PVA hydrogels loaded with a Brazilian propolis for burn wound healing applications

PVA hydrogels offer many suitable characteristics for burn wound dressings. However, unmodified PVA gels do not act against infection. Propolis is a natural antimicrobial agent suitable for incorporation into PVA gels. PVA–propolis gels were produced by freeze–thawing method, and their microstructure, mechanical, and swelling properties (in standard PBS and a PBS‐based solution with pH 4.0) were characterized. The propolis release profiles and the gel's antibacterial and cytotoxicity properties were also investigated. The presence of propolis in the gels interfered with the PVA crystallization profile and with the mechanical properties. All samples swelled at least 400% in both media. The propolis was mostly released to the media in the first day of immersion. PVA–propolis gels with concentrations of 15% propolis or more were active against the gram‐positive bacterium Staphylococcus aureus, which is associated with initial colonization of the wound. All PVA–propolis samples acted as barriers to microbial penetration. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42129.     

Polyvinyl alcohol and acidity-regulating KH2PO4 synergistically accelerated degradation of PBAT/PLA composites

Poly(butylene adipate-co-terephthalate) (PBAT)/polylactic acid (PLA) composites were prepared by water-soluble polyvinyl alcohol (PVA) and degradation-promoting agent (DPA) which were made from acidity-regulating KH₂PO₄ and halloysite by a physical layer-by-layer coating method. The effect of PVA and DPA on the biodegradation of PBAT/PLA composites in the cross-sectional morphology, thermal properties, molecular structure, due to degradation was evaluated using a host of characterization methods. The results showed that PVA had a good solubilizing effect on the composite system and improved the overall compatibility. DPA had little effect on the compatibility, crystallinity, and thermal stability of the composite system, but greatly accelerated the degradation. The interior of composite material containing DPA (Com-DPA) was shown to be severely damaged after 29 weeks of degradation, which was attributed to preferential degradation of amorphous regions of the composite by ester hydrolysis. Our results demonstrated the PVA and DPA worked synergistically to promote swelling and diffusivity of degradation products, and provided an acid environment for enhancing ester hydrolysis. This technology may have good prospects for accelerated degradation of materials in agricultural applications.     

In vitro degradation and protein release of semi‐IPN hydrogels consisted of poly(acrylic acid‐acrylamide‐methacrylate) and amylose

The enzymatic degradation mechanism of semi‐interpenetrating network (semi‐IPN) hydrogel of poly (acrylic acid‐acrylamide‐methacrylate) crosslinked by azocompound and amylose in vitro was investigated in the presence of Fungamyl 800L (α‐amylase) and rat cecum content (cecum bacteria). The degradation mechanism involves degradable competition, i.e., reduction of azo crosslinkage is dominant in the earlier period of degradation. Subsequently, the degradation of gels is continued by combination of reduction of azo crosslinkage and hydrolysis of amylose. The cumulative release ratios of Bovine serum albumin (BSA, as a model drug) loaded semi‐IPN gels are 25% in pH 2.2 buffer solutions and 74% in pH 7.4 buffer solutions within 48 h. Moreover, the release behavior of BSA from the semi‐IPN gels indicates that it follows Fickian diffusion mechanism in pH 2.2 media and non‐Fickian diffusion and polymer chains relaxation mechanism in pH 7.4 media. The results indicate that the release of BSA from the semi‐IPN gels was controlled via a combined mechanism of pH dependent swelling and specificity to enzymatic degradation. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

The investigation of thermal decomposition pathway and products of poly(vinyl alcohol) by TG‐FTIR

A generalized form of a semiquantitative method has been developed based on the multilinear least‐squares regression technique applied on the entire FTIR absorbance spectrum of a gaseous mixture to determine components concentration. Thermal degradation of poly(vinyl alcohol) samples with high, PVA(98), and low degree of hydrolysis, PVA(80), has been investigated by TG‐FTIR simultaneous analysis performed in an inert atmosphere. Analysis of gaseous products was carried out using a routine developed in Matlab and this routine returns the product concentration with a reasonable RMS error. The correlation coefficients of the original mixture spectrum with the mixed output were obtained at some specific peak temperatures using irAnalysis software. The first process is the loss of physically adsorbed water which followed by two main processes of thermal degradation. In spite of the similarity of evolved gaseous products, two samples showed some differences in components concentrations identified in the volatile mixture. Acetaldehyde has been identified as the main volatile product in the first thermal degradation step of PVA(98) and PVA(80). The second major degradation product of PVA(80) is acetic acid due to presence of more residual acetate group while 2‐butenal have been identified for PVA(98). Water was mainly produced in the first stage of thermal degradation of PVA(98) while it was identified in the first and second stages for PVA(80). This might be attributed to existence of a competition between water and residual acetate group for elimination that postpones the complete elimination of OH group to the second degradation stage. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42117.     

Selected properties of pH‐sensitive,biodegradable chitosan–poly(vinyl alcohol) hydrogel

Chitosan and poly(vinyl alcohol) (PVA) were used to form a semi‐interpenetrating polymeric network with glutaraldehyde as the cross‐linker. The molecular weight and degree of deacetylation of the chitosan were 612 kDa and 72 %, respectively. The chemical bonds formed by the cross‐linking reaction and transition of these bonds in different pH media were investigated. The gelation property of the chitosan–PVA pregel solution and mechanical properties of the hydrogel were studied. The FTIR spectra of the hydrogel before and after swelling at pH 3 and pH 7 indicated formation of Schiff's base (C?N) and ? NH₃⁺. They also showed pH‐induced transition of C?N to C? N, and ? NH₃⁺ to ? NH₂, as well as the instability of the Schiff's base. The chitosan is essential for hydrogel formation through Schiff's base reaction between the amino groups of the chitosan and the aldehyde groups of the glutaraldehyde. The addition of PVA improved the mechanical properties of the hydrogel. However, PVA tends to leach out at longer swelling times in the acidic medium due to hydrolysis of the gel networks, Schiff's base. Copyright © 2004 Society of Chemical Industry     

Uses of electron‐beam irradiation to prepare pH‐ and temperature‐sensitive hydrogels from reactive poly(vinyl alcohol) grafts

Thermosensitive poly(vinyl alcohol)‐graft‐(maleic anhydride), PVA‐MA, and poly(vinyl alcohol)‐graft‐(N‐isopropylacrylamide maleic anhydride) (PVA‐MA‐NIPAAm) copolymers containing carboxyl groups were prepared using electron beam irradiation at dose 80 kGy. The swelling ratios of the cross‐linked gels were measured at various temperatures. The LCST values were measured using DSC technique. The temperature dependence of the swelling ratios of the cross‐linked copolymers and terpolymers were measured at different temperatures. The swelling ratios of copolymers increased with increasing temperature up to 25–38°C, then decreased. The swelling behavior of both copolymers and terpolymers was referred to formation of hydrogen bonds between amide group of NIPAAm moieties and carboxyl group in MA moieties and to hydrophobic interaction due to methyl groups of NIPAAm. The swelling behaviors of these gels were analyzed in buffer solution at various pH. Swelling ratios of all gels were relatively high and they showed reasonable sensitive to pH. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis of spherical core‐shell poly(vinyl acetate)/poly(vinyl alcohol) particles for use in vascular embolization: Study of morphological and molecular modifications during shell formation

Transarterial vascular embolization and chemoembolization has become common medical procedures, where partially hydrolyzed poly(vinyl alcohol) (PVA) beads remains as one of the most used embolic agent materials. Although synthetic, PVA cannot be synthesized by direct polymerization and must be obtained by chemical modification of another polymer, usually poly(vinyl acetate) (PVAc). The aim of the present work is to synthesize spherical core‐shell PVAc/PVA particles and study the morphological and molecular modifications during shell formation. The polymer particles where produced in two stages, where first the PVAc core was obtained by suspension polymerization of vinyl acetate (VAc) and then the PVA shell synthesized through hydrolysis. Spherical PVAc particles were successfully produced and isolated using an optimized suspension polymerization process. During the shell formation, it was shown that none of the conditions used affected the overall morphology of the particles although changes in the final size distribution could be observed. However, it was possible to identify the process variables and reaction condition that affect the molecular weight averages and polydispersities of the final copolymer. POLYM. ENG. SCI., 55:2237–2244, 2015. © 2015 Society of Plastics Engineers     

Characterization of strong polyelectrolyte hydrogels based on poly(vinyl alcohol)

Maleic anhydride (MA) was grafted onto both partially and fully hydrolyzed poly(vinyl alcohol) (PVA) in the presence of an initiator. Strong polyelectrolyte polymers were prepared by sulfonation of PVA–MA grafts. The sulfonation was completed by reaction of hydroxyl groups of PVA–MA grafts with two different sulfonating reagents (chlorosulfonic acid and pyridine sulfonic acid). The sulfonation degree was evaluated by acid–base titration and ¹H NMR analysis. The solution behaviour of the prepared grafts was evaluated from viscosity measurements. Four kinds of water‐insoluble PVA–MA and PVA–MA‐SO₃H hydrogels were prepared by heat treatment, physical gelation and chemical crosslinking with different weight ratios of N,N‐methylene bisacrylamide (MBA) crosslinker. The swelling parameters were measured for all prepared gels in deionized water and aqueous solutions at different pH values from 2 to 12 having constant ionic strength (I = 0.1). All gels exhibit a different swelling behaviour upon environmental pH changes. Copyright © 2004 Society of Chemical Industry     

Xylan/polyvinyl alcohol blend and its performance as hydrogel

Xylan was first modified with maleic anhydride (MA) to obtain xylan‐MA. The derivative was then blended with polyvinyl alcohol (PVA) to generate xylan‐MA/PVA hydrogel. Xylan‐MA was prepared by reacting xylan with MA under an acidic condition. A ring opening of MA occurred, yielding ester linkages between xylan and MA, as verified by ¹³C‐NMR and FTIR. The effects of reaction temperature and weight ratio of xylan to MA on esterification were examined. Thermal stability of modified xylan derivatives was compared with that of pure xylan using TGA. The blends of xylan‐MA with PVA became crosslinked gel after being heated at high temperature. The influences of MA and PVA contents on strength and swelling behaviors of the gels were investigated. The cytotoxicity of the gels was also evaluated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1914–1918, 2006     

Poly(ester amide)s derived from tartaric and succinic acids: Changes in structure and properties upon hydrolytic degradation

The changes in structure and properties taking place in a set of tartaric acid‐based polyamides and poly(ester amide)s upon hydrolytic degradation were examined. Poly(hexamethylene 2,3‐di‐O‐methyl‐L ‐tartaramide)s, either pure or containing minor amounts of succinate ester groups (≤10%), were exposed to humidity or incubated in buffered water at pH 7.4 and 37°C, and their thermal and mechanical properties were evaluated as a function of time. Both moisture uptake and hydrolysis induced a noticeable decay in the tensile properties of polymers. These effects were greatly enhanced by the presence of ester groups, whereas no large differences were noticed for changes in the enantiomeric composition. Variations in the glass transition temperatures and melting points appeared to be slight, whereas crystallinity clearly increased with incubation time. The latter effect was most apparent in poly(ester amide)s with a nearly racemic composition, in which a crystal‐to‐crystal transition was observed to take place upon degradation. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 486–494, 2000     

Preparation and properties of physically crosslinked sodium carboxymethylcellulose/poly(vinyl alcohol) complex hydrogels

A series of physically crosslinked complex hydrogels of poly(vinyl alcohol) (PVA) and sodium carboxymethylcellulose (CMC) were prepared via physical mixing and a freeze/thaw technique. The morphology of the CMC/PVA complex gels was analyzed with differential scanning calorimetry and wide‐angle X‐ray diffraction. It was found that the crystallinity and melting temperature of the complex gels decreased, whereas the glass‐transition temperature increased, with an increase in the content of CMC. The reswelling of the complex gels was pH‐responsive and relied on the content of CMC and the freeze/thaw cycles. A network structure model of the complex gel was presented. PVA crystalline regions served as physical crosslinks; the interaction between CMC and PVA resulted in intramolecular entanglements. It was also found that the model drug hemoglobin was released completely from the complex hydrogels in 4 h, and its release rate increased with an increase in the content of CMC. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Radiopaque iodinated ethers of poly(vinyl iodobenzyl ether)s: Synthesis and evaluation for endovascular embolization

Leachable‐free radiopaque iodinated polymers were designed as long‐lived embolization materials visible by X‐ray tomography. This is a definite improvement over liquid embolics incorporating either radiopaque inorganic particles or iodinated polymers having hydrolysable ester bonds. Grafting 4‐iodobenzyl or 2,3,5‐triiodobenzyl groups to poly(vinyl alcohol) (PVAL) yields iodobenzyl ethers of PVAL having iodine contents in the range 40–70 wt %. Their solubility in solvents accepted for medical devices (DMSO and NMP), viscosity of concentrated solutions, precipitation behavior, radiopacity, and stability with respect to sterilization and hydrolysis were assessed. The solvent NMP allows the preparation of concentrated solutions of suitable viscosity for their application as liquid embolics. Precipitation in water yields a cohesive mass of material that can plug vascular malformations. A rationale to the properties is given in terms of the Hansen contributions to the Hildebrand solubility parameters. Iodobenzyl ethers of PVA resist hydrolysis whereas their corresponding iodobenzoyl esters leach iodinated fragments. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41791.     

Effect of macromer synthesis time on the properties of the resulting poly(β‐amino ester) degradable hydrogel

Poly(β‐amino ester) biodegradable hydrogels are common in biomedical applications because of their tunable properties and similarities to natural soft tissue. Previous work has shown property adjustments through the choice of monomers, the ratio between monomers and the addition of a crosslinking component. Here, we show that the reaction time for the creation of the macromer can affect the resulting hydrogel properties, and thus provides another method of tuning properties. Macromer was created through the reaction of isobutylamine with poly(ethylene glycol) diacrylate (n = 400). The reaction progress was analyzed using IR and GPC analysis. Hydrogels were created through UV photopolymerization from macromers synthesized for 24, 36, and 48 h. The degradation, compressive moduli, and swelling were measured in an aqueous solution. All showed significant differences between hydrogels of different macromer synthesis times. These differences likely stem from the incomplete macromer synthesis reaction and resulting PEG‐rich regions in hydrogels from shorter synthesis times. These regions will not readily degrade, but do increase the mechanical properties and extent of swelling. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Tear force of physically crosslinked poly(vinyl alcohol) gels with different submicrometer‐scale network structures

Poly(vinyl alcohol) (PVA) gels can be easily prepared by either the freeze‐thawing (FT gel) method or by the cast‐drying (CD gel) method. Although the resulting nanostructured networks of the FT and CD gels are similar, their physical properties are quite different; while CD gels are transparent and elastic, FT gels are opaque and less elastic. Moreover, the tear energy of the FT gels is much greater than that of the CD gels, which is a direct result of micrometer‐scale differences in their network structures. In order to control the distribution of microcrystallites on nano‐ and micrometer scales, FT gels were prepared from PVA solutions with different water contents. As a result, the gel gradually became more transparent as the initial water content was decreased; and accordingly, the tear energy decreased. Tear resistance was improved in the case of FT gels by repeating the number of FT cycles, whereas with CD gels, this was achieved by increasing the gelation temperature. These results indicate that the microscopic network structures are characterized by a micrometer‐scale bundled‐polymer (fibril), which determines the tear energy of FT gels. Simple methods to control the fibril network structure of FT gels using a unidirectional freezing method are presented herein, with the swelling and mechanical properties of modified FT gels discussed in terms of their multiple‐scale network structures. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41356.     

Bio‐nanocomposite films based on cellulose nanocrystals filled polyvinyl alcohol/chitosan polymer blend

Bio‐nanocomposite films based on polyvinyl alcohol/chitosan (PVA/CS) polymeric blend and cellulose nanocrystals (CNC) were prepared by casting a homogenous and stable aqueous mixture of the three components. CNC used as nanoreinforcing agents were extracted at the nanometric scale from sugarcane bagasse via sulfuric acid hydrolysis; then they were characterized and successfully dispersed into a PVA/CS (50/50, w/w) blend to produce PVA/CS–CNC bio‐nanocomposite films at different CNC contents (0.5, 2.5, 5 wt %). Viscosity measurement of the film‐forming solutions and structural and morphological characterizations of the solid films showed that the CNC are well dispersed into PVA/CS blend forming strong interfacial interactions that provide an enhanced load transfer between polymer chains and CNC, thus improving their properties. The obtained bio‐nanocomposite films are mechanically strong and exhibit improved thermal properties. The addition of 5 wt % CNC within a PVA/CS blend increased the Young's modulus by 105%, the tensile strength by 77%, and the toughness by 68%. Herein, the utilization of Moroccan sugarcane bagasse as raw material to produce high quality CNC has been explored. Additionally, the ability of the as‐isolated CNC to reinforce polymer blends was studied, resulting in the production of the aforementioned bio‐nanocomposite films with improved properties. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42004.     

Drug‐release behavior of chitosan‐g‐poly(vinyl alcohol) copolymer matrix

Chitosan‐g‐poly(vinyl alcohol) (PVA) copolymers with different grafting percent were prepared by grafting water‐soluble PVA onto chitosan. The drug‐release behavior was studied using the chitosan‐g‐PVA copolymer matrix containing prednisolone in a drug‐delivery system under various conditions. The relationship between the amount of the released drug and the square root of time was linear. From this result, the drug‐release behavior through the chitosan‐g‐PVA copolymer matrix is shown to be consistent with Higuchi's diffusion model. The drug‐release apparent constant (K_H) was slightly decreased at pH 1.2, but increased at pH 7.4 and 10 according to the increasing PVA grafting percent. Also, K_H was decreased by heat treatment and crosslinking. The drug release behavior of the chitosan‐g‐PVA copolymer matrix was able to be controlled by the PVA grafting percent, heat treatment, or crosslinking and was also less affected by the pH values than was the chitosan matrix. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 458–464, 1999     

Preparation of ketoprofen‐loaded high‐molecular‐weight poly(vinyl alcohol) gels

High‐molecular‐weight atactic poly(vinyl alcohol) (a‐PVA) gels loaded with (R,S)‐2‐(3‐benzoylphenyl)propionic acid (ketoprofen) were prepared from 5, 6, 7, and 8 g/dL solutions of a‐PVA with a number‐average degree of polymerization of 4000 in an ethylene glycol/water mixture with an aging method to identify the effect of the initial polymer concentration on the swelling behavior, morphology, and thermal properties of a‐PVA gels. Then, the release behavior of ketoprofen from a‐PVA gels was investigated. As the polymer concentration decreased, the ability for network formation decreased, and the degree of swelling of the a‐PVA gels increased. In addition, the enthalpy increased with an increase in the a‐PVA concentration, but the melting temperatures of the gels prepared at different initial polymer concentrations were the same; this indicated that tighter gel networks would be formed by a higher polymer chain density. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Preparation and characterization of polysaccaride interpolymer complexes: I‐PVA/ι‐carrageenan

Thermal and spectroscopic charaterization of PVA, iota carrageenan (IC), and their interpolymer complexes were studied in terms of stability, complex formation, and species determination by XRF, FTIR, Raman, DSC, and TGA. Thermogravimetry analysis showed that initial thermal degradation temperature of PVA/IC decreased from 276 to 256°C with an increase of IC content. The complexation of IC to PVA significantly increased, the thermal stability of IC, where as the thermal stability of PVA increased rather insignificantly. Fourier Transform Infrared (FTIR) and Raman spectroscopic results showed that PVA interacted with IC through ? OH groups of PVA and IC as shown by the frequency and scattering shift at ? OH band of FTIR and Raman spectra of each complex. The involvements of ester sulfate and ether groups of IC in interaction were not significant. In the results of the thermal and spectroscopic analysis, 17% content of PVA/IC is the most miscible and intercomplexable weight fraction of PVA/IC. The natural source of IC, which was unknown was characterized by XRF and found to be as potassium salt and Euchema specie of marine red algee of the class Rhodophceae. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Thermal hydrolysis of poly(l‐lactic acid) films and cytotoxicity of water‐soluble degradation products

In this study, the thermal hydrolysis of the poly(l ‐lactic acid) (PLLA) films was investigated for its potential use as a food‐packaging ecomaterial. The surface morphology, mass loss, molecular weight, thermal properties, and medium pH were routinely investigated; meanwhile, in particular, the composition and cytotoxicity of the water‐soluble degradation products were studied. The changes in the mass loss and molecular weight revealed a random chain‐scission mechanism. Differential scanning calorimetry analysis implied that the hydrolysis preferentially took place in the amorphous region. The medium pH decreased with time because of the accumulation of acid water‐soluble products in the medium. Liquid chromatography/mass spectrometry analysis proved that these products were composed of 1–13 lactic acid units, in which the content of l ‐lactic acid increased with time and reached 9.71 mmol/L after hydrolysis for 84 days. The in vitro cell culture indicated that the water‐soluble degradation products from the PLLA films had no cytotoxicity to human umbilical vein endothelial cells. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42064.     

Preparation of chemically crosslinked gels with maleate‐denatured poly(vinyl alcohol) and its application to drug release

Maleate‐denatured poly(vinyl alcohol) (M‐PVA) was crosslinked with heating. The mechanism of crosslinking was studied with several procedures: titration, Fourier transform infrared, and solubility. The carboxyl groups of M‐PVA consisted of carboxylates and a few free carboxyl groups. The crosslink was the ester linkage between hydroxyl and carboxyl groups. Several kinds of M‐PVA tablets were prepared under different conditions: pressures of 200–600 kgf/cm² and grain sizes of 75 (pass) to 250 μm (on). The swelling behavior of these chemically crosslinked tablets was studied in a buffer solution of pH 7.4, mainly at 37°C. Moreover, the effect of temperature from 5 to 50°C and the effect of repeated swell–dry cycles on the behavior of the tablets in a buffer solution [106 μm (on), 200 kgf/cm²] were studied. The release of p‐acetamidophenol from those tablets in the pH 7.4 buffer solution was studied. The different release patterns were due to the differences in the swelling behavior. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1178–1184, 2002; DOI 10.1002/app.10411