Mixing Block Copolymers with Phospholipids at the Nanoscale: From Hybrid Polymer/Lipid Wormlike Micelles to Vesicles Presenting Lipid Nanodomains.

Hybrids, i.e., intimately mixed polymer/phospholipid vesicles, can potentially marry in a single membrane the best characteristics of the two separate components. The ability of amphiphilic copolymers and phospholipids to self-assemble into hybrid membranes has been studied until now on the submicrometer scale using optical microscopy on giant hybrid unilamellar vesicles (GHUVs), but limited information is available on large hybrid unilamellar vesicles (LHUVs). In this work, copolymers based on poly(dimethylsiloxane) and poly(ethylene oxide) with different molar masses and architectures (graft, triblock) were associated with 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC). Classical protocols of LUV formation were used to obtain nanosized self-assembled structures. Using small-angle neutron scattering (SANS), time-resolved Förster resonance energy transfer (TR-FRET), and cryo-transmission electron microscopy (cryo-TEM), we show that copolymer architecture and molar mass have direct influences on the formation of hybrid nanostructures that can range from wormlike hybrid micelles to hybrid vesicles presenting small lipid nanodomains.

[1]  M. Prieto,et al.  Modulation of phase separation at the micron scale and nanoscale in giant polymer/lipid hybrid unilamellar vesicles (GHUVs). , 2017, Soft matter.

[2]  R. Kraut,et al.  Magneto-Thermal Release from Nanoscale Unilamellar Hybrid Vesicles , 2016 .

[3]  M. Libera,et al.  Chimeric lipid/block copolymer nanovesicles: Physico-chemical and bio-compatibility evaluation. , 2016, European journal of pharmaceutics and biopharmaceutics : official journal of Arbeitsgemeinschaft fur Pharmazeutische Verfahrenstechnik e.V.

[4]  Sanobar Khan,et al.  Durable proteo-hybrid vesicles for the extended functional lifetime of membrane proteins in bionanotechnology† †Electronic supplementary information (ESI) available: Additional supporting data and experimental methods. See DOI: 10.1039/c6cc04207d Click here for additional data file. , 2016, Chemical communications.

[5]  Matthias Schulz,et al.  Mixed Hybrid Lipid/Polymer Vesicles as a Novel Membrane Platform. , 2015, Macromolecular rapid communications.

[6]  Frederick A. Heberle,et al.  Scattering from phase-separated vesicles. I. An analytical form factor for multiple static domains , 2015 .

[7]  K. Goldie,et al.  Phospholipid-polymer amphiphile hybrid assemblies and their interaction with macrophages. , 2015, Biomicrofluidics.

[8]  M. Prieto,et al.  Phase Separation and Nanodomain Formation in Hybrid Polymer/Lipid Vesicles. , 2015, ACS macro letters.

[9]  Fabian Itel,et al.  Molecular Organization and Dynamics in Polymersome Membranes: A Lateral Diffusion Study , 2014 .

[10]  X. Qiu,et al.  Temperature-responsive telechelic dipalmitoylglyceryl poly(N-isopropylacrylamide) vesicles: real-time morphology observation in aqueous suspension and in the presence of giant liposomes. , 2014, Chemical communications.

[11]  Xiao Hu,et al.  Impact of amphiphilic triblock copolymers on stability and permeability of phospholipid/polymer hybrid vesicles , 2014 .

[12]  L. Bergström,et al.  Spontaneous transformations between surfactant bilayers of different topologies observed in mixtures of sodium octyl sulfate and hexadecyltrimethylammonium bromide. , 2014, Langmuir : the ACS journal of surfaces and colloids.

[13]  W. Paxton,et al.  Salt, shake, fuse--giant hybrid polymer/lipid vesicles through mechanically activated fusion. , 2014, Angewandte Chemie.

[14]  M. Schulz,et al.  Lateral surface engineering of hybrid lipid-BCP vesicles and selective nanoparticle embedding. , 2014, Soft matter.

[15]  L. Mori,et al.  Hybrid polymersomes: facile manipulation of vesicular surfaces for enhancing cellular interaction. , 2013, Journal of materials chemistry. B.

[16]  Olivier Sandre,et al.  Hybrid polymer/lipid vesicles: state of the art and future perspectives , 2013, Materials Today.

[17]  B. Liedberg,et al.  Hybrid, Nanoscale Phospholipid/Block Copolymer Vesicles , 2013 .

[18]  K. Landfester,et al.  Submicron hybrid vesicles consisting of polymer-lipid and polymer-cholesterol blends , 2013 .

[19]  Keishi Suga,et al.  Detection of nanosized ordered domains in DOPC/DPPC and DOPC/Ch binary lipid mixture systems of large unilamellar vesicles using a TEMPO quenching method. , 2013, Langmuir : the ACS journal of surfaces and colloids.

[20]  Stergios Pispas,et al.  PEO-b-PCL–DPPC chimeric nanocarriers: self-assembly aspects in aqueous and biological media and drug incorporation , 2013 .

[21]  Frederick A. Heberle,et al.  Bilayer thickness mismatch controls domain size in model membranes. , 2013, Journal of the American Chemical Society.

[22]  G. Feigenson,et al.  Hybrid and nonhybrid lipids exert common effects on membrane raft size and morphology. , 2013, Journal of the American Chemical Society.

[23]  L. Johansson,et al.  Dynamics and size of cross-linking-induced lipid nanodomains in model membranes. , 2012, Biophysical Journal.

[24]  Olivier Sandre,et al.  Hybrid polymer/lipid vesicles: fine control of the lipid and polymer distribution in the binary membrane , 2012 .

[25]  L. Johansson,et al.  Limitations of electronic energy transfer in the determination of lipid nanodomain sizes. , 2011, Biophysical journal.

[26]  D. Hammer,et al.  Improved tumor targeting of polymer-based nanovesicles using polymer-lipid blends. , 2011, Bioconjugate chemistry.

[27]  M. Schulz,et al.  Hybrid lipid/polymer giant unilamellar vesicles: effects of incorporated biocompatible PIB–PEO block copolymers on vesicle properties , 2011 .

[28]  T. Vanderlick,et al.  Giant phospholipid/block copolymer hybrid vesicles: mixing behavior and domain formation. , 2011, Langmuir : the ACS journal of surfaces and colloids.

[29]  N. Kučerka,et al.  Scattering from laterally heterogeneous vesicles. II. The form factor , 2007 .

[30]  Manuel Prieto,et al.  Lipid rafts have different sizes depending on membrane composition: a time-resolved fluorescence resonance energy transfer study. , 2005, Journal of molecular biology.

[31]  J. Nagle,et al.  Structure of lipid bilayers. , 2000, Biochimica et biophysica acta.

[32]  F. MacKintosh,et al.  Stability and Phase Behavior of Mixed Surfactant Vesicles , 1991 .

[33]  Kell Mortensen,et al.  Analytical treatment of the resolution function for small-angle scattering , 1990 .

[34]  J. Nagle,et al.  Structure of fully hydrated bilayer dispersions. , 1988, Biochimica et biophysica acta.

[35]  D. Mildner,et al.  Optimization of the experimental resolution for small‐angle scattering , 1984 .