More Like this

1. Activated Monomer Polymerization of an N -Sulfonylazetidine

   https://doi.org/10.1021/acsmacrolett.0c00019  

   Reisman, Louis; Rowe, Elizabeth A.; Jefcoat, Jennifer A.; Rupar, Paul A. (March 2020, ACS Macro Letters)
2. Biomimetic Glycosylated Polythreonines by N -Carboxyanhydride Polymerization

   https://doi.org/10.1021/acs.biomac.2c00020  

   Deleray, Anna C.; Kramer, Jessica R. (March 2022, Biomacromolecules)
3. Polymerization of Aniline Derivatives to Yield Poly[ N , N -(phenylamino)disulfides] as Polymeric Auxochromes

   https://doi.org/10.1021/acs.macromol.1c01548  

   Grace, James P.; Flitz, Evan S.; Hwang, Dae Sun; Bowden, Ned B. (November 2021, Macromolecules)
4. Photo-liberated amines for N -carboxyanhydride (PLANCA) ring-opening polymerization

   https://doi.org/10.1039/d1py00781e  

   Goodrich, Sofia L.; Hill, Megan R.; Olson, Rebecca A.; Sumerlin, Brent S. (July 2021, Polymer Chemistry)

   The polymerization of N -carboxyanhydrides (NCAs) affords access to a vast array of synthetic polypeptides with tunable molecular weights, functionalities, and architectures. The use of light to achieve spatiotemporal control over these polymerizations could expand their applicability to a variety of areas, including 3D printing and photolithography. In this report we utilized 2-(2-nitrophenyl)propyloxycarbonyl (NPPOC) as a photoprotecting group to cage a primary amine initiator that is activated upon UV irradiation. NPPOC photocages underwent quantitative deprotection and afforded better polymerization control compared to previously reported photocaged amines for NCA polymerizations. Furthermore, the addition of a small equivalence of base enhanced the control and resulted in polymers with lower dispersities. Overall, this method advances photo-controlled polypeptide synthesis by demonstrating high chain-end fidelity, efficient chain extension, and the ability to synthesize block copolymers. 

   more » « less
5. Synthesis of polypeptides via bioinspired polymerization of in situ purified N -carboxyanhydrides

   https://doi.org/10.1073/pnas.1901442116  

   Song, Ziyuan; Fu, Hailin; Wang, Jiang; Hui, Jingshu; Xue, Tianrui; Pacheco, Lazaro A.; Yan, Haoyuan; Baumgartner, Ryan; Wang, Zhiyu; Xia, Yingchun; et al (May 2019, Proceedings of the National Academy of Sciences)

   Ribozymes synthesize proteins in a highly regulated local environment to minimize side reactions caused by various competing species. In contrast, it is challenging to prepare synthetic polypeptides from the polymerization of N -carboxyanhydrides (NCAs) in the presence of water and impurities, which induce monomer degradations and chain terminations, respectively. Inspired by natural protein synthesis, we herein report the preparation of well-defined polypeptides in the presence of competing species, by using a water/dichloromethane biphasic system with macroinitiators anchored at the interface. The impurities are extracted into the aqueous phase in situ, and the localized macroinitiators allow for NCA polymerization at a rate which outpaces water-induced side reactions. Our polymerization strategy streamlines the process from amino acids toward high molecular weight polypeptides with low dispersity by circumventing the tedious NCA purification and the demands for air-free conditions, enabling low-cost, large-scale production of polypeptides that has potential to change the paradigm of polypeptide-based biomaterials. 

   more » « less