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 language | English (US) |
|---|---|
| Pages (from-to) | 8680-8683 |
| Number of pages | 4 |
| Journal | Journal of the American Chemical Society |
| Volume | 141 |
| Issue number | 22 |
| DOIs | |
| State | Published - Jun 5 2019 |
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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 journal › Article
}
TY - JOUR
T1 - Proximity-Induced Cooperative Polymerization in "hinged" Helical Polypeptides
AU - Chen, Chongyi
AU - Fu, Hailin
AU - Baumgartner, Ryan
AU - Song, Ziyuan
AU - Lin, Yao
AU - Cheng, Jianjun
PY - 2019/6/5
Y1 - 2019/6/5
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=85066863797&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85066863797&partnerID=8YFLogxK
U2 - 10.1021/jacs.9b02298
DO - 10.1021/jacs.9b02298
M3 - Article
C2 - 31016974
AN - SCOPUS:85066863797
VL - 141
SP - 8680
EP - 8683
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 22
ER -