Facile
regulation and enhancing of the performance of bioimmobilization
materials is a key factor for their applications for biosensing, biocatalysis,
bioreactor, and so on. Here, we propose a method of combined polymerizations
of chemical oxidation and metal organic coordination to develop enhanced
bioimmobilization matrices for high performance biosensing. Being
different from conventional methods that are based on sole polymerization,
the new method elaborated chemical oxidation to one-pot obtain oligomers
as ligands for metal–organic coordination polymerization. Two
kinds of thiol that could be chemically oxidized by H2O2 and be coordinated with NaAuCl4 were adopted as
monomers. Glucose oxidase was adopted as the representative biomolecule.
Chemical oxidation was proved to be efficient to lengthen monomers
to produce oligomers (ligands) with different lengths by adjusting
the concentrations of monomers and oxidant, as well as reaction time.
This dynamic prelengthening process not only endows the coexisting
biomolecules with active and protective oligomers shell to significantly
enhance the immobilization efficiency but also regulates the structure
of metal–organic coordination polymer. As crucial factors of
immobilization, the entrapment ratio of enzyme and mass-transfer efficiency
all achieved obvious increases compared with those based on sole chemical
oxidation polymerization or metal–organic coordination polymerization;
the entrapment ratio even reached an extreme value of 100%. Therefore,
the biosensing performance was greatly promoted with sensitivities
being among the best of those reported analogues. The biosensors also
exhibited satisfactory selectivity, stability, and feasibility for
blood serum samples. This method may provide a universal strategy
for regulating and enhancing performance of ligand-constructed polymers
and their composites for entrapment-based applications.