Peptide-based lipid mimetics with tunable core properties via thiol–alkyne chemistry

Ray, Jacob G.; Ly, Jack; Savin, Daniel A.

doi:10.1039/c1py00003a

Cited by 35 publications

(42 citation statements)

References 27 publications

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“…11); three different thiol functionalized lipophilic moieties [octadecane (ODT), cholesterol (Chol), and polyhedral oligomeric silsequioxane (POSS)] were conjugated to PLGA (DP ¼11, 16, and 36). 99 We explored the pH-responsive self-assembly of these copolymers with DLS, SLS, and TEM as a function of pH. Figure 12 shows R h versus pH plots of these various assemblies as well as representative TEM images.…”

Section: Feature Articlementioning

confidence: 99%

“…We believe this assembly motif will be an effective platform for the design of polymer vehicles for hydrophilic drugs whereby there are no concerns about designing molecules with a certain hydrophilic fraction to facilitate vesicle formation. 98,99,118 Polypeptide-Based A 2 B Star Copolymers There have been a few recent reports on the aqueous self-assembly of peptide-based A 2 B star copolymers, with two hydrophilic peptide chains attached to a hydrophobic B block. 59,119 Ding and coworkers studied poly(N-isopropyl acrylamide)-b-(PLys) 2 (PNIPAM-b-(PLys) 2 ),coupled through azide-alkyne chemistry.…”

Section: Feature Articlementioning

confidence: 99%

“…Recently, our group utilized thiol-yne coupling chemistry to create polypeptide-based AB 2 star copolymers. 98,99 In our earliest report, we studied the kinetics and self-assembly of AB 2 star copolymers composed of dodecane thiol doubly conjugated (either convergently or divergently) with PLys. These materials were shown to produce pH-responsive vesicles.…”

Section: Feature Articlementioning

confidence: 99%

“…98,99 As illustrated in Scheme 3, both convergent and divergent synthetic strategies can be used to create this topology. Starting with propargyl amine, the convergent approach first uses the amine to initiate ROP of the NCA followed by UV-initiated, radical-mediated thiol-yne chemistry between the acetylene group and hydrophobic thiols.…”

Section: Synthetic Techniques For Polypeptide-based Copolymers With Tmentioning

confidence: 99%

“…Both synthetic routes have proven to be effective in achieving the desired AB 2 topology. 98,99 A 2 B star copolymers have been synthesized containing two hydrophilic peptide blocks attached to a hydrophobic polymer. 59,101 Both of these reports took advantage of controlled radical techniques to create synthetic polymers that could be efficiently used to couple to synthesized polypeptide blocks or used as macroinitiators for ROP of the NCA.…”

Section: Synthetic Techniques For Polypeptide-based Copolymers With Tmentioning

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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Section: Feature Articlementioning

confidence: 99%