While controlled radical polymerisation (CRP) techniques have enabled the preparation of complex and well-defined macromolecules, the need to remove oxygen in these reactions limits minimum reaction volumes, concentrations, and reaction setup, and makes the synthesis of large polymer libraries extremely laborious. To circumvent these problems we have recently developed several methods for conducting controlled radical polymerisations in the presence of oxygen,[1] through the use of an enzyme,[1-3] photo-dye,[4] or photo-catalyst,[5-6] (Fig. 1). With such systems, CRPs can be conducted in low volume in microtiter plates (&lt;40 µL), without any degassing, across a range of monomer families and molecular weights. Block extensions can be performed in a single well without any purification by simple addition of the subsequent monomer, and complex star polymers can be prepared either via polymerisation from multi-arm RAFT agents or via an arm first approach. In the case of our ZnTPP system, conversion can even be monitored spectroscopically during polymerisation.[6] We have been applying these techniques to enable the use of polymerisation as an amplification mechanism in biosensing,[7] and in the design of biomaterials through high throughput synthesis and screening of structure-activity relationships.[6]

Oxygen tolerant polymerisation for the design of biomaterials

2019 Spring National Meeting

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