Synthesis of polypeptides via bioinspired polymerization of in situ purified
            <i>N</i>
            -carboxyanhydrides

Song, Ziyuan; Fu, Hailin; Wang, Jiang; Hui, Jingshu; Xue, Tianrui; Pacheco, Lazaro A.; Hui, Yan; Baumgartner, Ryan; Wang, Zhiyu; Xia, Yingchun; Wang, Xuefang; Yin, Lichen; Chen, Chongyi; Rodríguez‐López, Joaquín; Ferguson, Andrew L.; Lin, Yao; Cheng, Jianjun

doi:10.1073/pnas.1901442116

Cited by 103 publications

(165 citation statements)

References 43 publications

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“…After the 2-h polymerization in DCM, the end-group analysis showed <1% loss of terminal amine groups 19 , indicating negligible chain termination 10,12 . In addition, owing to the fast polymerization kinetics and the water-immiscibility of DCM 20,21 , the polymerization of NCA in DCM in the presence of 10 vol% water still resulted in well-defined polypeptide with predictable MW, similar to that obtained under anhydrous conditions (Fig. 2d and Supplementary Table 1).…”

Section: Resultsmentioning

confidence: 57%

Enzyme-mimetic self-catalyzed polymerization of polypeptide helices

Song

Baumgartner

et al. 2019

Nat Commun

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Enzymes provide optimal three-dimensional structures for substrate binding and the subsequent accelerated reaction. Such folding-dependent catalytic behaviors, however, are seldom mechanistically explored with reduced structural complexity. Here, we demonstrate that the α-helix, a much simpler structural motif of enzyme, can facilitate its own growth through the self-catalyzed polymerization of N-carboxyanhydride (NCA) in dichloromethane. The reversible binding between the N terminus of α-helical polypeptides and NCAs promotes rate acceleration of the subsequent ring-opening reaction. A two-stage, Michaelis–Menten-type kinetic model is proposed by considering the binding and reaction between the propagating helical chains and the monomers, and is successfully utilized to predict the molecular weights and molecular-weight distributions of the resulting polymers. This work elucidates the mechanism of helix-induced, enzyme-mimetic catalysis, emphasizes the importance of solvent choice in the discovery of new reaction type, and provides a route for rapid production of well-defined synthetic polypeptides by taking advantage of self-accelerated ring-opening polymerizations.

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Section: Resultsmentioning

confidence: 57%

Enzyme-mimetic self-catalyzed polymerization of polypeptide helices

Song

Baumgartner

et al. 2019

Nat Commun

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“…Finally, Cheng et al. reported the in situ purification of NCA during ROP when the polymerization was conducted in a CH 2 Cl 2 /water emulsion …”

Section: Methodsmentioning

confidence: 99%

Aqueous Ring‐Opening Polymerization‐Induced Self‐Assembly (ROPISA) of N‐Carboxyanhydrides

et al. 2019

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“…[12] Finally,C heng et al reported the in situ purification of NCA during ROP when the polymerization was conducted in aC H 2 Cl 2 /water emulsion. [13] Unfortunately,t he preparation of nanoassemblies from amphiphilic polypeptides requires as econd step of nanoprecipitation (Scheme 1A), which entails the addition of an onsolvent for the hydrophobic segment to ac opolymer solution in ac ommon solvent for both blocks. [14] This nanoprecipitation step is typically performed from toxic organic solvents,under relatively diluted conditions (< 1wt%)and is sensitive to scale,o verall hampering eventual regulatory approval.…”

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confidence: 99%