Binaphthol-derived phosphoric acids as efficient organocatalysts for the controlled ring-opening polymerization of γ-benzyl- -glutamate N-carboxyanhydrides

Liang, Jinpeng; Zhi, Xinmei; Zhou, Qiwen; Yang, Jing

doi:10.1016/j.polymer.2019.01.027

Cited by 12 publications

(12 citation statements)

References 52 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…We reasoned that the excessive carboxylic acid likely decreased the ROP rate through the competing reaction by partially protonating the chain propagating amine (acid–amine equilibrium). Similar effects were seen in cases where strong acids such as HCl, HBF 4 , and phosphoric acids were used for controlled ROP of NCAs, leading to significantly sacrificed reactivity, monomer conversion, and/or long induction period. ,, …”

Section: Resultsmentioning

confidence: 96%

“…Similar effects were seen in cases where strong acids such as HCl, HBF 4 , and phosphoric acids were used for controlled ROP of NCAs, leading to significantly sacrificed reactivity, monomer conversion, and/or long induction period. 23,25,58 Furthermore, the acid-catalyzed ROP was investigated in various solvents such as (deuterated) chloroform, nitrobenzene, acetonitrile, DMF, and DMSO at the feeding S4). The reactions displayed first-order kinetics in all solvents, among which chloroform showed a comparable k obs with DCM of (27.6 ± 0.2) × 10 −4 s −1 .…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Precision Synthesis of Polysarcosine via Controlled Ring-Opening Polymerization of N-Carboxyanhydride: Fast Kinetics, Ultrahigh Molecular Weight, and Mechanistic Insights

Wang,

Lu,

Wan

et al. 2024

J. Am. Chem. Soc.

View full text Add to dashboard Cite

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

show abstract

Section: Resultsmentioning

confidence: 96%

Section: Resultsmentioning

confidence: 99%

Precision Synthesis of Polysarcosine via Controlled Ring-Opening Polymerization of N-Carboxyanhydride: Fast Kinetics, Ultrahigh Molecular Weight, and Mechanistic Insights

Wang,

Lu,

Wan

et al. 2024

J. Am. Chem. Soc.

View full text Add to dashboard Cite

show abstract

“…[ 32,33 ] In a different investigation, the ROP of NCA with primary amine initiators using the (S)−1,1′‐binaphthyl‐based phosphoric acid organocatalytic system was carried out by Liang et al. [ 34 ] These organocatalysts facilitated the synthesis of poly(benzyl‐ l ‐glutamate) with expected molecular weight and narrow dispersities. Poly(methyl methacrylate)‐ b ‐polytyrosine (PMMA‐ b ‐Ptyr) copolymer conjugate was synthesized from a designed orthogonal dual initiator via the combination of ATRP of MMA, “click” chemistry and ROP of tyrosine‐NCA by Saha et al.…”

Section: Synthesis Approaches Toward Amino Acid‐derived Smart Polymersmentioning

confidence: 99%

Amino Acid‐Derived Smart and Functional Polymers for Biomedical Applications: Current Status and Future Perspectives

Kumar,

Sahu,

Banerjee

2023

Macro Chemistry & Physics

View full text Add to dashboard Cite

Amino acid‐derived smart and functional polymers have emerged as a promising class of biomaterials for diverse biomedical applications. In recent years, a wide range of such polymers with different compositions, macromolecular architectures and chain end functionalities have been prepared. Such polymers exhibited responsiveness to different external like chemical, physical, or biochemical stimuli. These stimuli include temperature, pH, metal ions, light, glucose, redox, or a combination of these factors. Thus developed smart and functional amino‐acid derived polymers have been employed in different biomedical and biotechnological applications, including but not limited to tissue engineering, drug delivery, wound healing, gene delivery, biosensors etc. Herein, we describe current state of the art and future perspectives of such amino acid‐derived smart and functional polymers which may be useful for researchers working towards the development of new amino acid‐derived polymeric materials for the construction of next generation of smart materials.This article is protected by copyright. All rights reserved

show abstract

“…In recent years, increasing efforts have been devoted to exploring new and efficient initiators and catalysts for NCA polymerization. Diverse initiators such as hexamethyldisilazane, used by Cheng [ 19 ], lithium hexamethyldisilazide, used by Liu [ 20 ]; trimethylsilyl and trimethylstannyl sulfide, used by Lu [ 21 , 22 ]; ammonium salts, used by Schlaad [ 23 , 24 ]; frustrated Lewis pairs, used by Yang [ 25 ]; catalysts such as cobalt and nickel organometallic catalysts, used by Deming [ 26 ]; organophosphates catalysts used by Yang [ 27 ]; and 1,1,3,3-tetramethylguanidine used by Cabral [ 28 ] have been reported for the controlled synthesis of PLL and other polypeptides. Very recently, Dong et al combined the inimer (initiator + monomer) ROP and photocaged chemistry to prepare hyperbranched and linear PLL.…”

Section: Synthesis Of Pll-based Polymersmentioning

confidence: 99%

Poly(α-l-lysine)-based nanomaterials for versatile biomedical applications: Current advances and perspectives

Zheng

Pan

Zhang

et al. 2021

Bioactive Materials

133

View full text Add to dashboard Cite

Poly(α- l -lysine) (PLL) is a class of water-soluble, cationic biopolymer composed of α- l -lysine structural units. The previous decade witnessed tremendous progress in the synthesis and biomedical applications of PLL and its composites. PLL-based polymers and copolymers, till date, have been extensively explored in the contexts such as antibacterial agents, gene/drug/protein delivery systems, bio-sensing, bio-imaging, and tissue engineering. This review aims to summarize the recent advances in PLL-based nanomaterials in these biomedical fields over the last decade. The review first describes the synthesis of PLL and its derivatives, followed by the main text of their recent biomedical applications and translational studies. Finally, the challenges and perspectives of PLL-based nanomaterials in biomedical fields are addressed.

show abstract

Binaphthol-derived phosphoric acids as efficient organocatalysts for the controlled ring-opening polymerization of γ-benzyl- -glutamate N-carboxyanhydrides

Cited by 12 publications

References 52 publications

Precision Synthesis of Polysarcosine via Controlled Ring-Opening Polymerization of N-Carboxyanhydride: Fast Kinetics, Ultrahigh Molecular Weight, and Mechanistic Insights

Precision Synthesis of Polysarcosine via Controlled Ring-Opening Polymerization of N-Carboxyanhydride: Fast Kinetics, Ultrahigh Molecular Weight, and Mechanistic Insights

Amino Acid‐Derived Smart and Functional Polymers for Biomedical Applications: Current Status and Future Perspectives

Poly(α-l-lysine)-based nanomaterials for versatile biomedical applications: Current advances and perspectives

Contact Info

Product

Resources

About