Core−Shell Molecular Bottlebrushes with Helical Polypeptide Backbone: Synthesis, Characterization, and Solution Conformations

Tang, Haoyu; Li, Yuanchao; Lahasky, Samuel H.; Sheiko, Sergei S.; Zhang, Donghui

doi:10.1021/ma1025994

Cited by 91 publications

(72 citation statements)

References 40 publications

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“…This was attributed to the increased steric repulsion between side chains, which destabilized the helical backbone conformation. 52 This result was consistent with our previous work. 39 Furthermore, all graft polypeptides exhibited higher a-helical contents at DP 20 in water (>99%) ( Table 2), indicating that increasing the polypeptide backbone lengths was especially beneficial to stabilize a-helical structures.…”

supporting

confidence: 94%

Controlled metal‐free polymerization toward well‐defined thermoresponsive polypeptides by polymerization at low temperature

Jiang

Wang

Zhang

et al. 2016

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

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A controlled metal-free synthetic methodology toward well-defined thermoresponsive polypeptides by decreasing the reaction temperature to 0 8C has been developed. Good control over the molecular weight in the polymerization of a trithiocarbonate-functionalized N-carboxyanhydride (MES-L-Glu-NCA) monomer was obtained using n-hexylamine as the initiator at 0 8C. It yielded homopolypeptide macrotransfer agent (PMESLG) with narrow molecular weight distribution (PDI < 1.3) and controllable chain length. Detailed 1 H NMR and MALDI-TOF-MS analysis clearly confirmed that frequently occurring side-reactions was absent at 0 8C, and the polymerization was controlled. The resultant PMESLG was applied to mediate the reversible addition-fragmentation chain transfer (RAFT) polymerization of oligo-ethylene-glycol acrylate (OEGA) for the metal-free synthesis of thermoresponsive polypeptides. These thermoresponsive polypeptides have wellcontrolled molecular weight, adopted regular a-helical conformation, and exhibited a lower critical solution temperature between 23 8C and 55 8C. To the best of our knowledge, there are very few reports about the synthesis of well-defined thermoresponsive graft polypeptides via NCA polymerization and RAFT. Consequently, this provides a new strategy for the synthesis of promising intelligent material for future biomedical applications.

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supporting

confidence: 94%

Controlled metal‐free polymerization toward well‐defined thermoresponsive polypeptides by polymerization at low temperature

Jiang

Wang

Zhang

et al. 2016

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

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“…DBCs with hetero-grafted PEO and PLA side-chains were added to a water/toluene mixture and found to stabilize mini-emulsion droplets 127 . Zhang et al synthesized core-shell bottlebrush polymers using a grafting-onto synthesis 129 . PLA-b-PEG side-chains were attached to a poly(γ-propyl-l-glutamate) (PPLG) backbone using copper-catalysed azide-alkyne click coupling, resulting in bottlebrushes with grafting densities of 82 -93 %.…”

Section: Non-associating Bottlebrushes For Encapsulation and Deliverymentioning

confidence: 99%

Structure, function, self-assembly, and applications of bottlebrush copolymers

et al. 2015

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Bottlebrush polymers are a type of branched or graft polymer with polymeric side-chains attached to a linear backbone, and the unusual architecture of bottlebrushes provides a number of unique and potentially useful properties. These include a high entanglement molecular weight, enabling rapid self-assembly of bottlebrush block copolymers into large domain structures, the self-assembly of bottlebrush block copolymer micelles in a selective solvent even at very low dilutions, and the functionalization of bottlebrush side-chains for recognition, imaging, or drug 2 delivery in aqueous environments. This review article focuses on recent developments in the field of bottlebrush polymers with an emphasis on applications of bottlebrush copolymers.Bottlebrush copolymers contain two (or more) different types of polymeric side-chains. Recent work has explored the diverse properties and functions of bottlebrush polymers and copolymers in solutions, films, and melts, and applications explored include photonic materials, bottlebrush films for lithographic patterning, drug delivery, and tumor detection and imaging. We provide a brief introduction to bottlebrush synthesis and physical properties and then discuss work related to: i) bottlebrush self-assembly in melts and bulk thin films, ii) bottlebrushes for photonics and lithography, iii) bottlebrushes for small molecule encapsulation and delivery in solution, and iv) bottlebrush micelles and assemblies in solution. We briefly discuss three potential areas for future research, including developing a more quantitative model of bottlebrush self-assembly in the bulk, studying the properties of bottlebrushes at interfaces, and investigating the solution assembly of bottlebrush copolymers.

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“…Recently, Zhang et al [17], proposed the synthesis of well-defined core-shell molecular bottlebrushes (polydispersity index, PDI, between 1.02 and 1.03) with a helical poly(L-glutamate) backbone and polylactide-b-poly(ethylene glycol) block copolymer as side chains through the "grafting to" strategy and using the azide-alkyne Huisgen 1,3-dipolar cycloaddition. These core-shell brushes exhibited a wormlike conformation related to the retention of the α-helical conformation in both solution and solid state.…”

Section: Liquid-phase Peptide Synthesis Preparation Of Peptide-synthmentioning

confidence: 99%

“…Moreover, both peptides have the possibility to be hydrolyzed resulting in poly(L-glutamic acid) (PLGA) and poly(L-lysine) (PLL), which show pH-responsive behavior displaying coil to helix transitions depending on the pH of the medium. Specifically, PLGA adopts α-helical conformations at low pHs (i.e., pH ≤ 6.3), while PLL becomes α-helical at high pHs (i.e., pH ≥ 8.4) [17]. Scheme X. Schematic representation of the proposed model for the self-assembly of the rod-rod diblock copolymer in poorly ordered packing (a), hexagonal in lamella (b), and cylinder (d) structures, respectively.…”

Section: Supramolecular Organization Of Peptide-synthetic Polymer Hybmentioning

confidence: 99%

Hybrid Block Copolymers Constituted by Peptides and Synthetic Polymers: An Overview of Synthetic Approaches, Supramolecular Behavior and Potential Applications

Morell

Puiggalı́

2013

Polymers

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Hybrid block copolymers based on peptides and synthetic polymers, displaying different types of topologies, offer new possibilities to integrate the properties and functions of biomacromolecules and synthetic polymers in a single hybrid material. This review provides a current status report of the field concerning peptide-synthetic polymer hybrids. The first section is focused on the different synthetic approaches that have been used within the last three years for the preparation of peptide-polymer hybrids having different topologies. In the last two sections, the attractive properties, displayed in solution or in the solid state, together with the potential applications of this type of macromolecules or supramolecular systems are highlighted.

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Core−Shell Molecular Bottlebrushes with Helical Polypeptide Backbone: Synthesis, Characterization, and Solution Conformations

Cited by 91 publications

References 40 publications

Controlled metal‐free polymerization toward well‐defined thermoresponsive polypeptides by polymerization at low temperature

Controlled metal‐free polymerization toward well‐defined thermoresponsive polypeptides by polymerization at low temperature

Structure, function, self-assembly, and applications of bottlebrush copolymers

Hybrid Block Copolymers Constituted by Peptides and Synthetic Polymers: An Overview of Synthetic Approaches, Supramolecular Behavior and Potential Applications

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