Automation-Assisted Photoinduced Atom Transfer Radical Polymerization

In short

ATRP is one of the workhorse reactions for making polymers with controlled length and composition, but it has historically needed inert, oxygen-free conditions, which rules out running it in an open well plate on a robot. Oxygen-tolerant chemistry removes that constraint. This paper puts photo-ATRP onto an automated liquid-handling platform and uses it to screen reaction components at a scale that is impractical by hand, including for methyl methacrylate, a monomer that propagates slowly enough to be genuinely awkward to optimise.

Why it matters

• Extends the group's automated platform from PET-RAFT and Enz-RAFT to ATRP, so a third major RDRP chemistry becomes accessible to high-throughput screening.
• Produces practical guidance on ligand and initiator selection for kinetically difficult monomers such as methyl methacrylate.
• Ships a Python package for experimental planning, so the workflow is reproducible outside the originating lab.

Abstract

Oxygen-tolerant reversible-deactivation radical polymerizations (RDRP) now allow many of these reactions to proceed in open labware, such as well plates. This enables the high-throughput synthesis of tailored polymers and lowers the knowledge barrier required to obtain these materials. Building on our previous work automating photoinduced electron/energy transfer reversible addition–fragmentation chain transfer (PET–RAFT) and enzyme-assisted RAFT (Enz-RAFT) polymerization, we now introduce automated atom transfer radical polymerization (ATRP). Here, we demonstrate the potential of this platform for the high-throughput optimization of ATRP chemistry. Furthermore, we demonstrate that this workflow can help provide insights into the selection of reaction components, such as ligands and initiators, for the polymerization of kinetically difficult monomers such as methyl methacrylate with smaller rates of propagation than acrylates. This coupling paves the way for data-driven optimization of ATRP reactions, accelerated by the generation of high-throughput data sets. To facilitate the integration of robotics for high-throughput applications in polymer synthesis and optimization of photo-ATRP, we have made a Python package available to assist with experimental planning.

Published abstract, reproduced from the version of record.

Keywords

• ATRP
• photo-ATRP
• laboratory automation
• high-throughput polymer synthesis
• oxygen tolerance
• reversible-deactivation radical polymerization

Cite this paper

Ramirez, C., Ahmed, E., Mare, E. D., Pineiro-Goncalves, M., Maroulis, A., Mulay, P., Radford, D. C. & Gormley, A. J. (2026). Automation-Assisted Photoinduced Atom Transfer Radical Polymerization. ACS Polymers Au, 6(1), 181-193. https://doi.org/10.1021/acspolymersau.5c00067

@article{ahmed2026automation,
  title   = {Automation-Assisted Photoinduced Atom Transfer Radical Polymerization},
  author  = {Ramirez, Cesar and Ahmed, Eman and Mare, Elena Di and Pineiro-Goncalves, Maria and Maroulis, Apostolos and Mulay, Prajakatta and Radford, D. Christopher and Gormley, Adam J.},
  journal = {ACS Polymers Au},
  volume  = {6},
  number  = {1},
  pages   = {181-193},
  year    = {2026},
  doi     = {10.1021/acspolymersau.5c00067}
}