J. Hodak et al., LAYER-BY-LAYER SELF-ASSEMBLY OF GLUCOSE-OXIDASE WITH A POLY(ALLYLAMINE)FERROCENE REDOX MEDIATOR, Langmuir, 13(10), 1997, pp. 2708-2716
We report the redox mediation of glucose oxidase (GOx) in a self-assem
bled structure of cationic poly(allylamine) modified by ferrocene (PAA
-Fc) and anionic GOx deposited electrostatically layer-by-layer on neg
atively charged alkanethiol-modified Au surfaces. Successive PAA-Fc an
d GOx layers were deposited by alternate immersion of the thiol-modifi
ed Au in the respective polyelectrolyte and enzyme solutions. The upta
ke of thiol, redox polymer, and GOx on the surface was monitored by qu
artz crystal microbalance. Cyclic voltammetry shows nearly ideal surfa
ce waves of ferrocene in the polymer with charge independent of sweep
rate; the redox surface concentration was obtained from integration of
the ferrocene/ferricinium voltammetric peaks. The redox charge increa
ses in step with the number of PAA-Be layers deposited. Enzyme catalys
is for the oxidation of beta-D-glucose was achieved with a multilayer
PAA-Fc/GOx assembly, with each GOx layer contributing equally to the c
atalytic response. Only a small fraction of the active assembled GOx m
olecules are ''electrically wired'' by the ferrocene polymer although
all of the enzyme could be oxidized by soluble ferrocenesulfonate when
added to solution.