Enzymatic chain scission kinetics of poly(epsilon-caprolactone) monolayers.

The hydrolytic and enzymatic degradation behavior of poly(epsilon-caprolactone) (PCL) is investigated using the Langmuir monolayer technique, and an improved data acquisition and data reduction procedure is presented. Hydrolytic and enzymatic monolayer degradation experiments of PCL with various molecular weights by Pseudomonas cepacia lipase have been carried out to analyze the influence of subphase pH, subphase temperature, enzyme concentration, and the packing density of polymer chains on the degradation kinetics. The enzymatic monolayer degradation results in an exponential increase in the number of dissolved degradation fragments with increasing degradation time, which confirms random chain scission to be the dominant scission mechanism. The increase in the enzymatic scission rate constant with decreasing initial average molecular weight of the polymers is assigned to the influence of the area density of polar terminal groups on the substrate-enzyme complex formation.

Auto-oscillation of surface tension.

Long-time auto-oscillation of the surface tension can evolve when in an aqueous system a diethyl phthalate droplet is placed under the free water surface. The experimental conditions for development of surface tension auto-oscillations are described. Based on a theoretical analysis the mechanism of these auto-oscillations is proposed. The mechanism of the auto-oscillations results from a switching between diffusion and convection transfer of diethyl phthalate in the solution. A periodic Marangoni flow on the water surface resulting from a surface layer instability is discussed. The solubility of the amphiphile in the water and its surface activity are the main characteristics that determine the system behavior.

Considerations on developmental aspects of biocompatible dialysis membranes.

Modern strategies in developing new polymers for dialysis membranes aim to improve their blood compatibility. To achieve such a goal, two approaches have been successfully applied: existing cellulosic polymers were modified, either by introducing functional groups through ester or ether bonds, by mixing synthetic polymers with bulk additives, or by using copolymerization techniques. As a detailed example, the first synthetically modified cellulose membrane, Hemophan, was prepared by substituting some hydrogen atoms in the cellulosic glucose unit by diethyl-amino-ethyl groups with the modification having a considerable impact on the membrane's hemocompatibility. It is further known that the hemocompatibility of hydrophobic synthetic membranes is improved by rendering these materials partially hydrophilic. We tested the hypothesis, whether the hemocompatibility of a material, which is hydrophilic per se, such as unmodified cellulose, is changed after the introduction of hydrophobic substituents. For this purpose, the number and nature of substituents have been systematically varied in order to alter surface properties, and these variations have been subsequently related to blood compatibility parameters. As expected, thrombin generation as well as complement- and cell-activation depend on the number and nature of the substituents whereby some of the substituents show a very narrow optimum if their hemocompatibility is related to the degree of substitution. Changes in hemocompatibility can be followed by physical methods, such as surface angle analyses and zeta potential determinations. Data show that alterations in the lipophilic/hydrophilic balance on the polymer surface may explain substituent-related changes in polymer hemocompatibility.(ABSTRACT TRUNCATED AT 250 WORDS)