Polymersomes with asymmetric membranes and self-assembled superstructures using pentablock quintopolymers resolved by electron tomography.

Polystyrene-block-poly(1,4-isoprene)-block-poly(dimethyl siloxane)-block-poly(tert-butyl methacrylate)-block-poly(2-vinyl pyridine), PS-b-PI-b-PDMS-b-PtBMA-b-P2VP, self-assembles in acetone into polymersomes with asymmetric (directional) PI-b-PDMS membranes. The polymersomes, in turn, self-assemble into superstructures. Analogically to supravesicular structures at a smaller length scale, we refer to them as suprapolymersome structures. Electron tomograms are shown to be invaluable in the structural assessment of such complex self-assemblies.

[1]  Jan Sijbers,et al.  Fast and flexible X-ray tomography using the ASTRA toolbox. , 2016, Optics express.

[2]  Olli Ikkala,et al.  Rational design of ABC triblock terpolymer solution nanostructures with controlled patch morphology , 2016, Nature Communications.

[3]  R. Mezzenga,et al.  Direct visualization of dispersed lipid bicontinuous cubic phases by cryo-electron tomography , 2015, Nature Communications.

[4]  Jan Sijbers,et al.  The ASTRA Toolbox: A platform for advanced algorithm development in electron tomography. , 2015, Ultramicroscopy.

[5]  Mitchell A. Winnik,et al.  Multidimensional hierarchical self-assembly of amphiphilic cylindrical block comicelles , 2015, Science.

[6]  F. Schacher,et al.  Hidden structural features of multicompartment micelles revealed by cryogenic transmission electron tomography. , 2014, ACS nano.

[7]  Youliang Zhao,et al.  Synthesis of an amphiphilic PEG-PCL-PSt-PLLA-PAA star quintopolymer and its self-assembly for pH-sensitive drug delivery , 2014 .

[8]  M. Vayer,et al.  Ruthenium staining for morphological assessment and patterns formation in block copolymer films , 2014 .

[9]  Maïté Marguet,et al.  Cascade reactions in multicompartmentalized polymersomes. , 2014, Angewandte Chemie.

[10]  Kyriaki S. Pafiti,et al.  High‐molecular‐weight symmetrical multiblock copolymers: Synthesis by RAFT polymerization and characterization , 2013 .

[11]  F. Schacher,et al.  Guided hierarchical co-assembly of soft patchy nanoparticles , 2013, Nature.

[12]  Ke Zhang,et al.  Disk-cylinder and disk-sphere nanoparticles via a block copolymer blend solution construction , 2013, Nature Communications.

[13]  A. Hirao,et al.  Precise Synthesis of Block Polymers Composed of Three or More Blocks by Specially Designed Linking Methodologies in Conjunction with Living Anionic Polymerization System , 2013 .

[14]  A. Takahara,et al.  Transmission electron microtomography in soft materials. , 2013, Microscopy.

[15]  Xinyu Zhang,et al.  Synthesis of linear amphiphilic tetrablock quaterpolymers with dual stimulus response through the combination of ATRP and RAFT by a click chemistry site transformation approach , 2013 .

[16]  Yong Gao,et al.  Cascade Molecule-Particle-Molecule Self-Assemblies for Fabricating Narrowly Size-Distributed Polymeric Superparticles with a Bicontinuous Nanostructure. , 2012, ACS macro letters.

[17]  I. Manners,et al.  Non-Centrosymmetric Cylindrical Micelles by Unidirectional Growth , 2012, Science.

[18]  S. Armes,et al.  Facile Synthesis of Methacrylic ABC Triblock Copolymer Vesicles by RAFT Aqueous Dispersion Polymerization , 2012 .

[19]  J. Szebeni,et al.  Flow cytometric analysis of supravesicular structures in doxorubicin-containing pegylated liposomes. , 2012, Chemistry and physics of lipids.

[20]  C. M. Bates,et al.  Multiblock Polymers: Panacea or Pandora’s Box? , 2012, Science.

[21]  Timothy P. Lodge,et al.  Multicompartment Block Polymer Micelles , 2012 .

[22]  K J Batenburg,et al.  Performance improvements for iterative electron tomography reconstruction using graphics processing units (GPUs). , 2011, Journal of structural biology.

[23]  S. Armes,et al.  Mechanistic insights for block copolymer morphologies: how do worms form vesicles? , 2011, Journal of the American Chemical Society.

[24]  H. RULLGÅRD,et al.  Simulation of transmission electron microscope images of biological specimens , 2011, Journal of microscopy.

[25]  Søren Holdt Jensen,et al.  Implementation of an optimal first-order method for strongly convex total variation regularization , 2011, ArXiv.

[26]  Simon J. Holder,et al.  New micellar morphologies from amphiphilic block copolymers: disks, toroids and bicontinuous micelles , 2011 .

[27]  T. Kyle Vanderlick,et al.  Specific adhesion between DNA-functionalized “Janus” vesicles: size-limited clusters , 2011 .

[28]  F. Schacher,et al.  Core-crosslinked compartmentalized cylinders. , 2011, Nanoscale.

[29]  G. Grason,et al.  ABC triblock copolymer vesicles with mesh-like morphology. , 2010, ACS nano.

[30]  U. Schubert,et al.  Multicompartment micelles from a metallo-supramolecular tetrablock quatercopolymer. , 2009, Chemical communications.

[31]  H. Paik,et al.  Synthesis of linear tetrablock quaterpolymers via atom transfer radical polymerization and a click coupling approach , 2009 .

[32]  Eda Gungor,et al.  One‐pot double click reactions for the preparation of H‐shaped ABCDE‐type quintopolymer , 2009 .

[33]  F. Schacher,et al.  Multicompartment Core Micelles of Triblock Terpolymers in Organic Media , 2009 .

[34]  John M. Layman,et al.  Microphase‐Separated Poly(vinylpyridine) Block Copolymer Prepared with a Novel Bifunctional Initiator , 2009 .

[35]  N. Hadjichristidis,et al.  Linear pentablock quintopolymers (l‐SIDMV) with five incompatible blocks: Polystyrene, polyisoprene‐1,4, poly(dimethylsiloxane), poly(tert‐butyl methacrylate), and poly(2‐vinylpyridine) , 2008 .

[36]  T. Lodge,et al.  Evolution of multicompartment micelles to mixed corona micelles using solvent mixtures. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[37]  Mitchell A. Winnik,et al.  Cylindrical Block Copolymer Micelles and Co-Micelles of Controlled Length and Architecture , 2007, Science.

[38]  Sheng Zhong,et al.  Block Copolymer Assembly via Kinetic Control , 2007, Science.

[39]  Zhenghong Lu,et al.  Interfacial Staining of a Phase-Separated Block Copolymer with Ruthenium Tetroxide , 2007 .

[40]  T. Lodge,et al.  Laterally nanostructured vesicles, polygonal bilayer sheets, and segmented wormlike micelles. , 2006, Nano letters.

[41]  A. Thünemann,et al.  Multicompartment micelles formed by self-assembly of linear ABC triblock copolymers in aqueous medium. , 2005, Angewandte Chemie.

[42]  Apostolos Avgeropoulos,et al.  Linear and non-linear triblock terpolymers. Synthesis, self-assembly in selective solvents and in bulk , 2005 .

[43]  M. Rubinstein,et al.  Diblock copolymer micelles in a dilute solution , 2005 .

[44]  F. Bates,et al.  ABCA tetrablock copolymer vesicles , 2004 .

[45]  D. Pochan,et al.  Toroidal Triblock Copolymer Assemblies , 2004, Science.

[46]  M. Hillmyer,et al.  Large area nanolithographic templates by selective etching of chemically stained block copolymer thin films , 2004 .

[47]  Yushu Matsushita,et al.  Observation of four-phase lamellar structure from a tetrablock quarterpolymer of the ABCD type , 2003 .

[48]  I. Hamley,et al.  Templating the patterning of gold nanoparticles using a stained triblock copolymer film surface , 2003 .

[49]  Frank S Bates,et al.  On the Origins of Morphological Complexity in Block Copolymer Surfactants , 2003, Science.

[50]  B. Sohn,et al.  Variations of the lamellar period in thin films of diblock copolymers by selective staining agents , 2002 .

[51]  N. Hadjichristidis,et al.  Synthesis of model linear tetrablock quaterpolymers and pentablock quintopolymers of ethylene oxide , 2002 .

[52]  T. Hashimoto,et al.  Four-Phase Triple Coaxial Cylindrical Microdomain Morphology in a Linear Tetrablock Quaterpolymer of Styrene, Isoprene, Dimethylsiloxane, and 2-Vinylpyridine , 2002 .

[53]  D. Hammer,et al.  Polymersomes: tough vesicles made from diblock copolymers. , 1999, Science.

[54]  N. McKeown,et al.  Synthesis and characterization of mesogenic phthalocyanines containing a single poly(oxyethylene) side chain : an example of steric disturbance of the hexagonal columnar mesophase , 1996 .

[55]  Lifeng Zhang,et al.  Multiple Morphologies of "Crew-Cut" Aggregates of Polystyrene-b-poly(acrylic acid) Block Copolymers , 1995, Science.

[56]  P. Couchman,et al.  Ruthenium tetraoxide staining of polymers for electron microscopy , 1983 .

[57]  F. Nudelman,et al.  Cryo-electron tomography: 3-dimensional imaging of soft matter , 2011 .

[58]  Dennis E. Discher,et al.  Polymer vesicles : Materials science: Soft surfaces , 2002 .