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  1. Synthetic polypeptides derived from the ring-opening polymerization of N -carboxyanhydrides can spontaneously fold into stable secondary structures under specific environmental conditions. These secondary structures and their dynamic transitions play an important role in regulating the properties of polypeptides in self-assembly, catalysis, polymerization, and biomedical applications. Here, we review the current strategies to modulate the secondary structures, and highlight the conformation-specific dynamic properties of synthetic polypeptides and the corresponding materials. A number of mechanistic studies elucidating the role of secondary structures are discussed, aiming to provide insights into the new designs and applications of synthetic polypeptides. We aim for this article to bring to people's attention synthetic polymers with ordered conformations, which may exhibit association behaviors and material properties that are otherwise not found in polymers without stable secondary structures. 
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  2. Abstract

    RecentlyO‐carboxyanhydrides (OCAs) have emerged as a class of viable monomers which can undergo ring‐opening polymerization (ROP) to prepare poly(α‐hydroxyalkanoic acid) with functional groups that are typically difficult to achieve by ROP of lactones. Organocatalysts for the ROP of OCAs, such as dimethylaminopyridine (DMAP), may induce undesired epimerization of the α‐carbon atom in polyesters resulting in the loss of isotacticity. Herein, we report the use of (BDI‐IE)Zn(OCH(CH3)COOCH3) ((BDI)Zn‐1, (BDI‐IE)=2‐((2,6‐diethylphenyl)amino)‐4‐((2,6‐diisopropylphenyl)imino)‐2‐pentene), for the controlled ROP of various OCAs without epimerization. Both homopolymers and block copolymers with controlled molecular weights, narrow molecular weight distributions, and isotactic backbones can be readily synthesized. (BDI)Zn‐1 also enables controlled copolymerization of OCAs and lactide, facilitating the synthesis of block copolymers potentially useful for various biomedical applications. Preliminary mechanistic studies suggest that the monomer/dimer equilibrium of the zinc catalyst influences the ROP of OCAs, with the monomeric (BDI)Zn‐1 possessing superior catalytic activity for the initiation of ROP in comparison to the dimeric (BDI)Zn complex.

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