A series
of polyelectrolyte multilayers (PEMs) has been fabricated
using polyanions and polycations that have repeat units (i) similar
in structure and composition (matched), (ii) partially similar in
structure and composition (semimatched), and (iii) very different
in structure and composition (mismatched). The primary aim of this
investigation was to determine whether the matching of the polyelectrolytes
can significantly influence the permeability properties of hyperthin
PEMs. While matching, per se, was not found to be a key factor in
defining membrane permeability, large differences in permeability
were observed (the permeances of N2 varied by a factor
of 20), which were correlated with the concentration of pendant aryl
groups present, i.e., the greater the concentration of these groups,
the higher the permeability. Analysis by AFM indentation measurements
further revealed that high-permeability PEMs tend to be more compliant
than low-permeability PEMs. These findings underscore the need for
considering a broad range of polyelectrolyte combinations when optimizing
a particular functional property of PEMs