Alkyne-X modification of polypeptoids

Secker, Christian; Robinson, Joshua W.; Schlaad, Helmut

doi:10.1016/j.eurpolymj.2014.08.028

Cited by 42 publications

(37 citation statements)

References 33 publications

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“…halides, sulfonates, carbonates, inorganic fluorides, perfluorinated sulfonimides, tricyanomethanide or dicyanamide). 33 The objective of this work is thus to enrich the structure/ properties relationship of this growing library by describing the synthesis of a new series of PTILs, relying on efficient postpolymerization sequential chemical modifications of preciselydefined chloride-functionalized polyacrylate and investigating the impact of different counter anions on their functional properties. They can be synthesized either by polymerization of IL monomers or by post-polymerization chemical modification of neutral polymers.…”

Section: Introductionmentioning

confidence: 99%

Triethylene glycol-based poly(1,2,3-triazolium acrylate)s with enhanced ionic conductivity

et al. 2015

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International audienceA series of cationic poly(acrylate ionic liquid)s having a triethylene glycol (TEG) spacer and a pendant 1,2,3-triazolium group is synthesized by post-polymerization sequential chemical modifications. A chloride-functionalized polyacrylate common precursor is first obtained by reversible addition-fragmentation chain transfer (RAFT) polymerization of a TEG-based chloride-functionalized acrylate. Sequential azidation, copper-catalyzed azide-alkyne cycloaddition with 1-pentyne and alkylation of the resulting 1,2,3-triazole by methyl iodide affords a poly(acrylate ionic liquid) having pendant 3-methyl-4-propyl-1,2,3-triazolium iodide groups. Further anion metathesis with three different fluorinated salts yields a series of 1,2,3-triazolium-based PILs with distinct counter anions. The polymer precursors and resulting poly(1,2,3-triazolium ionic liquid) s (PTILs) are characterized by H-1 NMR spectroscopy, size exclusion chromatography (SEC), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and broadband dielectric spectroscopy (BDS). Well-defined PTIL derivative with bis(trifluoromethane) sulfonimide anion (M-n = 113,600 g mol(-1) and D = 1.23) exhibits the lowest glass transition temperature (T-g = -36 degrees C), the highest thermal stability (T-d10 = 321 degrees C) and the highest anhydrous ionic conductivity (sigma(DC) = 1.1 x 10(-5) S cm(-1) at 30 degrees C) of the series

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Section: Introductionmentioning

confidence: 99%

Triethylene glycol-based poly(1,2,3-triazolium acrylate)s with enhanced ionic conductivity

et al. 2015

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“…Schlaad et al also reported that the resulting triazole moieties can be further quaternized with alkyl bromide to produce a polypeptoid ionic liquid (Scheme 9). [14] Apart from CuAAC, the propargyl N-substituents in PNPgG can also be deprotonated by strong base to initiate anionic ROP of ethylene oxide or serve to crosslink the polymer under heat. [79] The postpolymerization method proves to be an effective strategy to increase the N-substituent diversity of polypeptoids.…”

Section: Postpolymerization Modification Of Polypeptoidsmentioning

confidence: 99%

“…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.…”

Section: Introductionmentioning

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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“…The grafting efficiency was low for poly( N ‐propargyl glycine) homopolymers (<19%) and was significantly higher for poly[( N ‐propargyl glycine)‐ ran ‐( N ‐butyl glycine)] random copolymers (<94%), attributable to the different aggregation tendencies of the polymers in DMSO (reaction medium for CuAAC) which more or less restricts the access to the propargyl groups. Interestingly, the triazole linkers produced in CuAAC can be quaternized with alkyl bromide to yield a polypeptoid ionic liquid . Schlaad and coworkers also showed that the alkyne groups of poly( N ‐propargyl glycine) can be reacted with thiols (thiol‐yne chemistry) or deprotonated with strong phosphazene base ( t Bu‐P 4 ) and initiate anionic ROP of ethylene oxide …”

Section: Polypeptoid Synthesismentioning

confidence: 99%

“…Interestingly, the triazole linkers produced in CuAAC can be quaternized with alkyl bromide to yield a polypeptoid ionic liquid . Schlaad and coworkers also showed that the alkyne groups of poly( N ‐propargyl glycine) can be reacted with thiols (thiol‐yne chemistry) or deprotonated with strong phosphazene base ( t Bu‐P 4 ) and initiate anionic ROP of ethylene oxide …”

Section: Polypeptoid Synthesismentioning

confidence: 99%

Poly(α‐Peptoid)s Revisited: Synthesis, Properties, and Use as Biomaterial

Secker

Brosnan

Luxenhofer

et al. 2015

Macromolecular Bioscience

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Polypeptoids have been of great interest in the polymer science community since the early half of the last century; however, they had been basically forgotten materials until the last decades in which they have enjoyed an exciting revival. In this mini-review, we focus on the recent developments in polypeptoid chemistry, with particular focus on polymers synthesized by the ring-opening polymerization (ROP) of amino acid N-carboxyanhydrides (NCAs). Specifically, we will review traditional monomer synthesis (such as Leuchs, Katchalski, and Kricheldorf) and recent advances in polymerization methods to yield both linear, cyclic, and functional polymers, solution and bulk thermal properties, and preliminary results on the use of polypeptoids as biomaterials (i.e immunogenicity, biodistribution, degradability, and drug delivery).

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Alkyne-X modification of polypeptoids

Cited by 42 publications

References 33 publications

Triethylene glycol-based poly(1,2,3-triazolium acrylate)s with enhanced ionic conductivity

Triethylene glycol-based poly(1,2,3-triazolium acrylate)s with enhanced ionic conductivity

Polypeptoid polymers: Synthesis, characterization, and properties

Poly(α‐Peptoid)s Revisited: Synthesis, Properties, and Use as Biomaterial

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