Journal
BIOMACROMOLECULES
Volume 20, Issue 8, Pages 3200-3210Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.biomac.9b00892
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Funding
- National Science Foundation [DMR-1066116, DMR-1807127]
- P. Roy Vagelos Chair at the University of Pennsylvania
- Spanish Ministerio de Ciencia, Innovacion y Universidades [MAT2017-82669-R, BES-2015-072662]
- Government of Catalonia
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The use of stimuli-cleavable difunctional initiators containing a discrete single-type cleavable junction represents a general strategy to prepare mid-chain-degradable vinylic polymers. Here, we present a series of alpha-haloester-type programmed initiators encoding multiple single-type and dual-type cleavable junctions. Multiple single-cleavage groups increase the cleavage rate, whereas double-dual sites provide access to multiple mechanisms for cleavage. Single-electron transfer living radical polymerization was employed to generate well-defined mid-chain-cleavable poly(methyl acrylate)s designed with low-pH, low-pH/reduction, or low-pH/UV light cleavable linkages. Kinetic studies demonstrated that the polymerizations are living when using various catalytic Cu(0) sources (wire and powder), ligands (Me-6-TREN and TREN), and solvent sources (homogeneous and programmed biphasic). Moreover, structural analyses by NMR and matrix-assisted laser desorption/ionization-time-of-flight confirmed the near-perfect chain-end functionality of these stimuli-cleavable polymers derived from programmed initiators. A rigorous gel permeation chromatography study demonstrated that the combination of multiple acetal, disulfide, or 2-nitroresorcinol-derived acetal junctions offer attractive possibilities in terms of selective cleavage and orthogonal degradation.
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