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Capsules based on sodium alginate (SA) and sodium cellulose sulphate (SCS), have been prepared using polyvinylamines (PVAm) of varying intrinsic viscosities. The resulting capsules are relatively dense in nature, revealing a bursting force which is four times that observed for the classical SA/SCS/polymethylene-co-guanidine chemistry. Molar mass cutoffs were typically in the 10-70 kDa range. A mechanistic study was carried out where the reaction time, ionic strength and pH of the reaction mixture, as well as the stoichiometry of the polyanion blend and the PVAm molar mass were varied. It is postulated that both the SA-PVAm and the SCS-PVAm binary interactions contribute to the mechanical properties and the permeability of the resulting capsules. The polyvinylamine-based chemistry offers interesting alternatives to the PMCG system in that it provides a means to produce capsules at low, or zero, ionic strengths. Subtle changes in the pH, or the SA:SCS ratio, can also be used to tune the bursting force quite sensitively. The most appropriate capsules, for transplantation, would likely be formed at polyanion levels of 1.2 wt% with a PVAm molar mass below 17 kDa.

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Capsules have been prepared based on a polyanion blend of sodium alginate and sodium cellulose sulphate, gelled in the presence of calcium chloride and sodium chloride. In a second step a membrane was formed via the addition of polymethylene-co-guanidine (PMCG), an oligocation. A mechanistic study examined the influences of pH, ionic strength, gelation and reaction times as well as the molar mass of the polyanions on the transport and mechanical properties. The ratio of alginate-to-cellulose sulphate in the polyanion blend was also varied and it was found that both mechanical resistance to compression as well as the pore size of the membrane decreased as the percentage of cellulose sulphate was reduced. The maximum mechanical strength was observed to correspond to the minimum in viscosity of the polyanion blend with, for low NaCl levels, a 3:1 alginate:cellulose sulphate level providing the largest resistance to deformation. The ability to decouple the molar mass cut-off and mechanical resistance is viewed as an important advantage of alginate/cellulose sulphate/PMCG capsules. Capsules were transplanted into mice to a maximum of 102 days, after which animals were sacrificed and capsules retrieved. Over 90% of the capsules were recovered from the peritoneal cavity with the mechanical properties of the explanted capsules observed to decrease as a function of implantation time, likely as a result of ion exchange. The capsules were, however, relatively free from any rejection which is a quite unusual result for cation containing systems. It is believed that the reason PMCG-based microcapsules function well in vivo is that they provide a net negative charge on the surface. Higher molar mass polycations such as poly-L-lysine provide a net positive charge, inducing inflammation.

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An innovative way to fix preformed nanocrystalline TiO(2) on low-density polyethylene film (LDPE-TiO(2)) is presented. The LDPE-TiO(2) film was able to mediate the complete photodiscoloration of Orange II using about seven times less catalyst than a TiO(2) suspension and proceeded with a photonic efficiency of approximately 0.02. The catalyst shows photostability over long operational periods during the photodiscoloration of the azo dye Orange II. The LDPE-TiO(2) catalyst leads to full dye discoloration under simulated solar light but only to a 30% TOC reduction since long-lived intermediates generated in solution seem to preclude full mineralization of the dye. Physical insight is provided into the mechanism of stabilization of the LDPE-TiO(2) composite during the photocatalytic process by X-ray photoelectron spectroscopy (XPS). The adherence of TiO(2) on LDPE is investigated by electron microscopy (EM) and atomic force microscopy (AFM). The thickness of the TiO(2) film is seen to vary between 1.25 and 1.69 microm for an unused LDPE-TiO(2) film and between 1.31 and 1.50 microm for a sample irradiated 10h during Orange II discoloration pointing out to a higher compactness of the TiO(2) film after the photocatalysis.

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The metrics used, thus far, to assess bioartificial organ function are shown to be subjective and requiring validation. Therefore, four categories of correlations are proposed based on, respectively, device, in vitro and in vivo evaluations, and clinical function. Examples are presented whereby the correlations among individual indicators are used as a means to expedite the development of immunoisolated cells. Specifically, a case study illustrating the validation of in vitro indicators of in vivo graft function for the bioartificial pancreas (microencapsulated islets) is summarized. This has revealed thresholds with respect to given metrics relating to in vivo device function, the necessity to couple bioartificial organ design with transplant site selection, as well as the lack of objectivity involved in the evaluation and establishment of hypotheses. Specific quantitative indicators illustrate the need for quality-controlled measures, for example, relating to the tolerance of microcapsule diameter and membrane thickness distributions. Qualitative indices representing fibrosis and device properties (e.g., sphericity) are also used to describe the need for in vitro experiments in the development of bioartificial organs.

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A new generation of microcapsules based on the use of oligomers which participate in polyelectrolyte complexation reactions has been developed. These freeze-thaw stable capsules have been applied as a bioartificial pancreas and have resulted in normoglycemia for periods of six months in concordant xenotransplantations. The new chemistry permits the control of permeability and mechanical properties over a wide range and can be adapted both to microcapsule and hollow fiber geometries rendering it a robust tool for encapsulation in general. Methods, and metrics, for the characterization of the mechanical properties and permeability of microcapsules are presented.

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An enzymic transesterification was carried out in a continuously operated fixed bed reactor. The reaction system consisted of immobilized alpha-chymotrypsin (E.C. 3.4.21.1) catalysing the transfer of the L-phenylalanine radical from the racemic propyl ester to 1,4-butanediol, yielding L-phenylalanine 4-hydroxybutyl ester. The desired reaction was accompanied by alcoholysis due to the presence of 1-propanol liberated during the reaction and by hydrolysis of both the propyl and the hydroxybutyl ester. The problem of shifting pH during the reaction due to ester hydrolysis was overcome by adjusting the initial pH of the substrate feed solution appropriately in order to obtain a sufficiently high buffer capacity provided by the free amino group of the esters. Thus, it was possible to work with shifting pH, an obvious disadvantage for operating reactors of low backmixing for this kind of reaction system. The overall reaction scheme was characterized by the appearance of a maximum ester yield as a function of the operating time in case of batch reactors. Surprisingly, the yield was found to become constant as a function of space-time for continuous operation due to a steeper pH drop. The maximum productivity achieved with respect to the hydroxybutyl ester was about 65 mol d-1 l-1 referred to the catalyst volume.

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The maximum concentration of alpha-cyclodextrin for the enzymatic degradation of starch is limited to about 13.5 g X 1(-1). By addition of decanol, the equilibrium of the reaction system can be shifted towards an alpha-cyclodextrin yield of 50% even at high substrate concentrations. The main variables of the decanol process--pH, temperature, substrate quality, substrate, and enzyme concentration--have been studied. The cyclodextrin-glycosyltransferase from Klebsiella pneumoniae M5 al can preferentially be employed at pH 6 to 8, temperatures of 40 to 50 degrees C and a decanol concentration of 0.1 kg-1 starch. The dextrose equivalent of starch is important with respect to the maximum achievable starch concentration, but not with respect to the reaction. Under process conditions, the rate of alpha-cyclodextrin evolution is limited by the enzymatic reaction and not by mass transfer of decanol into the aqueous phase.

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The kinetics of glucose liberation from lactose by means of the beta-glactosidase from Aspergillus niger has been studied in a wide range of the main variables. The analysis shows that the kinetic models proposed so far are not adequate. The main finding is that the reaction rate is not linearly correlated to the enzyme concentration-it increase more than proportionally. This nonlinear relationship results because this lactase can distinguish between alpha-and beta-galactose alpha-Galactose acts as competitive and anticompetitive inhibitor while beta-galactose is a competitive one. The competitive inhibition of the alpha-anomer is approximately 12 times more sever than that of the beta-anomer. The kinetics, including a simplified model for the mutarotation of galactose is given for a temperature of 50 degrees C at a pH of 3.5-the most likely conditions for the application of this lactase in acid whey treatment.