Reversible Inside−Out Micellization of pH-responsive and Water-Soluble Vesicles Based on Polypeptide Diblock Copolymers

Rodríguez‐Hernández, Juan; Lecommandoux, Sébastien

doi:10.1021/ja043920g

Cited by 658 publications

(566 citation statements)

References 17 publications

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“…76 Lecommandoux and coworkers have reported schizophrenic behavior of double hydrophilic block copolymers (DHBCs) with two pH-responsive blocks. 68,72 In one report, they demonstrate reversible vesicle formation for a symmetric, zwitterionic PLGA 15 -b-PLys 15 copolypeptide. 72 Under mild pH conditions (5-9), conditions where both blocks have some degree of charged side groups, the chains existed as individual unimers.…”

Section: Assembly and Responsiveness Of Peptide-based Diblock Copolymersmentioning

confidence: 97%

“…68,72 In one report, they demonstrate reversible vesicle formation for a symmetric, zwitterionic PLGA 15 -b-PLys 15 copolypeptide. 72 Under mild pH conditions (5-9), conditions where both blocks have some degree of charged side groups, the chains existed as individual unimers. At low pH, the vesicles were comprised of charged PLys coronas and hydrophobic PLGA cores, whereas the corona and core blocks were reversed under alkaline conditions.…”

Section: Assembly and Responsiveness Of Peptide-based Diblock Copolymersmentioning

confidence: 97%

“…[55][56][57] Assemblies with Polypeptide Coronas The past two decades have seen several literature reports of aqueous assembly of block copolymers with peptide corona chains, whereby responsiveness is governed in part by changes in the secondary structure. 11,42,[58][59][60][61][62][63][64][65][66][67][68][69][70][71][72] Much of this research focus has been devoted to pH-responsive block copolymers containing peptides such as poly(L-lysine) (PLys) (pKa 10.3) 73 and poly(L-glutamic acid) (PLGA) (pKa 4.3) 70 which exhibit helix-coil transitions associated with the charged state of the amino or carboxylic acid side chains of PLys and PGlu respectively.…”

Section: Assembly and Responsiveness Of Peptide-based Diblock Copolymersmentioning

confidence: 99%

“…They additionally discuss the importance of the rod-like character in the hydrophobic peptide block (at either pH extreme) serving to drive the formation of flatter interface assemblies. 72 …”

Section: Assembly and Responsiveness Of Peptide-based Diblock Copolymersmentioning

confidence: 99%

See 3 more Smart Citations

Self‐assembly and responsiveness of polypeptide‐based block copolymers: How “Smart” behavior and topological complexity yield unique assembly in aqueous media

Ray¹,

Johnson²,

Savin³

2013

J Polym Sci B Polym Phys

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Polypeptide-based amphiphilic block copolymers are an attractive class of materials given their ability to form welldefined aqueous nanoassemblies that respond to external stimulus through secondary structure transitions. This report will highlight recent literature in the area of polypeptide-based block copolymer self-assembly, with the major focus being on how the responsive nature and structural complexity of the polypeptide blocks can be incorporated into systems with complex topologies such as ABA/BAB/ABC triblock copolymers, AB 2 and A 2 B star copolymers, and miktoarm l-ABC star terpolymers. In particular, the role of interfacial curvature changes and how they result in morphology transitions will be discussed. The 'smart' assembly properties of peptides in complex block copolymer topologies can lead to enhanced responsiveness, morphological complexity, and unique morphological transitions with varying solution conditions. V C 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013, 51, 508-523 KEYWORDS: amphiphiles; biomimetic; block copolymers; selfassembly INTRODUCTION Amphiphilic block copolymers are able to self-assemble into well-defined nanostructures in aqueous solution. [1][2][3][4][5] The equilibrium morphology and aggregation number of diblock copolymer assemblies is primarily determined by the balance of three energetic factors: (1) interfacial tension, (2) corona chain crowding, and (3) core chain stretching. The balance of these three factors dictates an equilibrium curvature for the aggregate. 6-8 Typically, solution morphologies formed by amphiphilic block copolymers follow a trend of increasing interfacial curvature. As the hydrophilic fraction is increased in the copolymer, vesicles, cylindrical micelles, and spherical micelles (in the order of increasing interfacial curvature,) are the most common morphologies (Figure 1). 5,9,10 Physically, this is explained as a balance between entropic freedom of the hydrophilic coronal chains and shielding of the hydrophobic blocks from the aqueous solution; as the hydrophilic fraction increases, the chains are more able to effectively stabilize these assemblies without close-packing, and the free energy of the system is lowered when the coronal chains are provided more entropic freedom/mobility through increased curvature.

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Section: Assembly and Responsiveness Of Peptide-based Diblock Copolymersmentioning

confidence: 97%

Section: Assembly and Responsiveness Of Peptide-based Diblock Copolymersmentioning

confidence: 97%

Section: Assembly and Responsiveness Of Peptide-based Diblock Copolymersmentioning

confidence: 99%

Section: Assembly and Responsiveness Of Peptide-based Diblock Copolymersmentioning

confidence: 99%

See 2 more Smart Citations

Self‐assembly and responsiveness of polypeptide‐based block copolymers: How “Smart” behavior and topological complexity yield unique assembly in aqueous media

Ray¹,

Johnson²,

Savin³

2013

J Polym Sci B Polym Phys

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“…One of the first bioinspired functions of artificial cell membrane to be investigated in self‐assembled systems was the ability to respond to internal stimuli such as the presence of biomolecules and enzymes,9, 10, 11, 12, 13, 14, 15 redox conditions,16, 17, 18 or ionic strength19 and pH20, 21, 22, 23 of the environment and external stimuli such as light24, 25 or temperature26, 27 to control the transport behaviors. Most of these “smart” systems developed were used to elicit cargo release by a single stimulus 28…”

Section: Introductionmentioning

confidence: 99%

Photo‐Cross‐Linked Dual‐Responsive Hollow Capsules Mimicking Cell Membrane for Controllable Cargo Post‐Encapsulation and Release

et al. 2016

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Multifunctional and responsive hollow capsules are ideal candidates to establish highly sophisticated compartments mimicking cell membranes for controllable bio‐inspired functions. For this purpose pH and temperature dual‐responsive and photo‐cross‐linked hollow capsules, based on silica‐templated layer‐by‐layer approach by using poly(N‐isopropyl acrylamide)‐block‐polymethacrylate) and polyallylamine, have been prepared to use them for the subsequent and easily available post‐encapsulation process of protein‐like macromolecules at room temperature and pH 7.4 and their controllable release triggered by stimuli. The uptake and release properties of the hollow capsules for cargos are highly affected by changes in the external stimuli temperature (25, 37, or 45 °C) and internal stimuli pH of the phosphate‐containing buffer solution (5.5 or 7.4), by the degree of photo‐cross‐linking, and the size of cargo. The photo‐cross‐linked and dual stimuli‐responsive hollow capsules with different membrane permeability can be considered as attractive material for mimicking cell functions triggered by controllable uptake and release of different up to 11 nm sized biomolecules.

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Bioinspired Polymers

LoPresti¹,

Battaglia²

2009

Encyclopedia of Polymer Science and Technology

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Nature has always been a font of inspiration for scientists. Biological systems have an amazingly wide spectrum of different ordered structures that show sophisticated and efficient functions. Inspiring either from natural biomaterials functions or structure, different classes of high performance polymeric materials have been developed (hi‐tech adhesives, self‐healing composites, dynamic lenses, synthetic polypeptides, etc.) with applications ranging from aerospace industry to drug delivery and artificial motion. After a rapid discussion of the most important bioinspired polymers, our attention in this review has been focused on biomimetic polymers with biomedical applications. A first section is dedicated to self‐assembling systems such as block copolymers and protein‐like polymers, whose functioning is based on supramolecular interactions. The second part is related to biomimetic molecular machines able to convert chemical energy into mechanical work, inspiring from biological machineries both at the microscopic level (cell trafficking and metabolism) and at the macroscopic scale (mammalian muscles and invertebrates motion).

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Reversible Inside−Out Micellization of pH-responsive and Water-Soluble Vesicles Based on Polypeptide Diblock Copolymers

Cited by 658 publications

References 17 publications

Self‐assembly and responsiveness of polypeptide‐based block copolymers: How “Smart” behavior and topological complexity yield unique assembly in aqueous media

Self‐assembly and responsiveness of polypeptide‐based block copolymers: How “Smart” behavior and topological complexity yield unique assembly in aqueous media

Photo‐Cross‐Linked Dual‐Responsive Hollow Capsules Mimicking Cell Membrane for Controllable Cargo Post‐Encapsulation and Release

Bioinspired Polymers

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