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

Polypept(o)ide‐Based Core–Shell Bottlebrush Polymers: A Versatile Platform for Drug Encapsulation DOI Creative Commons

Bonan Zhao,

Jinjia Wei, Rüdiger Berger

et al.

Macromolecular Bioscience, Journal Year: 2025, Volume and Issue: unknown

Published: April 22, 2025

Abstract Cylindrical bottlebrush polymers (CBPs) enable the precise adjustment of nanoparticle properties such as size, shape, and functionality exclusively by polymer synthesis. In addition, block copolymer side chains direct access to core–shell structure. this study, synthesis polypept(o)ides‐based CBPs is presented through a “grafting‐from” strategy. While, poly‐lysine (pLys) serves backbone, poly(γ‐benzyl‐ l ‐glutamic acid)‐block‐polysarcosine (pGlu(OBn)‐ b ‐pSar) copolymers form chains. This approach enables nanoparticles, referred brushes (CSBs), with hydrodynamic radius ( R h ) from 17 70 nm, molecular weights (1320–4000 kg mol −1 dispersity indices ≈1.3 determined size‐exclusion chromatography. Dasatinib chosen drug molecule model explore potential synthetical CSBs platform for encapsulation π – ‐interactions. An overall loading efficiency 10% achieved, which also displayed sustained release within 72 h, cellular uptake into human glioblastoma (U‐87 MG) cells, drug‐related therapeutic efficacy. While can be further optimized covalent attachment, these results establish strong foundation use in nanomedicine.

Language: Английский

Citations

0
Synthetic Polymers for Drug, Gene, and Vaccine Delivery DOI Creative Commons
Yajun Xu, Jie Chen, Jianxun Ding

et al.

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

Published: April 25, 2025

Language: Английский

Citations

0
Sequence-defined peptoids via iterative exponential growth DOI Creative Commons
Abigail Mae Clapperton,

Christine Hood,

Helen Tran

et al.

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

An iterative exponential growth (IEG) strategy relying on orthogonally protected monomers is developed for the synthesis of peptoids. This a scalable technique that allows precise control over sequence, chain length, and stereoconfiguration.

Language: Английский

Citations

0
Recyclable Polythioesters and Poly(thioester‐co‐peptoid)s via Ring‐Opening Cascade Polymerization of Amino Acid N‐Carboxyanhydrides DOI
Shuo Wang,

Zi‐You Tian,

Hua Lu

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(45)

Published: July 29, 2024

Polythioesters (PTEs) are emerging sustainable polymers for their degradability and recyclability. However, low polymerizability of monomers extensive side reactions often hampered the polymerization process. Moreover, copolymers containing both thioester other types functional groups in backbone highly desirable but rarely accomplished owing to several synthetic challenges. Here, we report ring-opening cascade (ROCAP) N-(2-(acetylthio)ethyl)-glycine N-carboxyanhydrides (TE-NCA) afford recyclable PTEs unprecedented poly(thioester-co-peptoid)s (P(TE-co-PP)s) a controlled manner. By developing appropriated carboxylic acid-tertiary amine dual catalysts, intramolecular S-to-N acyl shift is coupled into ROCAP process TE-NCA yield products with dispersity below 1.10, molecular weight (M

Language: Английский

Citations

2
Synthesis and In Situ Thermal Induction of β-Sheet Nanocrystals in Spider Silk-Inspired Copolypeptides DOI
Tianjian Yang, Tianrui Xue,

Jianan Mao

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(46), P. 31849 - 31859

Published: Nov. 6, 2024

Spider silk, known for its exceptional tensile strength, extensibility, and toughness, continues to inspire advancements in polymer materials science. Despite extensive research, synthesizing that encompass all these properties remains a significant challenge. This study addresses this challenge by developing high molecular-weight multiblock synthetic copolypeptides mimic the hierarchical structure mechanical of spider silk. Using autoaccelerated ring-opening polymerization

Language: Английский

Citations

2
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 International Edition, 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

Citations

1
Single-Center Trifunctional Organocatalyst Enables Fast and Controlled Polymerization on N-Carboxyanhydride DOI Creative Commons
Kang Chen, Yueming Wu, Minzhang Chen

et al.

ACS Central Science, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 29, 2024

Ring-opening polymerization on N-carboxyanhydrides (NCA) initiated by primary amines has been the dominantly used method to prepare polypeptides with widespread applications. However, this chemistry suffers from slow rate, limited controllability, and difficulty in preparing high molecular weight polypeptides. Herein, we develop a conjugated cationic catalyst featuring cation-dipole interaction, which remarkably enhances reaction rate controllability of NCA polymerization, simultaneously, afford short time predictable weights (DP = 20-500) narrow dispersities. Experimental data computational study altogether indicate that catalysts manifest single center triple functions activating C5-carbonyl NCAs enhance electrophilic activity monomer, carbamate intermediates accelerate decarboxylation, moderately passivating improve controllability. Notably, cationic-catalyst is well recyclable while keeping excellent catalytic performance. Thus, highly efficient strategy implies practical promising applications, representing new avenue design for chemistry.

Language: Английский

Citations

1
Enhanced rate of sarcosine N-carboxyanhydride polymerisation from a lysine dendrimer macroinitiator driven by neighbouring H-bonding effects DOI
R. England, Qing Yu,

Chloe Westley

et al.

Polymer Chemistry, Journal Year: 2024, Volume and Issue: 15(13), P. 1318 - 1330

Published: Jan. 1, 2024

In situ FTIR monitoring revealed that sarcosine N -carboxyanhydride polymerisations were catalysed using a lysine dendrimer macroinitiator owing to hydrogen bonding interactions between the core and monomer.

Language: Английский

Citations

0
Controlled Synthesis of Crystalline and Helical N-Alkyl Poly(l-alanine) DOI
Wenxiao Liu,

Xuehua Deng,

Yutong Dong

et al.

Macromolecules, Journal Year: 2024, Volume and Issue: 57(15), P. 7031 - 7042

Published: July 20, 2024

Language: Английский

Citations

0
Recyclable Polythioesters and Poly(thioester‐co‐peptoid)s via Ring‐Opening Cascade Polymerization of Amino Acid N‐Carboxyanhydrides DOI
Shuo Wang,

Zi‐You Tian,

Hua Lu

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(45)

Published: July 29, 2024

Abstract Polythioesters (PTEs) are emerging sustainable polymers for their degradability and recyclability. However, low polymerizability of monomers extensive side reactions often hampered the polymerization process. Moreover, copolymers containing both thioester other types functional groups in backbone highly desirable but rarely accomplished owing to several synthetic challenges. Here, we report ring‐opening cascade (ROCAP) N ‐(2‐(acetylthio)ethyl)‐glycine ‐carboxyanhydrides (TE‐NCA) afford recyclable PTEs unprecedented poly(thioester‐co‐peptoid)s (P(TE‐co‐PP)s) a controlled manner. By developing appropriated carboxylic acid‐tertiary amine dual catalysts, intramolecular S ‐to‐ acyl shift is coupled into ROCAP process TE‐NCA yield products with dispersity below 1.10, molecular weight ( M n ) up 84.5 kDa, precisely ratio peptoids. Random copolymerization sarcosine NCA (Sar‐NCA) gives thioester‐embedded polysarcosine facile degradation while maintaining water solubility. This work represents paradigm ROP NCAs, enriches realm polymerizations, provides powerful approach P(TE‐co‐PP)s that otherwise difficult or impossible make.

Language: Английский

Citations

0