Influence of plasticizer type and storage conditions on properties of poly(methyl vinyl ether-co-maleic anhydride) bioadhesive films

Poly(methyl vinyl ether-co-maleic anhydride) formed films from aqueous formulations with characteristics that are ideal as a basis for producing a drug-containing bioadhesive delivery system when plasticized with a monohydroxyl functionalized plasticizer. Hence, films containing a novel plasticizer, tripropylene glycol methyl ether (TPME), maintained their adhesive strength and tensile properties when packaged in aluminized foil for extended periods of time. Films plasticized with commonly used polyhydric alcohols, such as the glycerol in this study, underwent an esterification reaction that led to polymer crosslinking, as shown in NMR studies. These revealed the presence of peaks in the ester/carbonyl region, suggesting that glyceride residue formation had been initiated. Given the polyfunctional nature of glycerol, progressive esterification would result in a polyester network and an accompanying profound alteration in the physical characteristics. Indeed, films became brittle over time with a loss of both the aqueous solubility and bioadhesion to porcine skin. In addition, a swelling index was measurable after 7 days, a property not seen with those films containing TPME. This change in bioadhesive strength and pliability was independent of the packaging conditions, rendering the films that contain glycerol as unsuitable as a basis for topical bioadhesive delivery of drug substances. Consequently, films containing TPME have potential as an alternative formulation strategy.

Relationships between antioxidant activity, color, and flavor compounds of crystal malt extracts

Aqueous extracts were prepared from five barley crystal malts (color range 15-440 degrees EBC, European Brewing Convention units). Antioxidant activity was determined by using the 2,2'-azinobis(3-ethylbenothiazoline-6-sulfonic acid) (ABTS(.+)) radical cation scavenging method. Antioxidant activity increased with increasing color value although the rate of increase decreased with increasing color value. Color was measured in CIELAB space. Extracts of the 15, 23, and 72 degrees EBC malts followed the same dilution pathway as did the 148 degrees EBC sample at higher dilution levels, indicating that they could each be used to give the same color by appropriate dilution. The 440 degrees EBC sample followed a different dilution pathway, indicating that different compounds were responsible for color in this extract. Fifteen selected volatile compounds were monitored using gas chromatography/mass spectrometry (GC/MS). Levels of methylpropanal, 2-methylbutanal, and 3-methylbutanal were highest for the 72 degrees EBC sample. When odor threshold values of the selected compounds were taken into account, 3-methylbutanal was the most important contributor to flavor., Relationships between levels of the lipid oxidation products, hexanal and (E)-2-nonenal, and antioxidant activity were complex, and increasing antioxidant activity for samples in the range of 15-148 degrees EBC did-not result in reduced levels of these lipid-derived compounds. When different colored malt extracts were diluted to give the same a* and b* values, calculated antioxidant activity and amounts of 3-methylbutanal, hexanal, and (E)-2-nonenal decreased with increasing degrees EBC value.

Kinetics of the oxidation of methyl tert-butyl ether (MTBE) by potassium permanganate

The occurrence of the fuel oxygenate methyl tert-butyl ether (MTBE) in the environment has received considerable scientific attention. The pollutant is frequently found in the groundwater due to leaking of underground storage tanks or pipelines. Concentrations of more than several mg/L MTBE were detected in groundwater at several places in the US and Germany in the last few years. In situ chemical oxidation is a promising treatment method for MTBE-contaminated plumes. This research investigated the reaction kinetics for the oxidation of MTBE by permanganate. Batch tests demonstrated that the oxidation of MTBE by permanganate is second order overall and first order individually with respect to permanganate and MTBE. The second-order rate constant was 1.426 x 10(-6) L/mg/h. The influence of pH on the reaction rate was demonstrated to have no significant effect. However, the rate of MTBE oxidation by potassium permanganate is 2-3 orders of magnitude lower than of other advanced oxidation processes. The slower rates of MTBE oxidation by permanganate limit the applicability of this process for rapid MTBE cleanup strategies. However, permanganate oxidation of MTBE has potential for passive oxidation risk management strategies. (C) 2002 Elsevier Science Ltd. All rights reserved.

Physicochemical Characterization of Poly(ethylene glycol) Plasticized Poly(methyl vinyl ether-co-maleic acid) Films

The influence of the poly(ethylene glycol) (PEG) plasticizer content and molecular weight on the physicochemical properties of films cast from aqueous blends of poly(methyl vinyl ether-co-maleic acid) (PMVE/MA) was investigated with tensile mechanical testing, thermal analysis, and attenuated total reflectance/Fourier transform infrared spectroscopy. Unplasticized films and those containing high copolymer contents were very difficult to handle and proved difficult to test. PEG with a molecular weight of 200 Da was the most efficient plasticizer. However, films cast from aqueous blends containing 10% (w/w) PMVE/MA and either PEG 1000 or PEG 10,000 when the copolymer/plasticizer ratio was 4 : 3 and those cast from aqueous blends containing 15% (w/w) PMVE/MA and either PEG 1000 or PEG 10,000 when the copolymer/plasticizer ratio was 2 : 1 possessed mechanical properties most closely mimicking those of a formulation we have used clinically in photodynamic therapy. Importantly, we found previously that films cast from aqueous blends containing 10% (w/w) PMVE/MA performed rather poorly in the clinical setting, where uptake of moisture from patients' skin led to reversion of the formulation to a thick gel. Consequently, we are now investigating films cast from aqueous blends containing 15% (w/w) PMVE/MA and either PEG 1000 or PEG 10,000, where the copolymer/plasticizer ratio is 2 : 1, as possible Food and Drug Administration approved replacements for our current formulation, which must currently be used only on a named patient basis as its plasticizer, tripropylene glycol methyl ether, is not currently available in pharmaceutical grade

Investigation of swelling and network parameters of poly (ethylene glycol)-crosslinked poly (methyl vinyl ether-co-maleic acid) hydrogels

he influence of poly(ethylene glycol) (PEG) plasticiser content and molecular weight on the physicochemical properties of films cast from aqueous blends of poly(methyl vinyl ether-co-maleic acid) was investigated using thermal analysis, swelling studies, scanning electron microscopy (SEM) and attenuated total reflectance (ATR)-Fourier transform infrared (FTIR) spectroscopy. FTIR spectroscopy revealed a shift of the CO peak from 1708 to 1731 cm-1, indicating that an esterification reaction had occurred upon heating, thus producing crosslinked films. Higher molecular weight PEGs (10,000 and 1000 Da, respectively), having greater chain length, producing hydrogel networks with lower crosslink densities and higher average molecular weight between two consecutive crosslinks. Accordingly, such materials exhibited higher swelling rates. Hydrogels crosslinked with a low molecular weight PEG (PEG 200) showed rigid networks with high crosslink densities and, therefore, lower swelling rates. Polymer:plasticizer ratio alteration did not yield any discernable patterns, regardless of the method of analysis. The polymer–water interaction parameter (?) increased with increases in the crosslink density. SEM studies showed that porosity of the crosslinked films increased with increasing PEG MW, confirming what had been observed with swelling studies and thermal analysis, that the crosslink density must be decreased as the Mw of the crosslinker is increased. Hydrogels containing PMVE/MA/PEG 10,000 could be used for rapid delivery of drug, due to their low crosslink density. Moderately crosslinked PMVE/MA/PEG 1000 hydrogels or highly crosslinked PMVE/MA/PEG 200 systems could then be used in controlling the drug delivery rates. We are currently evaluating these systems, both alone and in combination, for use in sustained release drug delivery devices.