Triple G–C–T Base-Coded Nucleobase Self-Assembling Monomers Featuring Polymerizable Groups for 3D Printing

Self-assembling monomers (SAMs) offer a versatile strategy for enhancing the performance of photoresins in Digital Light Processing (DLP) 3D printing. In this work, we report the design and synthesis of two photoprintable, nucleobase-inspired SAMs featuring a triple G–C–T base-coded hydrogen-bonding motif. This SAM was formulated using 2-hydroxyethyl acrylate (2-HEA), 1,6-hexanediol diacrylate (HDDA), and diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO) to prepare UV-curable resins suitable for high-resolution DLP printing. Remarkably, the printed samples exhibited supramolecular self-assembly, facilitated by dynamic hydrogen bonding, demonstrating a notable enhancement in thermal and mechanical performance when compared to the control sample. Thermal properties evaluated by a differential scanning calorimeter revealed an increase in the glass transition temperature (Tg) from 15 °C to 54 °C for SAM-incorporated printed materials. Mechanical testing demonstrated a >200% increase in toughness and >150% improvement in tensile strength relative to the unmodified resin while maintaining or exceeding the original elongation at break (up to ∼74%). Variable-temperature FTIR spectroscopy confirmed the presence of thermally responsive supramolecular interactions. Notably, self-healing behavior was observed in both GCT-A 15 wt % and GCT-S 15 wt % formulations, indicating partial recovery of mechanical integrity under mild thermal conditions due to reversible hydrogen bonding. These findings demonstrate the potential of SAMs as functional additives for developing robust, thermally stable, and self-healing DLP-printed materials for advanced engineering applications.