Substrate-initiated synthesis of cell-penetrating poly(disulfide)s.
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.
School of Chemistry and Biochemistry, University of Geneva, Geneva, Switzerland.
Eun-Kyoung
EK
Bang
School of Chemistry and Biochemistry, University of Geneva, Geneva, Switzerland.
Giulio
G
Gasparini
School of Chemistry and Biochemistry, University of Geneva, Geneva, Switzerland.
Guillaume
G
Molinard
School of Chemistry and Biochemistry, University of Geneva, Geneva, Switzerland.
Aurélien
A
Roux
School of Chemistry and Biochemistry, University of Geneva, Geneva, Switzerland.
Naomi
N
Sakai
School of Chemistry and Biochemistry, University of Geneva, Geneva, Switzerland.
Stefan
S
Matile
D004220:Disulfides / Q000138:chemical synthesis* / Q000737:chemistry; D031541:Fluorescence Resonance Energy Transfer; D006863:Hydrogen-Ion Concentration; D015394:Molecular Structure; D058105:Polymerization; D011108:Polymers / Q000138:chemical synthesis* / Q000737:chemistry; D013696:Temperature
D004220:Disulfides; D011108:Polymers