Self‐promoted Controlled Ring‐opening Polymerization via Side Chain‐mediated Proton Transfer for the Synthesis of Tertiary Amine‐pendant Polypeptoids DOI Open Access

Mingzhen Liao,

Yao Yao,

Kunyu Gan

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 16, 2024

Abstract Proton transfer is essential in virtually all biochemical processes, with enzymes facilitating this by optimizing the proximity and orientation of reactants through site‐specific hydrogen bonds. also crucial rate‐determining step for ring‐opening polymerization N ‐carboxyanhydrides (NCAs), widely used to prepare various peptidomimetic materials. This study utilizes side chain‐assisted strategy accelerate rate chain propagation using NCAs tertiary amine pendants. moiety enables bond formation between incoming NCA polymer amino growing end. The forms a proton shuttle, via less constrained transition state, facilitate process. Moreover, chains enable precipitation monomers situ protonation during monomer synthesis. greatly facilitates synthesis these unreported monomers, allowing direct controlled amine‐pendant polypeptoids. chain‐promoted has rarely been reported. Additionally, chains, as functional groups, endow polymers unique properties including pH‐ thermo‐responsiveness, tunable p K s, siRNA transfection capability. self‐promoted synthesis, facile preparation, attractive make polypeptoids promising materials applications.

Language: Английский

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

18
Polymerization-induced self-assembly of N-substituted glycine N-carboxyanhydrides in selected solvents DOI

Qing Gao,

Hailin Fu, Hui Liu

et al.

European Polymer Journal, Journal Year: 2025, Volume and Issue: 225, P. 113720 - 113720

Published: Jan. 4, 2025

Language: Английский

Citations

1
Polypept(o)ides – Origins, Synthesis, Applications and Future Directions DOI Creative Commons
Tobias Bauer,

Leon Simić,

Joachim F. R. Van Guyse

et al.

Progress in Polymer Science, Journal Year: 2024, Volume and Issue: unknown, P. 101889 - 101889

Published: Sept. 1, 2024

Language: Английский

Citations

5
Unveiling Proton Transfer as the Key Process to Understand and Promote the Ring-Opening Polymerization of N-Carboxyanhydrides DOI Creative Commons
Shuo Wang, Hua Lu

Polymer science & technology., Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 23, 2025

Language: Английский

Citations

0
Strong Bioadhesives from Helical Polypeptides DOI

Jiangyan Shi,

Liufen Kong,

Ning Wang

et al.

ACS Macro Letters, Journal Year: 2025, Volume and Issue: 14(3), P. 299 - 305

Published: Feb. 21, 2025

Bioadhesives have emerged as versatile and powerful tools for tissue repair integration with biomedical devices, offering a wide range of applications that captured significant clinical scientific interest. Synthetic polypeptide adhesives are particularly promising candidates bioadhesives, but often face limitations in adhesive strength. In this study, inspired by marine proteins, the secondary structure hydrophobic–hydrophilic balance polypeptides were precisely regulated to transform polyelectrolyte strong adhesive. The resulting demonstrated an strength exceeding 1.0 MPa, more than 10× higher previously reported synthetic cohesion adhesion can be optimized adjusting content hydrophobic residue ratios. More helices enhance interactions between backbone side chains well substrates. addition, these exhibit excellent tolerance acids or alkalis, remarkable variable materials tissues, impressive sealing performance.

Language: Английский

Citations

0
Triphenylphosphine-Initiated Ring-Opening Polymerization for α-Helical Polypeptides and Application in Constructing Artificial Ion Channels DOI

Zexin Yan,

Tianlong Li, Jiawei Liu

et al.

Biomacromolecules, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 25, 2025

In this study, we have screened out an effective triphenylphosphine-derived initiator (2-TMOPP) for efficient ring-opening polymerization of α-amino acid N-carboxyanhydrides (NCA ROP) and demonstrated the potential prepared helical polypeptide as ion channel. By optimizing conditions, 2-TMOPP exhibited precise control over molecular weight polydispersity index polypeptides, universality different NCA monomers, ability to form α-helical secondary structures. further incorporating binding groups regulating length, PLCE was capable inserting into lipid bilayers possessing function transport (H+/K+ antiport) via a channel mechanism (EC50 = 12.75 ± 1.58 μg mL-1). also showed anticancer activity toward HeLa cells, with IC50 value approximately 69.67 1.20 mL-1 after 20 h coculture, showing possibility future practical application in biomedical fields.

Language: Английский

Citations

0
Organo‐Catalyst Catalyzed Ring Opening Polymerization of N ‐Carboxyanhydrides DOI Open Access
Chongyi Chen, Zhibo Li

Published: March 7, 2025

Language: Английский

Citations

0
Record-High-Molecular-Weight Polyesters from Ring-Opening Copolymerization of Epoxides and Cyclic Anhydrides Catalyzed by Hydrogen-Bond-Functionalized Imidazoles DOI
Zhiyuan Xie, Zhenjie Yang, Chenyang Hu

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: March 26, 2025

Polyesters, with potential for degradability and sustainability, are some of the most versatile polymer materials. However, limitation molecular weight (MW) presents a barrier to their applications. The synthesis polyesters high MW by ring-opening copolymerization (ROCOP) epoxides cyclic anhydrides is promising but rare challenging. Herein, we report series air-stable, hydrogen-bond-functionalized imidazole catalysts copolymerization. These can produce (4 examples) using cyclohexane oxide (CHO), propylene (PO), phenyl glycidyl ether (PGE), 4-vinyl-1-cyclohexene 1,2-epoxide (VCHO), phthalic anhydride (PA) record-high MW: Mn = 171.2 kDa poly(CHO-alt-PA), 518.5 poly(PO-alt-PA), 100.5 poly(PGE-alt-PA), 236.4 poly(VCHO-alt-PA). Furthermore, it achieve an unprecedented efficiency 15.6 kg polyester/g catalyst at molar ratio catalyst/PA/PO 1:40000:60000. achieved be attributed unique anionic-cationic coexisting ROCOP mechanism, which reduce transesterification, chain transfer, annulation side reactions. All showed excellent thermal stability, tensile strength, Young's modulus comparable commodity thermoplastics like polystyrene polylactic acid.

Language: Английский

Citations

0
Understanding Acid-Promoted Polymerization of N-Phenoxycarbonyl N-Substituted Glycine: Differences among Methyl, Ethyl, and Butyl Substituents DOI

Songyi Xu,

Tianwen Bai, Jun Ling

et al.

Macromolecules, Journal Year: 2025, Volume and Issue: unknown

Published: April 8, 2025

Language: Английский

Citations

0
Toward Quantitative End-Group Fidelity in the Synthesis of High Molecular Weight Polysarcosine DOI Creative Commons

Zlata Nagorna,

Matthias Barz, Joachim F. R. Van Guyse

et al.

ACS Macro Letters, Journal Year: 2025, Volume and Issue: unknown, P. 532 - 537

Published: April 15, 2025

Polymers applied in pharmaceutical applications need to meet stringent quality standards ensure reproducibility of product properties, such as efficacy and safety therapeutics. End-group fidelity is a crucial feature that ensures functional integrity, reproducible synthesis, robust therapeutic performance. The contemporary production poly(ethylene glycol) (PEG) exemplifies this requirement, which has consolidated its position gold standard applications. However, modest severe immune responses toward PEG patients generate the for alternative polymers development pharmaceuticals or cosmetics. Among alternatives, polysarcosine (pSar) displays PEG-like stealth properties vivo while displaying improved immunogenicity toxicity profiles, generating heterotelechelic pSar highest end-group integrity. Here, we compared current synthetic methods controlled synthesis over broad molecular weight range assessed by ion exchange chromatography. Subsequent isolation allowed identification impurities via mass spectrometry, thus yielding mechanistic insights into N-substituted N-carboxyanhydride ring-opening polymerization (ROP). Our results reveal nuanced role organocatalysts ROP, highlighting opportunities better catalysts. Finally, work showcases scalable purification method obtain high with quantitative fidelity.

Language: Английский

Citations

0