Chemical and Biomolecular Engineering - Research Publications
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ItemFenton-RAFT Polymerization: An "On-Demand" Chain-Growth Method(WILEY-V C H VERLAG GMBH, 2017-05-29)Fine control over the architecture and/or microstructure of synthetic polymers is fast becoming a reality owing to the development of efficient and versatile polymerization techniques and conjugation reactions. However, the transition of these syntheses to automated, programmable, and high-throughput operating systems is a challenging step needed to translate the vast potential of precision polymers into machine-programmable polymers for biological and functional applications. Chain-growth polymerizations are particularly appealing for their ability to form structurally and chemically well-defined macromolecules through living/controlled polymerization techniques. Even using the latest polymerization technologies, the macromolecular engineering of complex functional materials often requires multi-step syntheses and purification of intermediates, and results in sub-optimal yields. To develop a proof-of-concept of a framework polymerization technique that is readily amenable to automation requires several key characteristics. In this study, a new approach is described that is believed to meet these requirements, thus opening avenues toward automated polymer synthesis.
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ItemFenton-Chemistry-Mediated Radical Polymerization(Wiley, 2019-09-01)In this review, the power of a classical chemical reaction, the Fenton reaction for initiating radical polymerizations, is demonstrated. The reaction between the Fenton reagents (i.e., Fe2+ and H2O2) generates highly reactive hydroxyl radicals, which can act as radical initiators for the polymerization of vinyl monomers. Since the Fenton reaction is fast, easy to set up, cheap, and biocompatible, this unique chemistry is widely employed in various polymer synthesis studies via free radical polymerization or reversible addition–fragmentation chain transfer polymerization, and is utilized in a wide range of applications, such as the fabrication of biomaterials, hydrogels, and core‐shell particles. Biologically activated Fenton‐mediated radical polymerization, which can be performed in aerobic environments, are particularly useful for applications in biomedical systems.
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ItemBlood-Catalyzed RAFT Polymerization(WILEY-V C H VERLAG GMBH, 2018-08-06)The use of hemoglobin (Hb) contained within red blood cells to drive a controlled radical polymerization via a reversible addition-fragmentation chain transfer (RAFT) process is reported for the first time. No pre-treatment of the Hb or cells was required prior to their use as polymerization catalysts, indicating the potential for synthetic engineering in complex biological microenvironments without the need for ex vivo techniques. Owing to the naturally occurring prevalence of the reagents employed in the catalytic system (Hb and hydrogen peroxide), this approach may facilitate the development of new strategies for in vivo cell engineering with synthetic macromolecules.