1,1,3,3-Tetramethylguanidine-Promoted Ring-Opening Polymerization of <i>N</i>-Butyl <i>N</i>-Carboxyanhydride Using Alcohol Initiators

Chan, Brandon A.; Xuan, Sunting; Horton, Matthew; Zhang, Donghui

doi:10.1021/acs.macromol.5b02520

Cited by 46 publications

(43 citation statements)

References 71 publications

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“…Taking the advantages of high reactivity and productivity, ring‐opening polymerization (ROP) of N ‐substituted glycine N ‐carboxyanhydrides (NNCAs) is the most efficient method to synthesize polypeptoids . Recently, many efforts have been paid on NNCAs to achieve their living polymerizations using different initiators . Zhang and coworkers reported N ‐heterocyclic carbenes (NHCs)‐mediated living polymerization of NNCAs to prepare cyclic homo‐ and block‐polypeptoids, and investigated the mechanism detailedly .…”

Section: Introductionmentioning

confidence: 99%

Are N‐substituted glycine N‐thiocarboxyanhydride monomers really hard to polymerize?

Tao

Zheng

Kricheldorf³

et al. 2016

J. Polym. Sci. Part A: Polym. Chem.

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N-Substituted glycine N-thiocarboxyanhydrides (NNTAs) are promising cyclic monomers to synthesize polypeptoids with the advantages of easier preparation and higher stability during purification and storage than N-substituted glycine N-carboxyanhydrides (NNCAs). NNTAs were commonly considered too stable to polymerize for their low reactivity. In this contribution, we report controlled polymerizations of N-ethylglycine NTA (NEG-NTA) and sarcosine NTA (Sar-NTA) using primary amines as initiator under proper polymerization conditions. The controllability has been fully supported by 1 H NMR end group analyses, MALDI-ToF mass spectra, kinetic data, block copolymerizations by sequential monomer addition, and low polydispersities (1.14-1.17) of polypeptoids. Variation of the [NNTA]/[initiator] ratio allows well control of the molar mass, and degrees of polymerization (DPs) up to 287 can be reached for poly (N-ethylglycine) or DPs up to 262 for polysarcosine. NNTAs exhibit excellent activity and they are potential to synthesize polypeptoids with controllable polymerization.

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Section: Introductionmentioning

confidence: 99%

Are N‐substituted glycine N‐thiocarboxyanhydride monomers really hard to polymerize?

Tao

Zheng

Kricheldorf³

et al. 2016

J. Polym. Sci. Part A: Polym. Chem.

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“…2). Evidently, the polymerization was initiated by the BnNH 2 (and not by DIPEA or PhOH 27 ) and proceeded via the in situ formed Sar-NCA (and not via the Poc-Sar through polycondensation) as depicted in Scheme 1. Furthermore, the number-average molar mass of the polysarcosine was very close to the calculated molar mass, and the molar mass distribution was monomodal and narrow (Table 1).…”

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confidence: 99%

Synthesis of polysarcosine from air and moisture stable N-phenoxycarbonyl-N-methylglycine assisted by tertiary amine base

et al. 2016

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“…To investigate whether this method is useful SCHEME 3 TMG-promoted ROPs of Bu-NCAs using alcohol initiators to afford the linear PNBG polypeptoid. [62] Reprinted with permission from American Chemical Society with narrow dispersity and tunable ring sizes (Scheme 7). [37,66] The polymer molecular weight and the ring size can be adjusted by controlling the initial monomer to NHC feed ratio.…”

Section: Synthesis Of Linear Polypeptoidsmentioning

confidence: 99%

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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1,1,3,3-Tetramethylguanidine-Promoted Ring-Opening Polymerization of N-Butyl N-Carboxyanhydride Using Alcohol Initiators

Cited by 46 publications

References 71 publications

Are N‐substituted glycine N‐thiocarboxyanhydride monomers really hard to polymerize?

Are N‐substituted glycine N‐thiocarboxyanhydride monomers really hard to polymerize?

Synthesis of polysarcosine from air and moisture stable N-phenoxycarbonyl-N-methylglycine assisted by tertiary amine base

Polypeptoid polymers: Synthesis, characterization, and properties

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