期刊
MOLECULES
卷 27, 期 19, 页码 -出版社
MDPI
DOI: 10.3390/molecules27196292
关键词
self-immolative; electrocatalytic; depolymerization; polymer; poly(dithiothreitol); anthraquinone; disulfide; radical anion
资金
- Research Fund Denmark [9041-00096B]
We report the use of AQ center dot(-) as an electron carrier to trigger the catalytic depolymerization of pDTT polymers. The reaction is rapid and catalytic, with as little as a small amount of electrons needed for complete depolymerization. It is driven by thiyl radicals attacking disulfide bonds internally or between chains.
We report the use of electrogenerated anthraquinone radical anion (AQ center dot(-)) to trigger fast catalytic depolymerization of polymers derived from poly(dithiothreitol) (pDTT)-a self-immolative polymer (SIP) with a backbone of dithiothreitols connected with disulfide bonds and end-capped via disulfide bonds to pyridyl groups. The pDTT derivatives studied include polymers with simple thiohexyl end-caps or modified with AQ or methyl groups by Steglich esterification. All polymers were shown to be depolymerized using catalytic amounts of electrons delivered by AQ center dot(-). For pDTT, as little as 0.2 electrons per polymer chain was needed to achieve complete depolymerization. We hypothesize that the reaction proceeds with AQ center dot(-) as an electron carrier (either molecularly or as a pendant group), which transfers an electron to a disulfide bond in the polymer in a dissociative manner, generating a thiyl radical and a thiolate. The rapid and catalytic depolymerization is driven by thiyl radicals attacking other disulfide bonds internally or between pDTT chains in a chain reaction. Electrochemical triggering works as a general method for initiating depolymerization of pDTT derivatives and may likely also be used for depolymerization of other disulfide polymers.
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