Abstract
<jats:p> Physically crosslinked supramolecular polymers provide a platform for designing material properties through non-covalent interactions. In this study, we report photocurable supramolecular complex macromonomers formed through host and guest inclusion between methacrylated poly(L-lactide)- <jats:italic toggle="yes">b</jats:italic> -poly(ethylene glycol)- <jats:italic toggle="yes">b</jats:italic> -poly(L-lactide) (PLA-PEG-PLA) triblock precursor, denoted MPL, and three different cyclodextrins (α-CD, β-CD and 2-hydroxypropyl-β-CD (HP-β-CD)). The effect of cyclodextrin type on the chemical structure, inclusion geometry, thermal behaviour, and physicochemical properties of the resulting material, as well as on their photopolymerization process, was systematically studied using FTIR spectroscopy, 1D and 2D proton NMR techniques, and differential scanning calorimetry. Molecular docking was used to visualize plausible inclusion geometries. Variation in photoinitiator type and concentration in controlling the polymerization efficiency and their cellular cytocompatibility was evaluated. The results showed that the nature of cyclodextrin affects the strength of supramolecular association and systematically influences photo-initiated polymerization kinetics, network formation, and macroscopic material properties. Overall, this work highlights the design of cyclodextrin-mediated supramolecular macromonomer materials and outlines their potential as a tunable photo-curable host-guest polymer networks. </jats:p>