Biodegradable Films Based on Blends of Gelatin and Poly (Vinyl Alcohol): Effect of PVA Type or Concentration on Some Physical Properties of Films

The aim of this work was to develop biodegradable films based on blends of gelatin and poly (vinyl alcohol) (PVA), without a plasticizer. Firstly, the effect of five types of PVA with different degree of hydrolysis (DH) on the physical properties of films elaborated with blends containing 23.1% PVA was studied. One PVA type was then chosen for the study of the effect of the PVA concentration on the mechanical properties, color, opacity, gloss, and water solubility of the films. The five types of PVA studied allowed for films with different characteristics, but with no direct relationship with the DH of the PVA. Therefore, the PVA Celvol (R) 418 with a DH = 91.8% was chosen for the second part, because they produced films with greater tensile strength. The PVA concentration affected all studied properties of films. These results could be explained by the results of the DSC and FTIR analyses, which showed that some interactions between the gelatin and the PVA occurred depending on the PVA concentration, affecting the crystallinity of the films.

The effect of the degree of hydrolysis of the PVA and the plasticizer concentration on the color, opacity, and thermal and mechanical properties of films based on PVA and gelatin blends

The objective of this work was to study the color, opacity, crystallinity, and the thermal and mechanical properties of films based on blends of gelatin and five different types of PVA [poly(vinyl alcohol)], with and without a plasticizer. The effect of the degree of hydrolysis of the PVA and the glycerol concentration on these properties was studied using colorimetry, differential scanning calorimetry (DSC), X-ray diffraction (XRD) and tensile mechanical tests. All films were essentially colorless (Delta E* < 5) and with low opacity ( Y <= 2.1). The DSC results were typical of partially crystalline materials, showing some phase separation characterized by a glass transition (T(g) = 40-55 degrees C), related to the amorphous part of the material, followed by two endothermic peaks related to the melting (T(m) = 100-160 and 170-210 degrees C) of the crystallites. The XRD results confirmed the crystallinity of the films. The film produced with PVA Celvol((R)) 418 (DH = 91.8%) showed the highest tensile resistance (tensile strength = 38 MPa), for films without plasticizer. However, with glycerol, the above-mentioned PVA and the PVA Celvol((R)) 504 produced the least resistant films of all the PVA types. But, although the mechanical properties of the blended films depended on the type of PVA used, there was no direct relationship between these properties and the degree of hydrolysis of the PVA. The properties studied were more closely dependent on the glycerol concentration. Finally, the mechanical resistance of the films presented a linear relationship with the glass transition temperature of the films. (c) 2007 Elsevier Ltd. All rights reserved.

Influence of dentin cavity surface finishing on micro-tensile bond strength of adhesives

The current trend toward minimal-invasive dentistry has introduced innovative techniques for cavity preparation. Chemical vapor deposition (CVD) and laser-irradiation technology have been employed as an alternative to the common use of regular burs in high-speed turbines. Objectives. The purpose of this study was to assess the influence of alternative techniques for cavity preparation on the bonding effectiveness of different adhesives to dentin, and to evaluate the morphological characteristics of dentin prepared with those techniques. Methods. One etch&rinse adhesive (OptiBond FL, Kerr) and three self-etch systems (Adper Prompt L-Pop, 3M ESPE; Clearfil SE Bond, Kuraray; Clearfil S3 Bond, Kuraray) were applied on dentin prepared with a regular bur in a turbine, with a CVD bur in a turbine, with a CVD tip in ultrasound and with an ErCr:YSGG laser. The micro-tensile bond strength (mu TBS) was determined after storage in water for 24 h at 37 degrees C, and morphological evaluation was performed by means of field -emission -gun scanning electron microscopy (Feg-SEM). Results. Feg-SEM evaluation revealed different morphological features on the dentin surface after the usage of both the conventional and alternative techniques for cavity preparation, more specifically regarding smear-layer thickness and surface roughness. CVD bur-cut, CVD ultra-sonoabraded and laser-irradiated dentin resulted in lower mu TBSs than conventionally bur-cut dentin, irrespective of the adhesive employed. Significance. The techniques, such as CVD diamond-bur cutting, CVD diamond ultra-sonoabrasion and laser-irradiation, used for cavity preparation may affect the bonding effectiveness of adhesives to dentin, irrespective of their acidity or approach. (C) 2007 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Influence of Er,Cr : YSGG laser treatment on the microtensile bond strength of adhesives to dentin

Purpose: In light of the concept of minimally invasive dentistry, erbium lasers have been considered as an alternative technique to the use of diamond burs for cavity preparation. The purpose of this study was to assess the bonding effectiveness of adhesives to Er,Cr:YSGG laser-irradiated dentin using irradiation settings specific for cavity preparation. Materials and Methods: Fifty-four midcoronal dentin surfaces, obtained from sound human molars, were irradiated with an Er,Cr:YSGG laser or prepared with a diamond bur using a high-speed turbine. One etch-and-rinse (Optibond FL/Kerr) and three self-etching adhesives (Adper Prompt L-Pop/3M ESPE, Clearfil SE Bond/Kuraray, and Clearfil S-3 Bond/Kuraray) were used to bond the composite to dentin. The microtensile bond strength (mu TBS) was determined after 24 h of storage in water at 37 degrees C. The Kruskal-Wallis test was used to determine pairwise statistical differences (p < 0.05). Prepared dentin surfaces, adhesive interfaces, and failure patterns were analyzed using a stereo microscope and Field-emission gun Scanning Electron Microscopy (Feg-SEM). Results: Significantly lower mu TBS was observed to laser-irradiated than to bur-cut dentin (p < 0.05), irrespective of the adhesive employed. Feg-SEM photomicrographs of lased dentin revealed an imbricate patterned substrate and the presence of microcracks at the dentin surface. Conclusion: Morphological alterations produced by Er,Cr:YSGG laser-irradiation adversely influence the bonding effectiveness of adhesives to dentin. Keywords: dentin, adhesion, adhesives, laser, ErCr:YSGG.

Effect of blood contamination on the shear bond strength at resin/dentin interface in primary teeth

Purpose: To assess in vitro the shear bond strength at the resin/dentin interface in primary teeth after contamination with fresh human blood. Methods: 75 crowns of primary molars were embedded in acrylic resin and mechanically ground to expose a flat dentin surface. The specimens were randomly assigned to five groups (n=15), according to the surface treatment. Group I (control) had no blood contamination. The other groups were blood-contaminated and subjected to different post-contamination protocols: in Group 2, the surfaces were rinsed with water; in Group 3, the surfaces were air-dried; in Group 4, the surfaces were rinsed and air-dried; and in Group 5, no post-contamination treatment was done. In all groups, a 3-mm dentin bonding site was demarcated, Single Bond adhesive system was applied and resin composite cylinders were bonded. After 24 hours in distilled water, shear bond strength was tested at a crosshead speed of 0.5 mm/minute. Results: Means (in MPa) were: Group 1: 7.1 (+/- 4.2); Group 2: 4.0 (+/- 1.8); Group 3: 0.9 (+/- 0.7); Group 4: 3.9 (+/- 2.2) and Group 5: 1.3 (+/- 1.5). Data were analyzed statistically by the Kruskal-Wallis test at 5% significance level. Groups 2 and 4 were similar to each other (P > 0.05) and both ware similar to Group 1 (P > 0.05). These groups (2, 3 and 4) had statistically significantly higher bond strengths than Groups 3 and 5 (P < 0.05). Blood contamination negatively affected the shear bond strength to primary tooth dentin. Among the blood-contaminated groups, water-rinsed specimens had higher bond strengths than those that were exclusively air-dried or not submitted to any post-contamination protocol before adhesive application.

Film forming solutions based on gelatin and poly(vinyl alcohol) blends: Thermal and rheological characterizations

The objective of this work was to study the theological and thermal properties of film forming solutions (FFS) based on blends of gelatin and poly(vinyl alcohol) (PVA). The effect of the PVA concentration and plasticizer presence on the flow behavior, and viscoelastic and thermal properties of FFS was studied by steady-shear flow and oscillatory experiments, and also, by microcalorimetry. The FB presented Newtonian behavior at 30 degrees C, and the viscosity was not affected neither by the PVA concentration nor by the plasticizer. All FFS presented a phase transition during tests applying temperature scanning. It was verified that the PVA affected the viscoelastic properties of FFS by dilution of gelatin. This behavior was confirmed by microcalorimetric analysis. The behaviors of the storage (G`) and loss (G ``) moduli as a function of frequency of FFS obtained at 5 degrees C were typical of physical gels; with the G` higher than the G ``. The strength of the gels was affected by the PVA concentration. (C) 2009 Elsevier Ltd. All rights reserved.

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.

Bond Strength of Dental Adhesive Systems Irradiated with Ionizing Radiation

Purpose: The aim of the present paper was to determine the effect of different types of ionizing radiation on the bond strength of three different dentin adhesive systems. Materials and Methods: One hundred twenty specimens of 60 human teeth (protocol number: 032/2007) sectioned mesiodistally were divided into 3 groups according to the adhesives systems used: SB (Adper Single Bond Plus), CB (Clearfil SE Bond) and AP (Adper Prompt Self-Etch). The adhesives were applied on dentin and photo-activated using LED (Lec 1000, MMoptics, 1000 mW/cm(2)). Customized elastomer molds (0.5 mm thickness) with three orifices of 1.2 mm diameter were placed onto the bonding areas and filled with composite resin (Filtek Z-250), which was photo-activated for 20 s. Each group was subdivided into 4 Subgroups for application of the different types of ionizing radiation: ultraviolet radiation (UV), diagnostic x-ray radiation (DX), therapeutic x-ray radiation (TX) and without irradiation (control group, CG). Microshear tests were carried out (Instron, model 4411), and afterwards the modes of failure were evaluated by optical and scanning electron microscope and classified using 5 scores: adhesive failure, mixed failures with 3 significance levels, and cohesive failure. The results of the shear bond strength test were submitted to ANOVA with Tukey`s test and Dunnett`s test, and the data from the failure pattern evaluation were analyzed with the Mann Whitney test (p = 0.05). Results: No change in bond strength of CB and AP was observed after application of the different radiation types, only SB showed increase in bond strength after UV (p = 0.0267) irradiation. The UV also changed the failure patterns of SB (p = 0.0001). Conclusion: The radio-induced changes did not cause degradation of the restorations, which means that they can be exposed to these types of ionizing radiation without weakening the bond strength.

Enzyme immobilization on Ag nanoparticles/polyaniline nanocomposites

We show a simple strategy to obtain all efficient enzymatic broelectrochemical device, in which urease was immobilized oil electroactive nanostructured membranes (ENMs) made with polyaniline and silver nanoparticles (AgNP) stabilized in polyvinyl alcohol (PAni/PVA-AgNP). Fabrication of the modified electrodes comprised the chemical deposition of polyaniline followed by drop-coating of PVA-AgNP and urease, resulting in a final ITO/PAni/PVA-AgNP/urease electrode Configuration. For comparison. the electrochemical performance of ITO/PAni/urease electrodes (without Ag nanoparticles) was also studied. The performance of the modified electrodes toward Urea hydrolysis was investigated via amperometric measurements, revealing a fast increase in cathodic current with a well-defined peak upon addition of urea to the electrolytic solution. The cathodic currents for the ITO/PAni/PVA-AgNP urease electrodes were significantly higher than for the ITO/PAni/urease electrodes. The friendly environment provided by the ITO/PAni/PVA-AgNP electrode to the immobilized enzyme promoted efficient catalytic conversion of urea into ammonium and bicarbonate tons. Using the Michaelis-Menten kinetics equation, a K(M)(aPP) of 2.7 mmol L(-1) was obtained. indicating that the electrode architecture employed may be advantageous for fabrication of enzymatic devices with improved biocatalytic properties. Crown Copyright (C) 2009 Published by Elsevier B.V. All rights reserved.

Bond Strength and Etching Pattern of Adhesive Systems to Enamel: Effects of Conditioning Time and Enamel Preparation

Statement of the problem: The performance of self-etch systems on enamel is controversial and seems to be dependent on the application technique and the enamel preparation. Purpose of the Study: To examine the effects of conditioning time and enamel surface preparation on bond strength and etching pattern of adhesive systems to enamel. Materials and Methods: Ninety-six teeth were divided into 16 conditions (N = 6) in function of enamel preparation and conditioning time for bond strength test. The adhesive systems OptiBond FL (Kerr, Orange, CA, USA), OptiBond SOLO Plus (Kerr), Clearfil SE Bond (Kuraray, Osaka, Japan), and Adper Prompt L-Pop (3M ESPE, St. Paul, MN, USA) were applied on unground or ground enamel following the manufacturers` directions or doubling the conditioning time. Cylinders of Filtek Flow (0.5-mm height) were applied to each bonded enamel surface using a Tygon tube (0.7 mm in diameter; Saint-Gobain Corp., Aurora, OH, USA). After storage (24 h/37 degrees C), the specimens were subjected to shear force (0.5 mm/min). The data were treated by a three-way analysis of variance and Tukey`s test (alpha = 0.05). The failure modes of the debonded interfaces and the etching pattern of adhesives were observed using scanning electron microscopy. Results: Only the main factor ""adhesive"" was statistically significant (p < 0.001). The lowest bond strength value was observed for OptiBond FL. The most defined etching pattern was observed for 35% phosphoric acid and for Adper Prompt L-Pop. Mixed failures were observed for all adhesives, but OptiBond FL showed cohesive failures in resin predominantly. Conclusions: The increase in the conditioning time as well as the enamel pretreatment did not provide an increase in the resin-enamel bond strength values for the studied adhesives. CLINICAL SIGNIFICANCE The surface enamel preparation and the conditioning time do not affect the performance of self-etch systems to enamel. (J Esthet Restor Dent 20:322-336, 2008)

Diphtheria toxoid conformation in the context of its nanoencapsulation within liposomal particles sandwiched by chitosan

Chitosan (alpha alpha-(1-4)-amino-2-deoxy-beta beta-D-glucan) is a deacetylated form of chitin, a polysaccharide from crustacean shells. Its unique characteristics, such as positive charge, biodegradability, biocompatibility, nontoxicity, and rigid structure, make this macromolecule ideal for an oral vaccine delivery system. We prepared reverse-phase evaporation vesicles (REVs) sandwiched by chitosan (Chi) and polyvinylic alcohol (PVA). However, in this method, there are still some problems to be circumvented related to protein stabilization. During the inverted micelle phase of protein nanoencapsulation, hydrophobic interfaces are expanded, leading to interfacial adsorption, followed by protein unfolding and aggregation. Here, spectroscopic and immunological techniques were used to ascertain the effects of the Hoffmeister series ions on diphtheria toxoid (Dtxd) stability during the inverted micelle phase. A correlation was established between the salts used in aqueous solutions and the changes in Dtxd solubility and conformation. Dtxd alpha alpha-helical content was quite stable, which led us to conclude that encapsulation occurred without protein aggregation or without exposition of hydrophobic residues. Dtxd aggregation was 98% avoided by the kosmotropic, POPVA formulation in the presence of 50 mM of PO

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.

Coating of Cotton Yarn with Poly(vinyl alcohol) and Poly(N-vinyl-2-pyrrolidone) Crosslinked via Ultraviolet Radiation

The coating of cotton fiber is used in the textile industry to increase the mechanical resistance of the yarn and their resistance to vibration, friction, impact, and elongation, which are some of the forces to which the yarn is subjected during the weaving process. The main objective of this study was to investigate the use of synthetic hydrophilic polymers, poly(vinyl alcohol) (PVA), and poly(N-vinyl-2-pyrrolidone) (PVP) to coat 100% cotton textile fiber, with the aim of giving the fiber temporary mechanical resistance. For the fixation of the polymer on the fiber, UV-C radiation was used as the crosslinking process. The influence of the crosslinking process was determined through tensile testing of the coated fibers. The results indicated that UV-C radiation increased the mechanical resistance of the yarn coated with PVP by up to 44% and the yarn coated with PVA by up to 67% compared with the pure cotton yarn, that is, without polymeric coating and crosslinking. This study is of great relevance, and it is important to consider that UV-C radiation dispenses with the use of chemical substances and prevents the generation of toxic waste at the end of the process. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 119: 2560-2567, 2011