Sequence Programmable Peptoid Polymers for Diverse Materials Applications

Knight, Abigail; Zhou, Effie Y.; Francis, Matthew B.; Zuckermann, Ronald N.

doi:10.1002/adma.201500275

Cited by 207 publications

(229 citation statements)

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“…[67] In dilute methanol solution at room temperature, the cyclic PNMG 105 appropriate substrates where the monomer sequence is defined during the substrate design and synthesis. These methods may complement the stepwise synthetic strategy (ie, submonomer method) [118] commonly used to access sequence-specific oligomeric peptoids. Design and synthesis of hybrid polymeric materials comprises polypeptoid segments will also be a fruitful ground for future research.…”

Section: Immunogenicitymentioning

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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Section: Immunogenicitymentioning

confidence: 99%

Polypeptoid polymers: Synthesis, characterization, and properties

et al. 2017

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“…Ethyl methacrylate (EMA) was polymerized via RAFT technique in the presence of synthesized RAFT agent. To investigate effect of synthesized CTA on the structure and properties of polymer, monomer conversion, molecular weight, molecular weight distribution, chemical structure, and thermal behavior of synthesized polymers via RAFT and TRP mechanisms were studied via FT-IR, 1 H NMR, and 13 C NMR, gel permeation chromatography (GPC), and thermogravimetric analysis (TGA).…”

Section: Synthesis and Characterization Of Raft Agentmentioning

confidence: 99%

“…[1][2][3][4] Controlled/'living' radical polymerization (CLRP) techniques based on the common concept of alternating activation/deactivation processes are successful and efficient mechanisms to design structure and functionality in polymers with controlled molecular weight and narrow dispersity. [5][6][7][8] Among CLRP techniques, reversible addition-fragmentation chain transfer (RAFT) polymerization is one of the most versatile processes.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis and characterization of diethyl-dithiocarbamic acid 2-[4-(2-diethylthiocarbamoylsulfanyl-2-phenyl-acetyl)-2,5-dioxo-piperazin-1-yl]-2-oxo-1-phenyl-ethyl ester as new reversible addition-fragmentation chain transfer agent for polymerization of ethyl methacrylate

Abdollahi

Abdouss

Salami‐Kalajahi

et al. 2015

Designed Monomers and Polymers

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-Nezhad (2016) Synthesis and characterization of diethyl-dithiocarbamic acid 2-[4-(2-diethylthiocarbamoylsulfanyl-2-phenyl-acetyl)-2,5-dioxo-piperazin-1-yl]-2-oxo-1-phenyl-ethyl ester as new reversible addition-fragmentation chain transfer agent for polymerization of ethyl methacrylate, Designed Monomers and Polymers, 19:1, 56-66, DOI: 10.1080/15685551.2015 C NMR, FT-IR, elemental analysis, and melting point technique. Then, ethyl methacrylate was synthesized via free radical and RAFT polymerizations. To investigate the effect of the RAFT agent on the kinetic of polymerization, molecular weight, and polydispersity index (PDI) of polymers and also monomer conversion were monitored. Also, synthesized polymers were characterized by 1 H NMR, 13 C NMR, FT-IR, and TGA. Characterization analyses of synthesized RAFT agent were consistent with the structure. NMR and FTIR analyses confirmed end group incorporation of RAFT agent into polymer structure. According to results, poly(ethyl methacrylate) with low PDI (1.14) was obtained. Kinetic study indicated well-controlled polymerization of ethyl methacrylate by synthesized RAFT agent. TGA results showed that RAFT agent could reduce termination reactions and so reduce head-to-head bonds and chain-end unsaturation by keeping the concentration of radicals low enough.

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“…

The potential for chemical diversity of peptoid polymers was immediately apparent upon their development [1]. Appreciation for their structural diversity has been developing more slowly.

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confidence: 99%

TEM Investigations of Peptoid Structures

et al. 2017

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The potential for chemical diversity of peptoid polymers was immediately apparent upon their development [1]. Appreciation for their structural diversity has been developing more slowly. We have used EM imaging and electron diffraction to study some of these novel structures.Peptoids are similar to peptides in having the same carbon-nitrogen backbone. The differences derive from the fact that peptoid sidechains are attached to the nitrogen, rather than carbon as in peptides. With no resultant mechanism for forming the hydrogen bonds that stabilize helical structures in proteins, the expectations for secondary structures in peptoids are much more limited than in proteins. However the range of peptoid side chains is vastly greater than the 20 natural amino acids, which has led to a wide variety of self-assembling peptoid aggregates and ordered arrays. In recent years, a wide variety of peptoid polymers have been shown to be crystalline in the solid state. Inspired by successes and limitations of conventional polymer chemistry in developing membranes suitable for applications such as fuel cells and batteries, we have investigated use of the peptoid backbone as a scaffold for constructing membranes with better control of composition and properties. The overall goal is to obtain membranes with enhanced mechanical and electrical properties, starting from our current understanding of polymers such as polystyrene and polyethylene. Many membranes have been formed with derivatives of these as diblock copolymers containing hydrophilic and hydrophobic blocks. We have synthesized various polypeptoids with corresponding diblock motifs, taking advantage of the sequence specificity of peptoids.One of the first membrane-forming peptoids we looked at is based on alkyl/ethyleneoxy sidechain blocks. A surprise upon visualizing this material by cryo-EM was the appearance of tubes with a prominent 2.4-nm axial repeat that corresponds to the distance expected between backbones [2]. Figure 1 shows the chemical structure and an image of this material. A model for a single-layered structure was proposed (Fig. 1C), based on the idea that the molecules assemble as tiles in a highly ordered structure. Variants of this material also form thin, apparently monolayer sheets, from which we have obtained high resolution images and which show electron diffraction spots to at least 0.2 nm in addition to the 2.4 nm repeat (Fig. 1D). It appears that in the sheets the side chains run roughly perpendicular to the plane of the sheet, but we do not yet have an atomic model that accounts for all features in the diffraction patterns. Higher resolution imaging should lead to development of an accurate model.The most widely studied electrolyte membranes are based on sulfonated polymers such as Nafion. However, most sulfonic acid-based membranes are poor proton transporters, since very little water is retained at the high temperatures required for operation. Phosphonated polymers are attractive systems because they exhibit efficient proton transport under lo...

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Sequence Programmable Peptoid Polymers for Diverse Materials Applications

Cited by 207 publications

References 224 publications

Polypeptoid polymers: Synthesis, characterization, and properties

Polypeptoid polymers: Synthesis, characterization, and properties

Synthesis and characterization of diethyl-dithiocarbamic acid 2-[4-(2-diethylthiocarbamoylsulfanyl-2-phenyl-acetyl)-2,5-dioxo-piperazin-1-yl]-2-oxo-1-phenyl-ethyl ester as new reversible addition-fragmentation chain transfer agent for polymerization of ethyl methacrylate

TEM Investigations of Peptoid Structures

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