![Author ORCID: We display the ORCID iD icon alongside authors names on our website to acknowledge that the ORCiD has been authenticated when entered by the user. To view the users ORCiD record click the icon. [opens in a new tab]](https://chemrxiv.org/engage/assets/public/chemrxiv/images/logos/orcid.png)
Abstract
Benzophenone-based materials remain widely used as photoinitiators for ultraviolet light-induced free radical polymerizations. Traditionally, polymerization is spatially controlled using top-down techniques such as photomasks, which produce well-defined polymeric films. In contrast, we present an alternative method for controlling polymerization by employing supramolecular materials to localize the photoinitiator. This approach uses benzophenone-functionalized dipeptides that are specifically tuned to enable supramolecular gel noodle formation, which act as structural templates. We show that polymerization of acrylate monomers around the noodles can increase the Young’s modulus by up to two orders of magnitude and produce mechanically robust structures that can be handled. The self-assembly of the supramolecular photoinitiators is also explored using viscosity and SAXS measurements, providing an understanding of why only 4BPAcFF successfully form gel noodles. Our method offers a simple yet effective technique for localizing polymerisation, enabling fine-tuning of mechanical properties and the fabrication of intricate designs such as hollow-core structures.
Supplementary materials
Title
Supporting Information
Description
The materials and methods used throughout; the synthetic pathway to the gelators; photographs of the 4BPAcFF micellar solution (Figure S1); graph of Q* against concentration (Figure S2); strain and frequency sweeps of the bulk gels (Figure S3); photographs of the gel noodles at different concentrations (Figure S4); microscope images of 4BPAcFF at different concentrations (Figure S5); NMR of a 4BPAcFF and PETA mixture during irradiation (Figure S6); NMR of a 4BPAcFF noodle mixture after irradiation (Figure S7); schematic of the polymerization process (Figure S8); photographs and microscope images of the HEA-based materials (Figure S9); force-indentation curves for 4BPAcFF (Figure S10); thermal properties of the gelators (Figure S11); FTIR of the gelators and intermediates (Figure S12); fitting parameters for SAXS (Table S1 and S2); NMR spectra (Figure S13–36);
Actions
