Proximity-Induced Cooperative Polymerization in "hinged" Helical Polypeptides

Chongyi Chen, Hailin Fu, Ryan Baumgartner, Ziyuan Song, Yao Lin, Jianjun Cheng

Research output: Contribution to journalArticle

Abstract

Cooperative interactions and transitions are among the most important strategies utilized by biological systems to regulate a variety of physical and chemical processes. We report herein an auto-accelerated, rapid cooperative polymerization of N-carboxyanhydrides (NCAs) with initiators structurally as simple as linear aliphatic diamines for the synthesis of polypeptides. The polymerization initiated by diamines proceeds via the formation of "hinged" polypeptides, which are two blocks of helical chains connected head-to-head by the diamine molecules in the polymerization solution. The reactions follow a two-stage, cooperative polymerization kinetic; the cooperative interactions between the macrodipoles of the two hinged helical polypeptides dramatically accelerate the polymerization. Compared to the NCA polymerization initiated by the hexylamine (CH3(CH2)5NH2), the chain propagation rate of the NCA polymerization is increased by more than 600 times when initiated by its diamine analogue (1,6-diaminohexane, NH2(CH2)6NH2). This proximity-induced cooperative polymerization showcases the single helix as a remarkable cooperativity-enabling motif in synthetic chemistry.

Original languageEnglish (US)
Pages (from-to)8680-8683
Number of pages4
JournalJournal of the American Chemical Society
Volume141
Issue number22
DOIs
StatePublished - Jun 5 2019

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Polypeptides
polymerization
Polymerization
Peptides
Diamines
1,6-diaminohexane
Chemical Phenomena
Physical Phenomena
Biological systems
chemical process
kinetics
Molecules
Kinetics

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Proximity-Induced Cooperative Polymerization in "hinged" Helical Polypeptides. / Chen, Chongyi; Fu, Hailin; Baumgartner, Ryan; Song, Ziyuan; Lin, Yao; Cheng, Jianjun.

In: Journal of the American Chemical Society, Vol. 141, No. 22, 05.06.2019, p. 8680-8683.

Research output: Contribution to journalArticle

Chen, Chongyi ; Fu, Hailin ; Baumgartner, Ryan ; Song, Ziyuan ; Lin, Yao ; Cheng, Jianjun. / Proximity-Induced Cooperative Polymerization in "hinged" Helical Polypeptides. In: Journal of the American Chemical Society. 2019 ; Vol. 141, No. 22. pp. 8680-8683.
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