ORCID Profile
0000-0003-4403-5187
Current Organisation
University of Miami
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Publisher: Wiley
Date: 28-05-2023
Abstract: ortho ‐Phenylenes are one of the simplest classes of aromatic foldamers, adopting helical geometries because of aromatic stacking interactions. The folding and misfolding of ortho ‐phenylenes are slow on the NMR timescale at or below room temperature, allowing detection of folding states using 1 H NMR spectroscopy. Herein, an ortho ‐phenylene hexamer is coupled with a RAFT chain transfer agent (CTA) on each repeat unit. A variety of acrylic monomers are polymerized onto the CTA‐functionalized ortho ‐phenylene using PET‐RAFT to yield functionalized star polymers with ortho‐ phenylene cores. The steric bulk of the acrylate monomer units as well as the chain length of each arm of the star polymer is varied. 1 H NMR spectroscopy shows that the folding of the ortho ‐phenylenes do not vary, providing a robust helical core for star polymer systems.
Publisher: Springer Science and Business Media LLC
Date: 18-10-2021
Publisher: Royal Society of Chemistry (RSC)
Date: 2022
DOI: 10.1039/D2CC01223E
Abstract: Aromatic foldamer based networks are developed, where the foldamer unit acts as a molecular spring. Energy dissipation increases with the number of turns in the foldamer, consistent with mechanical unfolding of the molecular spring.
Publisher: Elsevier BV
Date: 2023
Publisher: American Chemical Society (ACS)
Date: 27-10-2023
Publisher: American Chemical Society (ACS)
Date: 22-03-2021
Publisher: American Chemical Society (ACS)
Date: 18-10-2021
DOI: 10.1021/JACS.1C08654
Abstract: Reversible addition-fragmentation chain transfer (RAFT) polymerization is one of the most powerful reversible deactivation radical polymerization (RDRP) processes. Rate retardation is prevalent in RAFT and occurs when polymerization rates deviate from ideal conventional radical polymerization kinetics. Herein, we explore beyond what was initially thought to be the culprit of rate retardation: dithiobenzoate chain transfer agents (CTA) with more active monomers (MAMs). Remarkably, polymerizations showed that rate retardation occurs in systems encompassing the use of trithiocarbonates and xanthates CTAs with varying monomeric activities. Both the simple slow fragmentation and intermediate radical termination models show that retardation of all these systems can be described by using a single relationship for a variety of monomer reactivity and CTAs, suggesting rate retardation is a universal phenomenon of varying severity, independent of CTA composition and monomeric activity level.
No related grants have been discovered for Kate Bradford.