title: Phenyl Trimethylsilyl Sulfide-Mediated Controlled Ring-Opening Polymerization of α-Amino Acid N-Carboxyanhydrides.
abstract: We describe here the first example of trimethylsilyl sulfide (S-TMS) mediated controlled ring-opening polymerization (ROP) of α-amino acid N-carboxyanhydrides (NCAs). We show that phenyl trimethylsilyl sulfide (PhS-TMS), an inexpensive and commercially available compound, mediates rapid ROP of a broad scope of NCA monomers, produces functional poly(amino acids) (PAAs) with controllable molecular weights (MWs), narrow polydispersity index (PDI), and an in situ generated phenyl thioester group at the C-terminus (PAA-SPhs). PhS-TMS offers more rapid chain initiation than previously reported hexamethyldisilazane (HMDS) initiator, ensuring a living polymerization with better control. Mechanistic studies suggest that a reactive trimethylsilyl carbamate (TMSC) was generated during the chain initiation and continued to regulate the chain propagation through a TMS transfer process. Considering the versatility of NCAs, and the potential of leveraging the C-terminal phenyl thioester for native chemical ligation (NCL), we believe this method may offer a powerful platform enabling the rapid generation of functional PAAs and their C-terminal conjugates for numerous biological applications.
authors.affiliation: Beijing National Laboratory for Molecular Sciences, Center for Soft Matter Science and Engineering, Key Laboratory of Polymer Chemistry and Physics of Ministry of Education, College of Chemistry and Molecular Engineering, Peking University , Beijing 100871, People's Republic of China.
authors.forename: Jingsong
authors.initials: J
authors.lastname: Yuan
authors.affiliation: Beijing National Laboratory for Molecular Sciences, Center for Soft Matter Science and Engineering, Key Laboratory of Polymer Chemistry and Physics of Ministry of Education, College of Chemistry and Molecular Engineering, Peking University , Beijing 100871, People's Republic of China.
authors.forename: Yunlong
authors.initials: Y
authors.lastname: Sun
authors.affiliation: Beijing National Laboratory for Molecular Sciences, Center for Soft Matter Science and Engineering, Key Laboratory of Polymer Chemistry and Physics of Ministry of Education, College of Chemistry and Molecular Engineering, Peking University , Beijing 100871, People's Republic of China.
authors.forename: Jingyu
authors.initials: J
authors.lastname: Wang
authors.affiliation: Beijing National Laboratory for Molecular Sciences, Center for Soft Matter Science and Engineering, Key Laboratory of Polymer Chemistry and Physics of Ministry of Education, College of Chemistry and Molecular Engineering, Peking University , Beijing 100871, People's Republic of China.
authors.forename: Hua
authors.initials: H
authors.lastname: Lu
mesh_terms: D000596:Amino Acids / Q000737:chemistry*; D000812:Anhydrides / Q000737:chemistry; D009842:Oligopeptides / Q000737:chemistry; D017646:Organosilicon Compounds / Q000737:chemistry; D058105:Polymerization; D014297:Trimethylsilyl Compounds / Q000737:chemistry*
chemical_list: D000596:Amino Acids; D000812:Anhydrides; D009842:Oligopeptides; D017646:Organosilicon Compounds; D014297:Trimethylsilyl Compounds; C024548:hexamethylsilazane