Poly(ε-lysine) and its derivatives via ring-opening polymerization of biorenewable cyclic lysine

Abstract

Poly(ε-lysine) (ε-PL) is an unusual cationic, naturally-occurring biopolymer furnished by microorganisms fermentation process. ε-PL has attracted extensive attention in the areas from food and cosmetic additives to pesticides and medicine...

Organocatalyzed Ring-Opening Polymerization of Cyclic Lysine Derivative: Sustainable Access to Cationic Poly(ε-lysine) Mimics

“…Our laboratory has described the ROP of a 2,5-dimethylpyrrole-protected cyclic lysine monomer to furnish ε-PL. − , In this study, we focused on the development of functional mimics of ε-PL by applying renewable lysine as feedstocks. Cyclic lysine (α-amino-ε-caprolactam) was synthesized according to our previous report .…”

“…Our previous reports have demonstrated that t- BuP 4 -catalyzed ROP of cyclic lysine monomers offered a viable approach for synthesizing ε-PL and its derivatives with high MWs under mild conditions. , After the successful preparation of the DMCL monomer derived from lysine, t- BuP 4 was used for the ROP of DMCL at 140 °C in dimethylacetamide (DMAC). With a 4.0 mol % loading of t -BuP 4 and 1 equivalent of the coinitiator N -benzoyl-α - dimethylamino-ε-caprolactam ( N -BzDMCL) relative to t -BuP 4 , the polymerization proceeded to reach 88% conversation after 3 h (Table , entry 1).…”

“…Phosphazene base t- BuP 4 , first reported by Schwesinger in 1987, , exhibits extreme activity for ROP of a wide range of cyclic monomers. − In 2016, Chen utilized t- BuP 4 to successfully catalyze the ROP of γ-butyrolactone, which is commonly considered to be a “nonpolymerizable” monomer . We have recently developed cyclization of lysine and a t- BuP 4 -catalyzed ROP platform, ,− which opens up a novel method for furnishing ε-PL and its derivatives with high MWs under mild polymerization conditions. Here, we demonstrate the synthesis and organopolymerization of dimethyl-protected cyclic lysine to provide cationic ε-PL mimics with quaternary ammonium groups of various pendent alkyls.…”

Advancing the Development of Recyclable Aromatic Polyesters by Functionalization and Stereocomplexation

“…Functionalities and tacticities of polymer chains have a significant influence on the physical and mechanical properties of polymeric materials [20–27] . As a synthetic toolbox, both direct polymerization of functionalized monomers and postpolymerization modification have been devoted to introducing diverse functionalities into polymers, enabling the fine‐tuning and improvement of the thermal and mechanical properties of the pristine polymer [20] .…”

“…Functionalities and tacticities of polymer chains have a significant influence on the physical and mechanical properties of polymeric materials. [20][21][22][23][24][25][26][27] As a synthetic toolbox, both direct polymerization of functionalized monomers and postpolymerization modification have been devoted to introducing diverse functionalities into polymers, enabling the fine-tuning and improvement of the thermal and mechanical properties of the pristine polymer. [20] Additionally, significant efforts have focused on synthesizing stereoregular polymers towards high-performance materials, [28][29][30][31][32][33] such as ROP of enantiopure monomers to isotactic polymers.…”