Stimuli‐Responsive Peptide‐Based ABA‐Triblock Copolymers: Unique Morphology Transitions With pH

Ray, Jacob G.; Naik, Sandeep; Hoff, Emily A.; Johnson, Ashley J.; Ly, Jack; Easterling, Charles P.; Patton, Derek L.; Savin, Daniel A.

doi:10.1002/marc.201100881

Cited by 39 publications

(38 citation statements)

References 45 publications

(71 reference statements)

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“…In this way, triblock copolymers with a degree of polymerization of the polylysine segments ranging from 27 to 46 were obtained and used to study the micelle-to-vesicle or micelle-to-disk transitions as function of pH. The unique responsive behavior of such system could be exploited in areas such as drug delivery, whereby a delivered drug could be spontaneously released upon pH-driven morphology transitions [29].…”

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

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

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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“…In addition, it is possible to exploit the use of ''click" reactions for more complex structures in a modular fashion. ABA triblock copolymers have been synthesized using the direct approach of initiating polymerization of an NCA using a diamino-functional macroinitiator (Scheme 1) 16,20,90 This topology contains hydrophilic polypeptide outer A blocks and a synthetic hydrophobic inner B block. In many of these cases, commercially available JeffamineV R polymers are used as the diamine.…”

Section: Synthetic Techniques For Polypeptide-based Copolymers With Tmentioning

confidence: 99%

“…16 Within our studies, we looked at three triblock copolymers: KPK27, KPK46, and KPK52. In-depth light scattering (DLS and SLS) and microscopy (TEM and AFM) techniques as well as circular dichroism spectroscopy were used to fully characterize the behavior of these systems.…”

Section: Synthetic Techniques For Polypeptide-based Copolymers With Tmentioning

confidence: 99%

“…11 The theoretical sizes of vesicles and worm-like micelles are difficult to predict, yet the thickness of these types of assemblies is often dictated by the chain length of the hydrophobic blocks. 12 Other non-typical morphologies such as multi-compartment micelles, [13][14][15] disk micelles, [16][17][18][19] nanotubes, 20 toroidal micelles, 21,22 bicontinuous micelles, 23,24 and corkscrew micelles 25 have been observed, often arising through structural complexity, solvent composition, or specific interactions.…”

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confidence: 99%

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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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“…[1][2][3][4] Changes of conformation and physical properties of the stimuli-sensitive component induced self-assembly of the block copolymers into micelle-like structures consisting of a hydrophobic core and a hydrophilic corona, which could serve as an efficient drug and gene delivery agent, and meanwhile could also prompt disassociation of polymeric micelles. [5][6][7][8] Synthetic block polymers in which each block possessed element responsive to different stimuli were extensively investigated.…”

Section: Introductionmentioning

confidence: 99%

Chemoenzymatic Synthesis of Dual-responsive Amphiphilic Block Copolymers and Drug Release Studies

Chen¹,

Li²,

Wang³

et al. 2013

Bulletin of the Korean Chemical Society

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Dual-responsive amphiphilic block copolymers were synthesized by combining enzymatic ring-opening polymerization (eROP) of ε-caprolactone (CL) and ATRP of N,N-dimethylamino-2-ethyl methacrylate (DMAEMA). The obtained block copolymers were characterized by gel permeation chromatography (GPC), 1 H NMR and FTIR-IR. The critical micelle concentration (CMC) of copolymer was determined by fluorescence spectra, it can be found that with hydrophilic block (PDMAEMA) increasing, CMC value of the polymer sample increased accordingly, and the CMC value was 0.012 mg/mL, 0.025 mg/mL and 0.037 mg/ mL for PCL 50 -b-PDMAEMA 68 , PCL 50 -b-PDMAEMA 89 , PCL 50 -b-PDMAEMA 112 , PCL 50 -b-PDMAEMA 89 was chosen as drug carrier to study in vitro release profile of anti-cancer drug (taxol). The temperature and pH dependence of the values of hydrodynamic diameter (Dh) of micelles, and self-assembly of the resulting block copolymers in water were evaluated by dynamic light scattering (DLS). The result showed that with the temperature increasing and pH decreasing, the Dh decreased. Drug-loaded nanoparticles were fabricated using paclitaxel as model. Transmission electron microscopy (TEM) and atomic force microscopy (AFM) had been explored to study the morphology of the hollow micelles and the nanoparticles, revealing well-dispersed spheres with the average diameters both around 80 nm. In vitro release kinetics of paclitaxel from the nanoparticles was also investigated in different conditions (pH and temperature, etc.), revealing that the drug release was triggered by temperature changes upon the lower critical solution temperature (LCST) at pH 7.4, and at 37 °C by an increase of pH.

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Stimuli‐Responsive Peptide‐Based ABA‐Triblock Copolymers: Unique Morphology Transitions With pH

Cited by 39 publications

References 45 publications

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

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

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

Chemoenzymatic Synthesis of Dual-responsive Amphiphilic Block Copolymers and Drug Release Studies

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