Amidine-Mediated Zwitterionic Ring-Opening Polymerization of <i>N</i>-Alkyl <i>N</i>-Carboxyanhydride: Mechanism, Kinetics, and Architecture Elucidation

Li, Ang; Lu, Lu; Li, Xin; He, Lilin; Do, Changwoo; Garno, Jayne C.; Zhang, Donghui

doi:10.1021/acs.macromol.5b02611

Cited by 51 publications

(42 citation statements)

References 66 publications

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“…[15,37,67,68] Bu-NCA similar to NHCs (Scheme 8). [69] The reaction occurs in a controlled manner in low dielectric solvents (eg, THF and toluene), allowing access of polypeptoids having low to medium molecular weights (DP < 300) and narrow PDI (1.02-1.12), similar to what has been reported for NHCs. By contrast, in DMF, only low molecular weight polymers (DP < 40) were formed regardless of the initial monomer to DBU ratios.…”

Section: Synthesis Of Linear Polypeptoidsmentioning

confidence: 64%

“…The cyclic polypeptoid architecture was verified by a combination of end-group analysis with NMR and MS method and AFM and SANS analysis. [69,70] While the ZROP of Bu-NCA using DBU initiators is comparable to that with NHC initiators in rate, DBU has the advantage of being air and moisture stable, in contrast to NHCs. This makes DBU a more robust initiator relative to NHCs towards the ZROP of R-NCAs.…”

Section: Synthesis Of Linear Polypeptoidsmentioning

confidence: 99%

“…[77] Treatment of the star-shaped polymers with glutathione SCHEME 8 DBU-mediated ZROPs of Bu-NCAs to afford cyclic PNBGs. [69] Reprinted with permission from American Chemical Society …”

Section: Fig Urementioning

confidence: 99%

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Polypeptoid polymers: Synthesis, characterization, and properties

et al. 2017

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Polypeptoids, a class of peptidomimetic polymers, have emerged at the forefront of macromolecular and supramolecular science and engineering as the technological relevance of these polymers continues to be demonstrated. The chemical and structural diversity of polypeptoids have enabled access to and adjustment of a variety of physicochemical and biological properties (eg, solubility, charge characteristics, chain conformation, HLB, thermal processability, degradability, cytotoxicity and immunogenicity). These attributes have made this synthetic polymer platform a potential candidate for various biomedical and biotechnological applications. This review will provide an overview of recent development in synthetic methods to access polypeptoid polymers with well-defined structures and highlight some of the fundamental physicochemical and biological properties of polypeptoids that are pertinent to the future development of functional materials based on polypeptoids. | I N TR ODU C TI ONPolypeptoids composed of N-substituted polyglycine backbones are structural mimics of polypeptides ( Figure 1). Because of N-substitution, polypeptoids lack stereogenic centers and hydrogen bonding interactions along the main chains, in sharp contrast to polypeptides.As a result, the global conformations of polypeptoids are strongly dependent on the N-substituent structures, giving rise to random coils or well-defined secondary structures [eg, polyproline I (PPI) helix [1][2][3][4][5][6] and R-sheets] [7][8][9][10][11][12] that are reminiscent of those of polypeptides. The polypeptoid backbone containing tertiary amide linkages is highly polar and hydrophilic. The physicochemical properties of polypeptoids can be tailored by the N-substituent structures, enabling control over the hydrophilicity and lipophilicity balance (HLB), charge characteristics, [13,14] backbone conformation, [1][2][3][4][5][6][7][8][9][10][11][12] solubility, [15][16][17][18][19][20] thermal and crystallization properties of the polypeptoids. [21][22][23][24] Without extensive hydrogen bonding, polypeptoids are thermally processable similar to conventional thermoplastics, [20][21][22][23][24] whereas polypeptides undergo thermal degradation before they can be melt-processed due to the extensive hydrogen bonding interactions. While polypeptoids exhibited enhanced proteolytic stability relative to peptides, [25,26] they can be oxidatively degraded under conditions that mimic tissue inflammation, [27] suggesting their potential in vivo uses as biodegradable materials.Recent advances in the controlled polymerization methods have enabled access to a suite of structurally well-defined polypeptoids with various N-substituent structures and molecular architectures, setting the stage for the future development of polypeptoid materials for various targeted applications. Several review articles on the synthesis, properties, and application of polypeptoids for biomedical or nonbiomedical uses have been published in recent years. [28][29][30][31][32] As a result, this...

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Section: Synthesis Of Linear Polypeptoidsmentioning

confidence: 64%

Section: Synthesis Of Linear Polypeptoidsmentioning

confidence: 99%

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Polypeptoid polymers: Synthesis, characterization, and properties

et al. 2017

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“…This may be due to the driving force of the crystallization of the solvophobic block (PNDG). The same authors also found that cyclic polypeptoids could be prepared by zwitterionic ring‐opening polymerization (ZROP) with 1,8‐diazabicycloundec‐7‐ene (DBU) as an initiator . Beside cyclic homopolymer, that is, poly( N ‐BuGly), random copolypeptoids, poly([ N ‐propargyl glycine]‐ r ‐[ N ‐butyl glycine])s, could also be synthesized by ZROP.…”

Section: Crystallization and Self‐assembly Of Polypeptoid Polymersmentioning

confidence: 99%

Recent advances in crystallization and self‐assembly of polypeptoid polymers

Zeng

Qiu

Wen

2019

Polymer Crystallization

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Poly(N‐substituted glycine)s, or polypeptoids, have attracted great interest from researchers due to their structural similarity to polypeptides. By taking advantage of relative ease of synthesis and good solubility in common solvents, polypeptoid polymers provide a versatile platform to generate peptide mimics with well‐defined chemical structures and architectures. As a class of peptidomimetic polymers, a deep understanding on the impact of side‐chain structures, main‐chain topologies, and backbone conformations with respect to the aggregation behaviors is the prerequisite for developing peptidomimetic polymers toward macromolecular and supramolecular engineering. This mini‐review highlights recent developments in the crystallization and self‐assembly of homopolymers, block copolymers, and macrocycles of polypeptoids.

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“…Typically, two different synthetic strategies toward polypeptoids are possible: iterative submonomer route and ring‐opening polymerization (ROP) of N ‐substituted α‐amino acid‐ N ‐carboxyanhydrides (NNCAs) . Polypeptoids with absolute monodispersity and controlled sequence can be harvested by submonomer approach.…”

Section: Introductionmentioning

confidence: 99%

Polypeptoids synthesis based on Ugi reaction: Advances and perspectives

2019

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Polypeptoids are peptidomimetic polymers invented in the early 1990s. Although polypeptoid chemistry is developing rapidly, the simple synthesis of polypeptoids and sequence‐controlled polypeptoids still remains a challenge. Fortunately, we have seen a drastic rising trend in the area of Ugi reaction for polypeptoid chemistry. In the following article, recent examples of the Ugi reaction for polypeptoids synthesis will be presented, as will their suitability for sequence‐defined peptide‐peptoid hybrids. The advantages and limitations of the Ugi reaction will be discussed, which is important for the simple and general synthesis of polypeptoids.

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Amidine-Mediated Zwitterionic Ring-Opening Polymerization of N-Alkyl N-Carboxyanhydride: Mechanism, Kinetics, and Architecture Elucidation

Cited by 51 publications

References 66 publications

Polypeptoid polymers: Synthesis, characterization, and properties

Polypeptoid polymers: Synthesis, characterization, and properties

Recent advances in crystallization and self‐assembly of polypeptoid polymers

Polypeptoids synthesis based on Ugi reaction: Advances and perspectives

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