Photochemistry has revolutionized the field of polymer–biomacromolecule conjugation. Ligation reactions necessitate biologically benign conditions, and photons have a significant energy advantage over what is available thermally at ambient temperature, allowing for rapid and unique reactivity. Photochemical reactions also afford many degrees of control, specifically, spatio-temporal control, light source tunability, and increased oxygen tolerance. Light-initiated polymerizations, in particular photo-atom-transfer radical polymerization (photo-ATRP) and photoinduced electron/energy transfer reversible addition–fragmentation chain transfer polymerization (PET-RAFT), have been used for grafting from proteins, DNA, and cells. Additionally, the spatio-temporal control inherent to light-mediated chemistry has been utilized for grafting biomolecules to hydrogel networks for many applications, such as 3-D cell culture. While photopolymerization has clear advantages, there are factors that require careful consideration in order to obtain optimal control. These factors include the photocatalyst system, light intensity, and wavelength. This Perspective aims to discuss recent advances of photochemistry for polymer biomacromolecule conjugation and potential considerations while tailoring these systems.
This content will become publicly available on September 7, 2023
PET-RAFT Increases Uniformity in Polymer Networks
Photoinduced electron/energy transfer (PET)-reversible addition–fragmentation chain transfer polymerization (RAFT) and conventional photoinitiated RAFT were used to synthesize polymer networks. In this study, two different metal catalysts, namely, tris[2-phenylpyridinato-C2,N]iridium(III) (Ir(ppy)3) and zinc tetraphenylporphyrin (ZnTPP), were selected to generate two different catalytic pathways, one with Ir(ppy)3 proceeding through an energy-transfer pathway and one with ZnTPP proceeding through an electron-transfer pathway. These PET-RAFT systems were contrasted against a conventional photoinitated RAFT process. Mechanically robust materials were generated. Using bulk swelling ratios and degradable cross-linkers, the homogeneity of the networks was evaluated. Especially at high primary chain length and cross-link density, the PET-RAFT systems generated more uniform networks than those made by conventional RAFT, with the electron transfer-based ZnTPP giving superior results to those of Ir(ppy)3. The ability to deactivate radicals either by RAFT exchange or reversible coupling in PET RAFT was proposed as the mechanism that gave better control in PET-RAFT systems.
- Publication Date:
- NSF-PAR ID:
- 10355021
- Journal Name:
- ACS Macro Letters
- Volume:
- 11
- Page Range or eLocation-ID:
- 1156 to 1161
- ISSN:
- 2161-1653
- Sponsoring Org:
- National Science Foundation
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