Poly(epsilon-caprolactone) and poly(epsilon-caprolactone)-polyvinylpyrrolidone-iodine blends as ureteral biomaterials: characterisation of mechanical and surface properties, degradation and resistance to encrustation in vitro.

This study describes the physicochemical properties and in vitro resistance to encrustation of solvent cast films composed of either poly(epsilon-caprolactone) (PCL), prepared using different ratios of high (50,000) to low (4000) (molecular weight) m.wt., or blends of PCL and the polymeric antimicrobial complex, poly(vinylpyrrolidone)-iodine (PVP-I). The incorporation of PVP-I offered antimicrobial activity to the biomaterials. Films were characterised in terms of mechanical (tensile analysis, dynamic mechanical thermal analysis) and surface properties (dynamic contact angle analysis, scanning electron microscopy), whereas degradation (at 37degreesC in PBS at pH 7.4) was determined gravimetrically. The resistance of the films to encrustation was evaluated using an in vitro encrustation model. Reductions in the ratio of high:low-m.wt. PCL significantly reduced the ultimate tensile strength, % elongation at break and the advancing contact angle of the films. These effects were attributed to alterations in the amorphous content and the more hydrophilic nature of the films. Conversely, there were no alterations in Young's modulus, the viscoelastic properties and glass-transition temperature. Incorporation of PVP-I did not affect the mechanical or rheological properties of the films, indicative of a limited interaction between the two polymers in the solid state. Manipulation of the high:low m.wt. ratio of PCL significantly altered the degradation of the films, most notably following longer immersion periods, and resistance to encrustation. Accordingly, maximum degradation and resistance to encrustation was observed with the biomaterial composed of 40:60 high:low m.wt. ratios of PCL; however, the mechanical properties of this system were considered inappropriate for clinical application. Films composed of either 50:50 or 60:40 ratio of high:low m.wt. PCL offered an appropriate compromise between physicochemical properties and resistance to encrustation. This study has highlighted the important usefulness of degradable polymer systems as ureteral biomaterials

Mycobacterium avium ssp. paratuberculosis: its incidence, heat resistance and detection in milk and dairy products

Mycobacterium avium ssp. paratuberculosis (MAP) causes Johne's disease in cattle and other ruminants and has been implicated as a possible cause of Crohn's disease in humans. The organism gains access to raw milk directly through excretion into the milk within the udder and indirectly through faecal contamination during milking. MAP has been shown to survive commercial pasteurization in naturally infected milk, even at the extended holding time of 25 s. Pasteurized milk must therefore be considered a vehicle of transmission of MAP to humans. isolation methods for MAP from milk are problematical, chiefly because of the absence of a suitable selective medium. This makes food surveillance programs and research on this topic difficult. The MAP problem can be addressed in two main ways: by devising a milk-processing strategy that ensures the death of the organism: and/or strategies at farm level to prevent access of the organism into raw milk. Much of the research to date has been devoted to determining ifa problem exists and, if so, the extent of the problem. Little has been directed at possible solutions. Given the current state of information on this topic and the potential consequences for the dairy industry research is urgently needed so that a better understanding of the risks and the efficacy of possible processing solutions can be determined.

Importance of electronegativity differences and surface structure in molecular dissociation reactions at transition metal surfaces

The dissociative adsorption of N-2 has been studied at both monatomic steps and flat regions on the surfaces of the 4d transition metals from Zr to Pd. Using density functional theory (DFT) calculations, we have determined and analyzed the trends in both straight reactivity and structure sensitivity across the periodic table. With regards to reactivity, we find that the trend in activation energy (Ea) is determined mainly by a charge transfer from the surface metal atoms to the N atoms during transition state formation, namely, the degree of ionicity of the N-surface bond at the transition state. Indeed, we find that the strength of the metal-N bond at the transition state (and therefore the trend in Ea) can be predicted by the difference in Mulliken electronegativity between the metal and N. Structure sensitivity is analyzed in terms of geometric and electronic effects. We find that the lowering of Ea due to steps is more pronounced on the right-hand side of the periodic table. It is found that for the early transition metals the geometric and electronic effects work in opposition when going from terrace to step active site. In the case of the late 4d metals, however, these effects work in combination, producing a more marked reduction in Ea.

Characterisation of the Interaction of Lactate Dehydrogenase With Tween-20 Using Isothermal Titration Calorimetry, Interfacial Rheometry and Surface Tension Measurements

In this study the nature of the interaction between Tween-20 and lactate dehydrogenase (LDH) was investigated using isothermal titration calorimetry (ITC). In addition the effects of the protein and surfactant on the interfacial properties were followed with interfacial rheology and surface tension measurements in order to understand the mechanism by which the surfactant prevents protein adsorption to the air– water interface. Comparisons were made with Tween-40 and Tween-80 in order to further investigate the mechanism. ITC measurements indicated a weak, probably hydrophobic, interaction between Tween-20 and LDH. Prevention of LDH adsorption to the air–water interface by the Tween surfactants was correlated with surface energy rather than surfactant CMC. While surface pressure appears to be the main driving force for the displacement of LDH from the air–water interface by Tween-20 a solubilisation mechanism may exist for other protein molecules. More generally the results of this study highlight the value of the use of ITC and interfacial measurements in characterising the surface behaviour of mixed surfactant and protein systems.

Phase transition and decomposition temperatures, heat capacities and viscosities of pyridinium ionic liquids

Ionic liquids are organic salts with low melting points. Many of these compounds are liquid at room temperature in their pure state. Since they have negligible vapor pressure and would not contribute to air pollution, they are being intensively investigated for a variety of applications, including as solvents for reactions and separations, as non-volatile electrolytes, and as heat transfer fluids. We present melting temperatures, glass transition temperatures, decomposition temperatures, heat capacities, and viscosities for a large series of pyridinium-based ionic liquids. For comparison, we include data for several imidazolium and quaternary ammonium salts. Many of the compounds do not crystallize, but form glasses at temperatures between 188 K and 223 K. The thermal stability is largely determined by the coordinating ability of the anion, with ionic liquids made with the least coordinating anions, like bis(trifluoromethylsulfonyl)imide, having the best thermal stability. In particular, dimethylaminopyridinium bis(trifluoromethylsulfonyl)imide salts have some of the best thermal stabilities of any ionic liquid compounds investigated to date. Heat capacities increase approximately linearly with increasing molar mass, which corresponds with increasing numbers of translational, vibrational, and rotational modes. Viscosities generally increase with increasing number and length of alkyl substituents on the cation, with the pyridinium salts typically being slightly more viscous than the equivalent imidazolium compounds. (c) 2005 Elsevier Ltd. All rights reserved.