Presented in this
work is the use of a molecular descriptor, termed
the α parameter, to aid in the design of a series of novel,
terpene-based, and sustainable polymers that were resistant to biofilm
formation by the model bacterial pathogen Pseudomonas
aeruginosa. To achieve this, the potential of a range
of recently reported, terpene-derived monomers to deliver biofilm
resistance when polymerized was both predicted and ranked by the application
of the α parameter to key features in their molecular structures.
These monomers were derived from commercially available terpenes (i.e., α-pinene, β-pinene, and carvone), and
the prediction of the biofilm resistance properties of the resultant
novel (meth)acrylate polymers was confirmed using a combination of
high-throughput polymerization screening (in a microarray format)
and in vitro testing. Furthermore, monomers, which
both exhibited the highest predicted biofilm anti-biofilm behavior
and required less than two synthetic stages to be generated, were
scaled-up and successfully printed using an inkjet “valve-based”
3D printer. Also, these materials were used to produce polymeric surfactants
that were successfully used in microfluidic processing to create microparticles
that possessed bio-instructive surfaces. As part of the up-scaling
process, a novel rearrangement was observed in a proposed single-step
synthesis of α-terpinyl methacrylate via methacryloxylation,
which resulted in isolation of an isobornyl–bornyl methacrylate
monomer mixture, and the resultant copolymer was also shown to be
bacterial attachment-resistant. As there has been great interest in
the current literature upon the adoption of these novel terpene-based
polymers as green replacements for petrochemical-derived plastics,
these observations have significant potential to produce new bio-resistant
coatings, packaging materials, fibers, medical devices, etc.