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Alternating Sulfone Copolymers Depolymerize in Response to Both Chemical and Mechanical Stimuli.

ABSTRACT: This work describes the depolymerization of poly(vinyl acetate-alt-sulfur dioxide) (PVAS) as initiated by chemical and mechanical stimuli. In recent years, macromolecules that are able to depolymerize in response to specific stimuli have been highly sought because of their ability to amplify signal for sensing and drug delivery. Examples include self-immolative polymers from alkoxyphenol derivatives and polyaldehydes. We show here that alternating copolymers of sulfur dioxide and vinyl acetate are able to undergo similar depolymerization into their monomer components in response to various chemical and mechanical stimuli. Certain vinyl monomers such as vinyl acetate are able to polymerize with sulfur dioxide in a perfectly alternating manner, and the resulting copolymer possesses a low ceiling temperature. We show that this polymer is able to break down into its monomer components when subjected to UV/acetone, various Reactive Oxygen Species (ROS), and ultrasonication. In the case of UV, the acetone reacted via a Norrish reaction to produce free radicals that caused clean monomer production. For ROS, the polymer showed reactivity to both oxidizing and radical-containing ROS. Through kinetic studies, these polymers were shown to proceed via a two-part, first-order kinetic model with a fast initiation phase and a slow depolymerization phase. Finally, the polymers were subjected to probe ultrasonication, and depolymerization occurred as well. Most tellingly, the polymer again showed a fast initiation step and continued to depolymerize even after ultrasonication stopped. This class of polymers shows potential for drug delivery in response to both endogenous chemical and externally-applied mechanical cues.

SUBMITTER: Kumar K

PROVIDER: S-EPMC5417697 | biostudies-literature | 2015 Sep

REPOSITORIES: biostudies-literature

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Alternating Sulfone Copolymers Depolymerize in Response to Both Chemical and Mechanical Stimuli.

Kumar Kaushlendra K Goodwin Andrew P AP

ACS macro letters 20150813 9

This work describes the depolymerization of poly(vinyl acetate-<i>alt</i>-sulfur dioxide) (PVAS) as initiated by chemical and mechanical stimuli. In recent years, macromolecules that are able to depolymerize in response to specific stimuli have been highly sought because of their ability to amplify signal for sensing and drug delivery. Examples include self-immolative polymers from alkoxyphenol derivatives and polyaldehydes. We show here that alternating copolymers of sulfur dioxide and vinyl ac ...[more]

PMID: 28480129

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Project description:The importance of noncovalent interactions in the realm of biological materials continues to inspire efforts to create artificial supramolecular polymeric architectures. These types of self-assembled materials hold great promise as environmentally stimuli-responsive materials because they are capable of adjusting their various structural parameters, such as chain length, architecture, conformation, and dynamics, to new surrounding environments upon exposure to appropriate external stimuli. Nevertheless, in spite of considerable advances in the area of responsive materials, it has proved challenging to create synthetic self-assembled materials that respond to highly disparate analytes and whose environmentally induced changes in structure can be followed directly through both various spectroscopic and X-ray diffraction analyses. Herein, we report a new set of artificial self-assembled materials obtained by simply mixing two appropriately chosen, heterocomplementary macrocyclic receptors, namely a tetrathiafulvalene-functionalized calix[4]pyrrole and a bis(dinitrophenyl)-meso-substituted calix[4]pyrrole. The resulting polymeric materials, stabilized by combination of donor-acceptor and hydrogen bonding interactions, undergo dynamic, reversible dual guest-dependent structural transformations upon exposure to two very different types of external chemical inputs, namely chloride anion and trinitrobenzene. The structure and dynamics of the copolymers and their analyte-dependent responsive behavior was established via single crystal X-ray crystallography, SEM, heterocomplementary isodesmic analysis, 1- and 2D NMR, and dynamic light scattering spectroscopies. Our results demonstrate the benefit of using designed heterocomplementary interactions of two functional macrocyclic receptors to create synthetic, self-assembled materials for the development of "smart" sensory materials that mimic the key biological attributes of multianalyte recognition and substrate-dependent multisignaling.

Dataset Information

Alternating Sulfone Copolymers Depolymerize in Response to Both Chemical and Mechanical Stimuli.

Publications

Alternating Sulfone Copolymers Depolymerize in Response to Both Chemical and Mechanical Stimuli.

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