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WIREs Nanomed Nanobiotechnol
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Preparation and development of block copolypeptide vesicles and hydrogels for biological and medical applications

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There have been many recent advances in the controlled polymerization of α‐amino acid‐N‐carboxyanhydride (NCA) monomers into well‐defined block copolypeptides. Transition metal initiating systems allow block copolypeptide synthesis with excellent control over number and lengths of block segments, chain length distribution, and chain‐end functionality. Using this and other methods, block copolypeptides of controlled dimensions have been prepared and their self‐assembly into organized structures studied by many research groups. The ability of well‐defined block copolypeptides to assemble into supramolecular copolypeptide vesicles and hydrogels has led to the development of these materials for use in biological and medical applications. These assemblies have been found to possess unique properties that are derived from the amino acid building blocks and ordered conformations of the polypeptide segments. Recent work on the incorporation of active and stimulus‐responsive functionality in these materials has tremendously increased their potential for use in biological and medical studies. This article is categorized under: Therapeutic Approaches and Drug Discovery > Emerging Technologies Implantable Materials and Surgical Technologies > Nanomaterials and Implants Implantable Materials and Surgical Technologies > Nanotechnology in Tissue Repair and Replacement Biology-Inspired Nanomaterials > Peptide-Based Structures

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(a) Schematic of experimental design to evaluate the release of nerve growth factor (NGF) from K180L20 hydrogel (diblock copolypeptide hydrogel, DCH) depots in vivo. NGF is known to induce hypertrophy of basal forebrain cholinergic (ChAT) neurons in the caudate putamen (CP) and medial septum (MS). Depots of DCH with NGF were injected into the CP on one side of the brain. (b) Effects of NGF released from DCH depots on local forebrain cholinergic neurons in ipsilateral caudate putamen. Graph shows mean cell area in mm2 of cholinergic neurons in various treatment groups and at various treatment times as indicated. n = 4 per group; *P < 0.01 relative to carrier only; **P < 0.01 for group comparisons as indicated; ns, nonsignificant; ANOVA with Newman–Keuls post hoc pair‐wise comparisons. (Reprinted with permission from Ref . Copyright 2012 Elsevier Ltd)
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(a) Schematic representations of block copolypeptide hydrogel composition and structure. Block copolypeptides are composed of variable‐length chains of hydrophilic (blue) and hydrophobic (red) amino acids. In aqueous solution, hydrophobic segments associate into elongated fibrillar assemblies that entangle to form three‐dimensional (3D) networks with hydrophilic segments exposed. (b) In aqueous solutions, hydrophobic segments associate to form elongated fibrillar tape‐like assemblies that branch and entangle to form 3D networks with hydrophilic segments exposed. (c–f) Light microscopic images of 3% K180L20 at 1 (c), 2 (d), 4 (e), and 8 (f) weeks after injection of 2 μL into the striatum in cresyl violet‐stained tissue sections showing time‐dependent migration of cells into block copolypeptide hydrogel deposits in vivo. Essentially no cells are present in the deposits after 1 week in vivo (c). After 2 weeks in vivo (d), a number of cells have migrated into, and are scattered throughout the deposits and after 4 (e) and 8 weeks (f) the deposits are densely packed with cells. Arrowheads indicate the borders of deposit and host tissue. Scale bar: c–f = 25 mm. (Reprinted with permission from Ref . Copyright 2009 Elsevier Ltd)
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Schematic showing (a) structure and redox properties, (b) self‐assembly of MO65(L0.5/F0.5)20 copolypeptides into vesicles, and (c) proposed enzymatic rupture of vesicles. (Reprinted with permission from Ref . Copyright 2013 American Chemical Society)
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(a) Structure and schematic of R60L20 block copolypeptides. (b) Schematic of proposed vesicle self‐assembled structure. (c) Laser scanning confocal microscopy (LSCM) image of 1.0‐µm extruded vesicles (bar = 5 µm). (Reprinted with permission from Ref . Copyright 2007 Nature Publishing Group)
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(a) Polymerization of α‐amino acid‐N‐carboxyanhydride (NCA) monomers into polypeptides. (b) Formation of active species in transition metal‐initiated NCA polymerization. (c) Stepwise batch formation of triblock copolypeptides by successive addition of different NCA monomers to a cobalt initiator.
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Implantable Materials and Surgical Technologies > Nanomaterials and Implants
Therapeutic Approaches and Drug Discovery > Emerging Technologies
Implantable Materials and Surgical Technologies > Nanotechnology in Tissue Repair and Replacement
Biology-Inspired Nanomaterials > Peptide-Based Structures

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