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Substrate-initiated synthesis of cell-penetrating poly(disulfide)s.

ABSTRACT: Lessons from surface-initiated polymerization are applied to grow cell-penetrating poly(disulfide)s directly on substrates of free choice. Reductive depolymerization after cellular uptake should then release the native substrates and minimize toxicity. In the presence of thiolated substrates, propagators containing a strained disulfide from asparagusic or, preferably, lipoic acid and a guanidinium cation polymerize into poly(disulfide)s in less than 5 min at room temperature at pH 7. Substrate-initiated polymerization of cationic poly(disulfide)s and their depolymerization with dithiothreitol causes the appearance and disappearance of transport activity in fluorogenic vesicles. The same process is further characterized by gel-permeation chromatography and fluorescence resonance energy transfer.

SUBMITTER: Bang EK

PROVIDER: S-EPMC4601153 | biostudies-literature | 2013 Feb

REPOSITORIES: biostudies-literature

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Substrate-initiated synthesis of cell-penetrating poly(disulfide)s.

Bang Eun-Kyoung EK Gasparini Giulio G Molinard Guillaume G Roux Aurélien A Sakai Naomi N Matile Stefan S

Journal of the American Chemical Society 20130204 6

Lessons from surface-initiated polymerization are applied to grow cell-penetrating poly(disulfide)s directly on substrates of free choice. Reductive depolymerization after cellular uptake should then release the native substrates and minimize toxicity. In the presence of thiolated substrates, propagators containing a strained disulfide from asparagusic or, preferably, lipoic acid and a guanidinium cation polymerize into poly(disulfide)s in less than 5 min at room temperature at pH 7. Substrate-i ...[more]

PMID: 23363440

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