliphatic block copolyester was synthesized in bulk from transesterification techniques between poly((R)-3-hydroxybutyrate) (PHB) and poly(isosorbide succinate) (PIS). Additionally, other two block copolyesters were synthesized in bulk either from transesterification reactions involving PHB and poly(l-lactide) (PLLA) or from ring-opening copolymerization of l-lactide and hydroxyl-terminated PHB, as result of a previous transesterification reactions with isosorbide. Two-component blends of PHB and PIS or PLLA were also prepared as comparative systems. SEC, MALDI-TOF mass spectrometry (MALDI-TOFMS), (1)H and (13)C NMR spectroscopy, WAXD, solubility tests, and TG thermal analysis were used for characterization. The block copolymer structures of the products were evidenced by MALDI-TOFMS, (13)C NMR, and WAXD data. The block copolymers and the corresponding binary blends presented different solubility properties, as revealed by solubility tests. Although the incorporation of PIS sequences into PHB main backbone did not enhance the thermal stability of the product, it reduced its crystallinity, which could be advantageous for faster biodegradation rate. These products, composed of PHB and PIS or PLLA sequences, are an interesting alternative in biomedical applications.

Identification of lift-off mechanism failure for salt drill-in drilling fluid containing polymer filter cake through adsorption/desorption studies

Drilling fluid`s contact with the productive zone of horizontal or complex wells can reduce well productivity by fluid invasion in the borehole wall. Salted drilling drill-in fluid containing polymers has often been applied in horizontal or complex petroleum wells in the poorly consolidated sandstone reservoirs of the Campos basin, Rio de Janeiro, Brazil. This fluid usually consists of natural polymers such as starch and xanthan gum, which are deposited as a filter cake on the wellbore wall during the drilling. Therefore, the identification of a lift-off mechanism failure, which can be detachment or blistering and pinholing, will enable formulation improvements. increasing the chances of success during filter cake removal in open hole operations. Likewise, knowledge of drill-in drilling fluid adsorption/desorption onto sand can help understand the filter cake-rock adhesion mechanism and consequently filter cake lift-off mechanism failures. The present study aimed to identify the lift-off failure mechanism for this type of fluid filter cake studying adsorption/desorption onto SiO(2) using solutions of natural polymers, lubricants, besides the fluid itself. Ellipsometry was employed to measure this process. The adsorption/desorption studies showed that the adsorbed layer of drilling fluid onto the walls of the rock pores is made up of clusters of polymers, linked by hydrogen bonds, which results in a force of lower cohesion compared to the electrostatic interaction between silica and polymers. Consequently, it was found that the most probable filter cake failure mechanism is rupture (blistering and pinholing), which results in the formation of ducts within the filter cake. (C) 2009 Elsevier B.V. All rights reserved.

Nitric oxide sensing by cytochrome c bonded to a conducting polymer modified glassy carbon electrode

A nitric oxide biosensor based on cytochrome c (an heme protein) covalently immobilized to poly(5-amino-1-naphthol) by using cyanuric chloride as a bridge was developed. The immobilization was studied by cyclic voltammetry and quartz crystal microbalance. The nitric oxide detection as a function of poly(5-amino-1-naphthol) amount was recorded, and the best result was obtained with the electrode prepared by 70 cycles. The sensitivity and detection limit were 0.015 mu A cm(-2)/mu mol L(-1) and 2.85 mu mol L(-1), respectively. (C) 2009 Elsevier B.V. All rights reserved.

On the energy transfer from a polymer host to the rhenium(I) complex in OLEDs

Photoluminescence and electroluminescence of PVK films doped with fac-[ClRe(CO)(3)(bpy)], bpy=2,2`-bipyridine, are investigated. Photoluminescence spectra of spin-coated PVK films (lambda(exc)=290 nm) exhibit a broad band centered at 405 nm. As the concentration of dopant increases, the polymer emission is quenched and a band at 555 nm appears (isosbestic point at 475 nm). In OLEDs with ITO/PEDOT:PSS/PVK/butylPBD/Al architecture doped with fac-[ClRe(CO)(3)(bpy)], the polymer host emission is completely quenched even at the lowest concentration of dopant. The electroluminescence spectra of the devices show that there is an efficient energy transfer from the host to the dopant, which exhibits a very intense emission at 580 nm. (C) 2009 Elsevier B.V. All rights reserved.

A selective conductive polymer-based sensor for volatile halogenated organic compounds (VHOC)

A novel poly(p-xylylene), PPX, derivative bearing alkoxyphenyl side groups was electrochemically synthesized in 87% yield. The polymer, poly(4`-hexyloxy-2,5-biphenyleneethylene) (PHBPE), presented a fraction (92%) soluble in common organic solvents. It showed to be thermally resistant up to 185 degrees C. UV-vis analysis revealed an E-gap of 3.5 eV Gas sensors made from thin films of 10-camphorsulfonic acid-doped PHBPE deposited on interdigitated electrodes exhibited significant changes in electrical conductance upon exposure to five VHOCs: 1,2-dichloroethane, bromochloromethane, trichloromethane, dichloromethane and tetrachloromethane. The conductance decreased after exposure to tetrachloromethane and increased after exposure to all the other VHOCs. Three-dimensional plots of relative response versus time of half response versus time of half recovery showed good discrimination between the five VHOCs tested. (c) 2008 Elsevier B.V. All rights reserved.