Conformation and gas permeability of poly(α‐amino acid) membranes

The permeability of some poly(ϵ-amino acid) (PAA) membranes like such of poly(N,δ-carbobenzoxy-L-lysine) (PCBL), poly(N,δ-carbobenzoxy-L-ornithine) (PCBO) as well as of copolymers of L-lysine and carbobenzoxy-L-lysine to oxygen and carbon dioxide were determined at different water content especially with regard to their use for artificial lungs. The conformations of these polymer membranes were studied by means of IR-spectra and X-ray diffraction. The results on the diffusion coefficient obtained for PCBL and PCBO were analysed in terms of Eyring's theory. They suggest that the microvoids in the interstices between the α-helices, assumed on the basis of X-ray analyses, play an important role, especially below the glass transition temperature Tg of the side-chains. This seems also to contribute partly to the diffusion of gas through the membrane even above Tg and results in an abnormally high “apparent activation energy” of diffusion in the wet state below Tg. It was found that the permeability of the membrane of partially decarbobenzoxylated PCBL for oxygen in a certain temperature range is higher than that for carbon dioxide. This has never been observed for any other synthetic polymer, because usually carbon dioxide has a higher solubility in these materials than oxygen. In the case of the partially decarbobenzoxylated PCBL membranes, however, the diffusion coefficient of carbon dioxide, and therefore the permeation of this gas, decreases much more than that of oxygen with increasing decarbobenzoxylation accompanied by the formation of β-structure and concomitantly the formation of intermolecular hydrogen bonds. Obviously, this phenomenon may be responsible for the permselectivity of these membranes for oxygen compared with carbon dioxide.