Polypeptoid Brushes by Surface-Initiated Polymerization of N-Substituted Glycine <i>N</i>-Carboxyanhydrides

Schneider, Maximilian; Fetsch, Corinna; Amin, Ihsan; Jordan, Rainer; Luxenhofer, Robert

doi:10.1021/la4009174

Cited by 57 publications

(53 citation statements)

References 49 publications

(110 reference statements)

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“…Zhang and co-workers conducted N-heterocyclic carbene-mediated living polymerization of N-substituted glycine NCAs, which produced cyclic PSar-b-PNBG block copolymers with quantitative yields and low PDIs. 66 In this work, we prepared P(Sar-r-NBG) random copolymers through the primary-amine initiated polymerization of N-substituted glycine NTAs. 65 The polymers self-assembled in aqueous solution, and were used as emulsifiers, micelles, or polymersomes with a hydrophilic corona and a hydrophobic core or membrane.…”

Section: Synthesis and Characterization Of P(sar-r-nbg)mentioning

confidence: 99%

Polypeptoids with tunable cloud point temperatures synthesized from N-substituted glycine N-thiocarboxyanhydrides

Tao

Wang

et al. 2015

Polym. Chem.

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N-substituted glycine N-thiocarboxyanhydrides (NTAs) are alternative monomers for preparing polypeptoids. With an easy synthetic approach and stability during purification and storage, they have much more potential for mass production than the corresponding N-carboxyanhydrides (NCAs). Thermoresponsive copolypeptoids are synthesized by copolymerization of sarcosine NTA (Sar-NTA) with N-butylglycine NTA (NBG-NTA) initiated by benzylamine in THF at 60°C. Polypeptoids with a degree of polymerization over 150 are obtained for the first time through primary amine-initiated NTA polymerizations. The molecular weights (MWs) and compositions of poly(sarcosine-r-N-butylglycine)s [P(Sar-r-NBG)s] are controlled by the feed molar ratios of [Sar]/[NBG]/[benzylamine]. The thermal behaviors of the copolypeptoids are investigated. Reactivity ratios of Sar-NTA and NBG-NTA are determined as 1.70(7) and 0.63(7), indicating a random distribution of the two monomers in the polypeptoid products. The structure and precise amino chain end of P(Sar-r-NBG) are confirmed by MALDI-ToF mass analysis. P(Sar-r-NBG)s have lower critical solution temperatures (LCST) and exhibit reversible phase transitions in aqueous solution. Their cloud point temperatures (T cp s) are tunable between 27 and 71°C by adjusting the sarcosine molar fraction in copolymers. In addition, T cp transitions depend on the MWs and the concentrations of the polypeptoids,as well as salt additives, to a certain degree. A biocompatibility study on P(Sar-r-NBG) reveals a controlled cytotoxicity related to the composition of polypeptoids. Easily accessible from NTA polymerizations, polypeptoids are therefore novel degradable materials with LCST for biomedical applications. † Electronic supplementary information (ESI) available. See

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Section: Synthesis and Characterization Of P(sar-r-nbg)mentioning

confidence: 99%

Polypeptoids with tunable cloud point temperatures synthesized from N-substituted glycine N-thiocarboxyanhydrides

Tao

Wang

et al. 2015

Polym. Chem.

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“…[58] The surface-confined polymerization of Me-NCAs and Bu-NCAs using a surface-tethered primary amine initiator has also been investigated by Luxenhofer and Jordan et al to produce hydrophilic, hydrophobic, or amphiphilic polypeptoid homopolymer or block copolymer brushes. [59] Polypeptoid thin films up to 40 nm can be produced by this method. Surface-confined growth of polypeptoid brushes in conjunction with micro-patterning has also enabled access to micro-patterned polypeptoid thin films.…”

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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“…However, the need for purification after each step, and the possible detrimental influence of the surface on chemical reactions could be problematic. Recently, surface-initiated polymerization (SIP) reactions (Islam et al 2014; Lei et al 2014; Wang et al 2011) have been demonstrated to occur on various forms of solid substrates (bulk surface, powders, and nanoparticles) composed of gold (Yenice et al 2015), silica (Prucker and Ruhe 1998a; Prucker and Ruhe 1998b; Schneider et al 2013), or fumed silica (Hou et al 2010). …”

Section: Introductionmentioning

confidence: 99%

Surface-initiated ring-opening metathesis polymerization (SI-ROMP) to attach a tethered organic corona onto CdSe/ZnS core/shell quantum dots

Vatansever

Hamblin

2016

J Nanopart Res

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Core–shell CdSe/ZnS quantum dots (QDs) are useful as tunable photostable fluorophores for multiple applications in industry, biology, and medicine. However, to achieve the optimum optical properties, the surface of the QDs must be passivated to remove charged sites that might bind extraneous substances and allow aggregation. Here we describe a method of growing an organic polymer corona onto the QD surface using the bottom-up approach of surface-initiated ring-opening metathesis polymerization (SI-ROMP) with Grubbs catalyst. CdSe/ZnS QDs were first coated with mercaptopropionic acid by displacing the original trioctylphosphine oxide layer, and then reacted with 7-octenyl dimethyl chlorosilane. The resulting octenyl double bonds allowed the attachment of ruthenium alkylidene groups as a catalyst. A subsequent metathesis reaction with strained bicyclic monomers (norbornene-dicarbonyl chloride (NDC), and a mixture of NDC and norbornenylethylisobutyl-polyhedral oligomeric silsesquioxane (norbornoPOSS)) allowed the construction of tethered organic homo-polymer or co-polymer layers onto the QD. Compounds were characterized by FT-IR, 1H-NMR, X-ray photoelectron spectroscopy, differential scanning calorimetry, and transmission electron microscopy. Atomic force microscopy showed that the coated QDs were separate and non-aggregated with a range of diameter of 48–53 nm.

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Polypeptoid Brushes by Surface-Initiated Polymerization of N-Substituted Glycine N-Carboxyanhydrides

Cited by 57 publications

References 49 publications

Polypeptoids with tunable cloud point temperatures synthesized from N-substituted glycine N-thiocarboxyanhydrides

Polypeptoids with tunable cloud point temperatures synthesized from N-substituted glycine N-thiocarboxyanhydrides

Polypeptoid polymers: Synthesis, characterization, and properties

Surface-initiated ring-opening metathesis polymerization (SI-ROMP) to attach a tethered organic corona onto CdSe/ZnS core/shell quantum dots

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