Amperometric quantification of polar organic solvents based on a tyrosinase biosensor

A novel amperometric biosensor for quantification of the electrochemically inert polar organic solvents based on tyrosinase electrode was preliminarily reported. The biosensor was fabricated by simply syringing an aqueous solution of tyrosinase/PVAVP (PVAVP: copolymer of poly(vinyl alcohol) grafting with 4-vinylpyridine) onto glassy carbon electrode surface followed by drying the modified electrode at +4 degrees C in a refrigerator. The current generated from electrochemical reduction of quinone is a probe signal. The biosensor can be used for quantification of polar organic solvents, and its mechanism was characterized with in situ steady-state amperometry-quartz crystal microbalance experiments. The detection limit, sensitivity, and dynamic range for certain organic solvents are dependent on the kind and concentration of the substrate probe and the hydrophobicity of the immobilization matrix. The response time for all the tested organic solvents is less than 2 min.

Amperometric biosensor for hydrogen peroxide based on sol-gel/hydrogel composite thin film

A reagentless amperometric hydrogen peroxide biosensor was developed. Horseradish peroxidase (HRP) was immobilized in a novel sol-gel organic-inorganic hybrid matrix that is composed of silica sol and a grafting copolymer of poly(vinyl alcohol) with 4-vinylpyridine (PVA-g-PVP). Tetrathiafulvalene (TTF) was employed as a mediator and could lower the operating potential to -50 mV (versus Ag/AgCl). The sensor achieved 95% of the steady-state current in 15 s. Linear calibration for hydrogen peroxide was up to 1.3 mM with the detection limit of 2.5 x 10(-7)M. The enzyme electrode retained about 94% of its initial activity after 30 days of storage in a dry state at 4 degreesC.

Amperometric glucose biosensor based on sol-gel organic-inorganic hybrid material

A new type of sol-gel organic-inorganic hybrid material was developed and used for the production of biosensors. This material is composed of silica sol and a grafting copolymer of poly(vinyl alcohol) with 4-vinylpyridine. It prevents the cracking of conventional sol-gel-derived glasses and eliminates the swelling of the hydrogel. The optimum composition of the hybrid material was first examined, and then glucose oxidase was immobilized in this matrix to demonstrate its application. The characteristics of the biosensor were studied by cyclic voltammetry and chronoamperometry. The biosensor exhibited a series of good properties: high sensitivity (600 nA mmol(-1)L(-1)), short response time (11 s) and remarkable long-term stability in storage (at least 5 months). In addition, the characteristics of the second-generation biosensor with the use of tetrathiafulvalene as a mediator mere discussed.

Development and characterization of polymeric nanoparticles(NPs) made from functionalized poly (D,L- lactide) (PLA)polymers

Les nanoparticules polymériques biodégradable (NPs) sont apparues ces dernières années comme des systèmes prometteurs pour le ciblage et la libération contrôlée de médicaments. La première partie de cette étude visait à développer des NPs biodégradables préparées à partir de copolymères fonctionnalisés de l’acide lactique (poly (D,L)lactide ou PLA). Les polymères ont été étudiés comme systèmes de libération de médicaments dans le but d'améliorer les performances des NPs de PLA conventionnelles. L'effet de la fonctionnalisation du PLA par insertion de groupements chimiques dans la chaîne du polymère sur les propriétés physico-chimiques des NPs a été étudié. En outre, l'effet de l'architecture du polymère (mode d'organisation des chaînes de polymère dans le copolymère obtenu) sur divers aspects de l’administration de médicament a également été étudié. Pour atteindre ces objectifs, divers copolymères à base de PLA ont été synthétisés. Plus précisément il s’agit de 1) copolymères du poly (éthylène glycol) (PEG) greffées sur la chaîne de PLA à 2.5% et 7% mol. / mol. de monomères d'acide lactique (PEG2.5%-g-PLA et PEG7%-g-PLA, respectivement), 2) des groupements d’acide palmitique greffés sur le squelette de PLA à une densité de greffage de 2,5% (palmitique acid2.5%-g-PLA), 3) de copolymère « multibloc » de PLA et de PEG, (PLA-PEG-PLA)n. Dans la deuxième partie, l'effet des différentes densités de greffage sur les propriétés des NPs de PEG-g-PLA (propriétés physico-chimiques et biologiques) a été étudié pour déterminer la densité optimale de greffage PEG nécessaire pour développer la furtivité (« long circulating NPs »). Enfin, les copolymères de PLA fonctionnalisé avec du PEG ayant montré les résultats les plus satisfaisants en regard des divers aspects d’administration de médicaments, (tels que taille et de distribution de taille, charge de surface, chargement de drogue, libération contrôlée de médicaments) ont été sélectionnés pour l'encapsulation de l'itraconazole (ITZ). Le but est dans ce cas d’améliorer sa solubilité dans l'eau, sa biodisponibilité et donc son activité antifongique. Les NPs ont d'abord été préparées à partir de copolymères fonctionnalisés de PLA, puis ensuite analysés pour leurs paramètres physico-chimiques majeurs tels que l'efficacité d'encapsulation, la taille et distribution de taille, la charge de surface, les propriétés thermiques, la chimie de surface, le pourcentage de poly (alcool vinylique) (PVA) adsorbé à la surface, et le profil de libération de médicament. L'analyse de la chimie de surface par la spectroscopie de photoélectrons rayon X (XPS) et la microscopie à force atomique (AFM) ont été utilisés pour étudier l'organisation des chaînes de copolymère dans la formulation des NPs. De manière générale, les copolymères de PLA fonctionnalisés avec le PEG ont montré une amélioration du comportement de libération de médicaments en termes de taille et distribution de taille étroite, d’amélioration de l'efficacité de chargement, de diminution de l'adsorption des protéines plasmatiques sur leurs surfaces, de diminution de l’internalisation par les cellules de type macrophages, et enfin une meilleure activité antifongique des NPs chargées avec ITZ. En ce qui concerne l'analyse de la chimie de surface, l'imagerie de phase en AFM et les résultats de l’XPS ont montré la possibilité de la présence de davantage de chaînes de PEG à la surface des NPs faites de PEG-g-PLA que de NPS faites à partie de (PLA-PEG-PLA)n. Nos résultats démontrent que les propriétés des NPs peuvent être modifiées à la fois par le choix approprié de la composition en polymère mais aussi par l'architecture de ceux-ci. Les résultats suggèrent également que les copolymères de PEG-g-PLA pourraient être utilisés efficacement pour préparer des transporteurs nanométriques améliorant les propriétés de certains médicaments,notamment la solubilité, la stabilité et la biodisponibilité.

Reusable Recording Medium Based on MBPVA and Vinyl Acetate

A new photopolymerizable recording media is introduced based on poly (vinyl alcohol) and vinyl acetate sensitized with methylene blue. It is observed that this MBPVA/VAc system can be reused a number of times without significant decrease in diffraction efficiency. The PVA-VAc ratio was optimized at 2:1. Diffraction efficiency of 6.3% was obtained without any fixing at a dye concentration of 9.3 10 4 mol/l at an exposure of 750 mJ/cm2. The material is attractive on account of its reusability.

Reusable Recording Medium Based on MBPVA and vinyl Acetate

A new photopolymerizable recording media is introduced based on poly (vinyl alcohol) and vinyl acetate sensitized with methylene blue. It is observed that this MBPVA/VAc system can be reused a number of times without significant decrease in diffraction . The PVA-VAc ratio was optimized at 2:1. Diffraction efficiency of 6.3% was obtained without any fixing at a dye concentration of 9.3 10 4 mol/l at an exposure of 750 mJ/cm2. The material is attractive on account of its reusability.

Reusable recording medium based on MBPVA and vinyl acetate

A new photopolymerizable recording media is introduced based on poly (vinyl alcohol) and vinyl acetate sensitized with methylene blue. It is observed that this MBPVA/VAc system can be reused a number of times without significant decrease in diffraction efficiency. The PVA-VAc ratio was optimized at 2:1. Diffraction efcienc4y of 6.3% was obtained without any fixing at a dye concentration of 9.3 x 10- mol/l at an exposure of 750mJ/cm2. The material is attractive on account of its reusability.

Reusable Recording Medium Based on MBPVA and Vinyl Acetate

A new photopolymerizable recording media is introduced based on poly (vinyl alcohol) and vinyl acetate sensitized with methylene blue. It is observed that this MBPVA/VAc system can be reused a number of times without significant decrease in diffraction efficiency. The PVA-VAc ratio was optimized at 2:1. Diffraction efcienc4y of 6.3% was obtained without any fixing at a dye concentration of 9.3 x 10- mol/l at an exposure of 750mJ/cm2. The material is attractive on account of its reusability.

Reusable Recording Medium based on MBPVA and Vinyl Acetate

A new photopolymerizable recording media is introduced based on poly (vinyl alcohol) and vinyl acetate sensitized with methylene blue. It is observed that this MBPVA/VAc system can be reused a number of times without significant decrease in diffraction efficiency. The PVA-VAc ratio was optimized at 2:1. Diffraction efcienc4y of 6.3% was obtained without any fixing at a dye concentration of 9.3 x 10- mol/l at an exposure of 750mJ/cm2. The material is attractive on account of its reusability.

Pervaporation dehydration of isopropyl alcohol with NaY zeolite incorvorated hybrid membranes

With a solution technique, NaY zeolite incorporated, tetraethylorthosilicate-crosslinked poly(vinyl alcohol) membranes were prepared. The resulting membranes were tested for their ability to separate isopropyl alcohol/water mixtures by pervaporation in the temperature range of 30-50 degrees C. The effects of the zeolite content and feed composition on the pervaporation performance of the membranes were investigated. The experimental results demonstrated that both flux and selectivity increased simultaneously with increasing zeolite content in the membranes. This was explained on the basis of the enhancement of hydrophilicity, selective adsorption, and establishment of a molecular sieving action attributed to the creation of pores in the membrane matrix. The membrane containing 15 mass % zeolite exhibited the highest separation selectivity of 3991 with a flux of 5.39 X 10(-2) kg/m(2) h with 10 mass % water in the feed at 30 degrees C. The total flux and flux of water were close to each other for almost all the studied membranes, and this suggested that the membranes could be used effectively to break the azeotropic point of water/isopropyl alcohol mixtures to remove a small amount of water from isopropyl alcohol. From the temperature-dependent diffusion and permeation values, the Arrhenius activation parameters were estimated. The activation energy values obtained for water were significantly lower than those for isopropyl alcohol, and this suggested that the developed membranes had a higher separation efficiency for water/isopropyl alcohol systems. The activation energy values for total permeation and water permeation were found to be almost the same for all the membranes, and this signified that coupled transport was minimal because of the highly selective nature of the membranes. Positive heat of sorption values were observed in all the membranes, and this suggested that Henry's mode of sorption was predominant. (c) 2008 Wiley Periodicals, lnc.

Rheological properties of tin oxide suspensions

The rheological properties of tin oxide slurries were studied experimentally and theoretically. The deflocculants used were ammonium polyacrilate (PAA) and the copolymer poly(vinyl butyral-co-vinyl alcohol-co-vinyl acetate) (PVB-PVA-PVAc), in water and ethanol, respectively. The amount of deflocculant was optimized for different solid contents by means of viscosity measurements. In spite of the high stability of PVB-dispersed slurries, a high solid concentration was not obtained. On the other hand, a slurry with a 56.4 vol.% of solids was attained when PAA was used. A theoretical study of the adsorption of PAA in its dissociated (basic solution) and non-dissociated (acidic solution) forms on SnO 2 (110) is presented. This analysis was made by means of the PM3 method using a large cluster Sn 15O 28 for the surface model. The calculated adsorption energy is larger for the ionized PAA than for the non-ionized form, indicating that alkaline slurries favor PAA adsorption on the SnO 2 surface. © 2002 Elsevier Science Ltd. All rights reserved.

Fractal dimension and Shannon's entropy analyses of the architectural complexity caused by the inflammatory reactions induced by highly crystalline polyvinyl alcohol) microspheres implanted in subcutaneous tissues of the Wistar rats

The results of the histopathological analyses after the implantation of highly crystalline PVA microspheres in subcutaneous tissues of Wistar rats are here in reported. Three different groups of PVA microparticles were systematically studied: highly crystalline, amorphous, and commercial ones. In addition to these experiments, complementary analyses of architectural complexity were performed using fractal dimension (FD), and Shannon's entropy (SE) concepts. The highly crystalline microspheres induced inflammatory reactions similar to the ones observed for the commercial ones, while the inflammatory reactions caused by the amorphous ones were less intense. Statistical analyses of the subcutaneous tissues of Wistar rats implanted with the highly crystalline microspheres resulted in FD and SE values significantly higher than the statistical parameters observed for the amorphous ones. The FD and SE parameters obtained for the subcutaneous tissues of Wistar rats implanted with crystalline and commercial microparticles were statistically similar. Briefly, the results indicated that the new highly crystalline microspheres had biocompatible behavior comparable to the commercial ones. In addition, statistical tools such as FD and SE analyses when combined with histopathological analyses can be useful tools to investigate the architectural complexity tissues caused by complex inflammatory reactions. © 2012 WILEY PERIODICALS, INC.

A reduction of diffusion in PVA Fricke hydrogels

A modification to the PVA-FX hydrogel whereby the chelating agent, xylenol orange, was partially bonded to the gelling agent, poly-vinyl alcohol, resulted in an 8% reduction in the post irradiation Fe3+ diffusion, adding approximately 1 hour to the useful timespan between irradiation and readout. This xylenol orange functionalised poly-vinyl alcohol hydrogel had an OD dose sensitivity of 0.014 Gy−1 and a diffusion rate of 0.133 mm2 h−1. As this partial bond yields only incremental improvement, it is proposed that more efficient methods of bonding xylenol orange to poly-vinyl alcohol be investigated to further reduce the diffusion in Fricke gels.

Gel-coated ion-exchange resin: A new kinetic model

Regenerable 'gel-coated' cationic resins with fast sorption kinetics and high sorption capacity have application potential for removal of trace metal ions even in large-scale operations. Poly(acrylic acid) has been gel-coated on high-surface area silica (pre-coated with ethylene-vinyl acetate copolymer providing a thin barrier layer) and insolubilized by crosslinking with a low-molecular-weight diepoxide (epoxy equivalent 180 g) in the presence of benzyl dimethylamine catalyst at 70 degrees C, In experiments performed for Ca2+ sorption from dilute aqueous solutions of Ca(NO,),, the gel-coated acrylic resin is found to have nearly 40% higher sorption capacity than the bead-form commercial methacrylic resin Amberlite IRC-50 and also several limes higher rate of sorption. The sorption on the gel-coated sorbent under vigorous agitation has the characteristics of particle diffusion control with homogeneous (gel) diffusion in resin phase. A new mathematical model is proposed for such sorption on gel-coated ion-exchange resin in finite bath and solved by applying operator-theoretic methods. The analytical solution so obtained shows goad agreement with experimental sorption kinetics at relatively low levels (< 70%) of resin conversion.

Mordenite-incorporated PVA-PSSA membranes as electrolytes for DMFCs

Composite membranes with mordenite (MOR) incorporated in poly vinyl alcohol (PVA)–polystyrene sulfonic acid (PSSA) blend tailored with varying degree of sulfonation are reported. Such a membrane comprises a dispersed phase of mordenite and a continuous phase of the polymer that help tuning the flow of methanol and water across it. The membranes on prolonged testing in a direct methanol fuel cell (DMFC) exhibit mitigated methanol cross-over from anode to the cathode. The membranes have been tested for their sorption behaviour, ion-exchange capacity, electrochemical selectivity and mechanical strength as also characterized by Fourier transform infrared spectroscopy and thermogravimetric analysis. Water release kinetics has been measured by magnetic resonance imaging (NMR imaging) and is found to be in agreement with the sorption data. Similarly, methanol release kinetics studied by volume-localized NMR spectroscopy (point resolved spectroscopy, PRESS) clearly demonstrates that the dispersion of mordenite in PVA–PSSA retards the methanol release kinetics considerably. A peak power-density of 74 mW/cm2 is achieved for the DMFC using a PVA–PSSA membrane electrolyte with 50% degree of sulfonation and 10 wt.% dispersed mordenite phase. A methanol cross-over current as low as 7.5 mA/cm2 with 2 M methanol feed at the DMFC anode is observed while using the optimized composite membrane as electrolyte in the DMFC, which is about 60% and 46% lower than Nafion-117 and PVA–PSSA membranes, respectively, when tested under identical conditions.