In this study, we
compare poly(glycerol monomethacrylate) (PGMA)
of different chain lengths and architectures (linear and two-arm)
with poly(poly(ethylene glycol) methyl ether methacrylate) (PPEGMA)
as an alternative polymer platform for the synthesis of a new generation
of protein–polymer conjugates. Mono- and two-arm functional
atom-transfer radical polymerization (ATRP) initiators were designed
and selectively attached to lysozyme at the N-terminus via reductive
amination. Site-specific, grafting from activator regenerated by electron
transfer (ARGET) ATRP was carried out in phosphate buffer, and the
reaction parameters were optimized to obtain polymer conjugates with
predetermined molar mass and topology. The activity preservation under
proteolytic and high-temperature conditions showed a clear dependence
on the structure of the repeating unit and on the macromolecular architecture.
These results highlighted the potential of PGMA as a poly(ethylene
glycol) (PEG) alternative for the half-life extension of biotherapeutics.
Moreover, this synthetic approach may inspire the design of a new
class of protein–polymer conjugates through an optimal combination
of macromolecular composition and topology.
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