Engineering Noncovalent Molecular Interactions during Polymerization for Tunable Polyampholyte Properties

Conventional free radical polymerization is a prevalent synthesis technique, yet it faces limitations in achieving precisely-controlled copolymers with emergent properties due to the statistical nature and lack of control over noncovalent interactions. This study addresses these challenges by developing a methodology that enables the precise tuning of noncovalent interactions during polymerization through the use of vapor-phase comonomers within a reduced-pressure environment. Utilizing initiated CVD (iCVD), polyampholyte copolymers, which are conventionally difficult to control in terms of composition and solubility, were synthesized with tailored noncovalent interactions. By designing vapor-phase molecular complexes guided by quantum chemical calculations, we demonstrated the synthesis of polyampholytes with a broad range of noncovalent interaction strengths. These interactions altered the hydrophilicity and hydrophobicity of polyampholytes beyond those of the homopolymers. Critically, these tuned interactions significantly influenced biofilm formation by common bacteria, providing a pathway to polyampholyte materials with enhanced or reduced biofilm growth, ranging from 5% to 205% of those grown on homopolymers for applications in engineered living materials or antifouling coatings. This research elucidates a scalable, cost-effective approach to designing functional materials with tailored emergent properties, creating new possibilities for applications across varied sectors, from filtration to biomaterials.