Tug‐of‐War between Two Distinct Catalytic Sites Enables Fast and Selective Ring‐Opening Copolymerizations DOI
Jianqun Wang,

Yinuo Zhu,

Maosheng Li

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(36)

Published: July 15, 2022

Ring-opening copolymerizations have emerged as a powerful approach towards the creation of sustainable polymers. Typical H-bonding catalysts for ring-opening are subject to single catalytic site. Here we describe H-bond-donor/Lewis-acidic-boron organocatalyst featuring two distinct sites in one molecule. The copolymerization epoxides with anhydride mediated by these modular, and tunable achieves high selectivity (>99 % polyester selectivity) markedly higher activity compared either di-thiourea analogues or any combinations them. Calculations experimental studies reveal that superior performance arises from tug-of-war between differentiated sites: thiourea pulls off propagating chain-end boron center, simultaneously enhancing role monomer activation also nucleophilicity propagation intermediates.

Language: Английский

Ring opening polymerization of α-amino acids: advances in synthesis, architecture and applications of polypeptides and their hybrids DOI
Alicia Rasines Mazo, Stephanie Allison‐Logan, Fatemeh Karimi

et al.

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 49(14), P. 4737 - 4834

Published: Jan. 1, 2020

Polypeptides have attracted considerable attention in recent decades due to their inherent biodegradability and tunable cytocompatibility. Macromolecular design conjunction with rational monomer composition can direct architecture, self-assembly chemical behavior, ultimately guiding the choice of appropriate application within biomedical field. This review focuses on applications polypeptides alongside synthetic advances ring opening polymerization α-amino acid N-carboxyanhydrides achieved past five years. Key architectures obtained through NCA ROP or combination other methods are reviewed, as these play an important role wide range towards which been applied.

Language: Английский

Citations

240
Recent Advances in Poly(α-L-glutamic acid)-Based Nanomaterials for Drug Delivery DOI Creative Commons
Yu Zhang, Wenliang Song, Yiming Lu

et al.

Biomolecules, Journal Year: 2022, Volume and Issue: 12(5), P. 636 - 636

Published: April 25, 2022

Poly(α-L-glutamic acid) (PGA) is a class of synthetic polypeptides composed the monomeric unit α-L-glutamic acid. Owing to their biocompatibility, biodegradability, and non-immunogenicity, PGA-based nanomaterials have been elaborately designed for drug delivery systems. Relevant studies including latest research results on discussed in this work. The following related topics are summarized as: (1) brief description strategies PGAs; (2) an elaborated presentation evolving applications PGA areas delivery, rational design, precise fabrication, biological evaluation; (3) profound discussion further development delivery. In summary, unique structures superior properties enables represent as enormous potential biomaterials-related areas.

Language: Английский

Citations

78
Precision Synthesis of Polysarcosine via Controlled Ring-Opening Polymerization of N-Carboxyanhydride: Fast Kinetics, Ultrahigh Molecular Weight, and Mechanistic Insights DOI
Shuo Wang, Mingyuan Lu,

Sikang Wan

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(8), P. 5678 - 5692

Published: Feb. 15, 2024

The rapid and controlled synthesis of high-molecular-weight (HMW) polysarcosine (pSar), a potential polyethylene glycol (PEG) alternative, via the ring-opening polymerization (ROP) N-carboxyanhydride (NCA) is rare challenging. Here, we report well-controlled ROP sarcosine NCA (Sar-NCA) that catalyzed by various carboxylic acids, which accelerate rate up to 50 times, enables robust pSar with an unprecedented ultrahigh molecular weight (UHMW) 586 kDa (DP ∼ 8200) exceptionally narrow dispersity (D̵) below 1.05. Mechanistic experiments density functional theory calculations together elucidate role acid as bifunctional catalyst significantly facilitates proton transfer processes avoids charge separation suggest ring opening NCA, rather than decarboxylation, rate-determining step. UHMW demonstrates improved thermal mechanical properties over low-molecular-weight counterparts. This work provides simple yet highly efficient approach generates new fundamental understanding useful not only for Sar-NCA but also other NCAs.

Language: Английский

Citations

23
Recent Advances and Future Developments in the Preparation of Polypeptides via N-Carboxyanhydride (NCA) Ring-Opening Polymerization DOI
Yueming Wu, Kang Chen, Jiangzhou Wang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(35), P. 24189 - 24208

Published: Aug. 22, 2024

Polypeptides have the same or similar backbone structures as proteins and peptides, rendering them suitable important biomaterials. Amino acid N-carboxyanhydrides (NCA) ring-opening polymerization has been most efficient strategy for polypeptide preparation, with continuous advance in design of initiators, catalysts reaction conditions. This Perspective first summarizes recent progress NCA synthesis purification. Subsequently, we focus on various initiators polymerization, accelerating enhancing controllability advances approach polymerization. Finally, discuss future research directions open challenges.

Language: Английский

Citations

20
Recent Advances and Future Perspectives of Synthetic Polypeptides from N-Carboxyanhydrides DOI
Ziyuan Song, Zhengzhong Tan, Jianjun Cheng

et al.

Macromolecules, Journal Year: 2019, Volume and Issue: 52(22), P. 8521 - 8539

Published: Oct. 7, 2019

Synthetic polypeptides, the analogues of natural proteins, are important biomaterials that have found broad biomedical applications. Ring-opening polymerization N-carboxyanhydrides offers a reliable way to prepare high-molecular-weight polypeptides in large scale with diverse side-chain functionalities. The past two decades seen significant advances polypeptide field, development various controlled methodologies, deeper understanding on secondary structures, and discovery new assembly behaviors In this Perspective, we highlight several key chemical synthesis materials application synthetic discuss promising future directions area.

Language: Английский

Citations

102
A moisture-tolerant route to unprotected α/β-amino acid N-carboxyanhydrides and facile synthesis of hyperbranched polypeptides DOI Creative Commons

Zi‐You Tian,

Zhengchu Zhang, Shuo Wang

et al.

Nature Communications, Journal Year: 2021, Volume and Issue: 12(1)

Published: Oct. 4, 2021

Abstract A great hurdle in the production of synthetic polypeptides lies access N -carboxyanhydrides (NCA) monomers, which requires dry solvents, Schlenk line/gloveboxe, and protection side-chain functional groups. Here we report a robust method for preparing unprotected NCA monomers air under moisture. The employs epoxy compounds as ultra-fast scavengers hydrogen chloride to allow assisted ring-closure prevent from acid-catalyzed decomposition moist conditions. broad scope group tolerance are demonstrated by facile synthesis over 30 different α/β-amino acid NCAs, including many otherwise inaccessible with reactive groups, at high yield, purity, up decagram scales. utility NCAs is two water-soluble that promising candidates drug delivery protein modification. Overall, our strategy holds potential facilitating expanding industrial application polypeptides.

Language: Английский

Citations

90
Controlled synthesis of polypeptides DOI
Yang Liu, Di Li, Jianxun Ding

et al.

Chinese Chemical Letters, Journal Year: 2020, Volume and Issue: 31(12), P. 3001 - 3014

Published: April 23, 2020

Language: Английский

Citations

88
Degradable polymers via olefin metathesis polymerization DOI Creative Commons
Hao Sun, Yifei Liang, Matthew P. Thompson

et al.

Progress in Polymer Science, Journal Year: 2021, Volume and Issue: 120, P. 101427 - 101427

Published: June 7, 2021

Language: Английский

Citations

74
α-Amino acid N-carboxyanhydride (NCA)-derived synthetic polypeptides for nucleic acids delivery DOI
Yong Liu, Lichen Yin

Advanced Drug Delivery Reviews, Journal Year: 2020, Volume and Issue: 171, P. 139 - 163

Published: Dec. 16, 2020

Language: Английский

Citations

71
Accelerated polymerization of N-carboxyanhydrides catalyzed by crown ether DOI Creative Commons
Yingchun Xia, Ziyuan Song, Zhengzhong Tan

et al.

Nature Communications, Journal Year: 2021, Volume and Issue: 12(1)

Published: Feb. 2, 2021

Abstract The recent advances in accelerated polymerization of N -carboxyanhydrides (NCAs) enriched the toolbox to prepare well-defined polypeptide materials. Herein we report use crown ether (CE) catalyze NCA initiated by conventional primary amine initiators solvents with low polarity and hydrogen-bonding ability. cyclic structure CE played a crucial role catalysis, 18-crown-6 enabling fastest kinetics. fast kinetics outpaced common side reactions, preparation polypeptides using an α-helical macroinitiator. Experimental results as well simulation methods suggested that changed binding geometry between propagating amino chain-end, which promoted molecular interactions lowered activation energy for ring-opening reactions NCAs. This work not only provides efficient strategy functionalized C-termini, but also guides design catalysts polymerization.

Language: Английский

Citations

68