FROM MECHANOCHEMISTRY TO BIOCONTAINMENT: ENGINEERING FUNCTIONAL COMPLEXITY IN 3D PRINTED POLYMER NETWORKS

Abstract

Light-based 3D printing has expanded the ways in which we think about and can fabricate new objects, yet the performance and functional versatility of 3D printed polymer networks remains constrained by classical trade-offs between mechanical properties and application requirements. This necessitates advancements in material technology to match the capabilities of this emerging manufacturing method. This dissertation spans molecular mechanochemistry, soft-matter fracture mechanics, and 3D printing through molecular and macromolecular engineering strategies. Integrating force-responsive motifs and catalytic functionality into photocurable network architectures across three complementary systems enables tunable, tailorable properties and function. First, cyclobutane-based mechanophores are integrated as scissile crosslinks in 3D-printed elastomers, enhancing fracture energy and tear resistance without sacrificing elastic modulus. Second, globular proteins are harnessed for their hidden length, entraining entropic energy dissipation that blunts crack propagation. These biohybrid network strategies are then extended to engineered living materials through 3D printing of core-shell bioreactor capsule. An outer shell functionalized with recombinant human lysozyme creates a redundant, physico-biochemical barrier that combines physical encapsulation from the synthetic polymer network with contact-mediated antimicrobial activity from the enzyme, preventing cell escape from these bioreactors for over 50 days. Together, these systems establish a design framework for resilient, multifunctional, and biologically active polymer networks.