Synthetic polyion-counterion transport systems in polymersomes and gels.

Transport across the membranes of polymersomes remains difficult in part due to the great thickness of the polymer bilayers. Here, we report that dynamic polyion-counterion transport systems are active in fluorogenic polymersomes composed of poly(dimethylsiloxane)-b-poly(2-methyloxazoline) (PDMS-PMOXA). These results suggest that counterion-activated calf-thymus DNA can act as cation carrier that moves not only across lipid bilayer and bulk chloroform membranes but also across the "plastic" membranes of polymersomes. Compared to egg yolk phosophatidylcholine (EYPC) lipsosomes, activities and activator scope in PDMS-PMOXA polymersomes are clearly reduced. Embedded in agar gel matrices, fluorogenic PDMS-PMOXA polymersomes respond reliably to polyion-counterion transporters, with high contrast, high stability and preserved selectivity. Compared to standard EYPC liposomes, it cannot be said that PDMS-PMOXA polymersomes are better. However, they are different, and this difference could be interesting for the development of sensing devices.

[1]  Philip A. Gale,et al.  Using small molecules to facilitate exchange of bicarbonate and chloride anions across liposomal membranes. , 2009, Nature chemistry.

[2]  Markus Antonietti,et al.  Vesicles and Liposomes: A Self‐Assembly Principle Beyond Lipids , 2003 .

[3]  Jong-Mok Kim,et al.  Cytoplasmic delivery of liposomal contents mediated by an acid-labile cholesterol-vinyl ether-PEG conjugate. , 2009, Bioconjugate chemistry.

[4]  Stefan Matile,et al.  Recent synthetic transport systems. , 2011, Chemical Society reviews.

[5]  I. Hamachi,et al.  MCM-enzyme-supramolecular hydrogel hybrid as a fluorescence sensing material for polyanions of biological significance. , 2009, Journal of the American Chemical Society.

[6]  Stephan Marsch,et al.  Toward intelligent nanosize bioreactors: a pH-switchable, channel-equipped, functional polymer nanocontainer. , 2006, Nano letters.

[7]  David N Sheppard,et al.  Development of synthetic membrane transporters for anions. , 2007, Chemical Society reviews.

[8]  I. Hamachi,et al.  Montmorillonite-supramolecular hydrogel hybrid for fluorocolorimetric sensing of polyamines. , 2011, Journal of the American Chemical Society.

[9]  T. Takeuchi,et al.  DNA aptamers as analyte-responsive cation transporters in fluorogenic vesicles: signal amplification by supramolecular polymerization. , 2009, Journal of the American Chemical Society.

[10]  M. R. Imam,et al.  Proton Transport from Dendritic Helical‐Pore‐Incorporated Polymersomes , 2009 .

[11]  Andrew D. Miller,et al.  DODAG; a versatile new cationic lipid that mediates efficient delivery of pDNA and siRNA. , 2010, Journal of controlled release : official journal of the Controlled Release Society.

[12]  Scott L. Cockroft,et al.  Palladium(II)-mediated assembly of biotinylated ion channels. , 2011, Chemistry.

[13]  M. Mayor,et al.  Experimental evidence for the functional relevance of anion-pi interactions. , 2010, Nature chemistry.

[14]  Jeffery T. Davis,et al.  Recent advances in the transmembrane transport of anions. , 2010, Chemical Society reviews.

[15]  B. Nordén,et al.  Counterion-mediated membrane penetration: cationic cell-penetrating peptides overcome Born energy barrier by ion-pairing with phospholipids. , 2007, Biochimica et biophysica acta.

[16]  Martin Müller,et al.  Oxidation-responsive polymeric vesicles , 2004, Nature materials.

[17]  S. Matile,et al.  Amplifier-mediated activation of cell-penetrating peptides with steroids: multifunctional anion transporters for fluorogenic cholesterol sensing in eggs and blood. , 2009, Angewandte Chemie.

[18]  T. Takeuchi,et al.  Pattern generation with synthetic sensing systems in lipid bilayer membranes , 2011 .

[19]  D. Seebach,et al.  Permeation of a β -heptapeptide derivative across phospholipid bilayers , 2007 .

[20]  S. Regen,et al.  Bioconjugate-based molecular umbrellas. , 2009, Bioconjugate chemistry.

[21]  Wolfgang Meier,et al.  Highly permeable polymeric membranes based on the incorporation of the functional water channel protein Aquaporin Z , 2007, Proceedings of the National Academy of Sciences.

[22]  Y. Kobuke,et al.  Transmembrane nanopores from porphyrin supramolecules. , 2008, Journal of the American Chemical Society.

[23]  R. Nolte,et al.  Synthesis of polymer-biohybrids: from small to giant surfactants. , 2009, Accounts of chemical research.

[24]  K. G. Rajeev,et al.  Rational design of cationic lipids for siRNA delivery , 2010, Nature Biotechnology.

[25]  R. Fischer,et al.  Break on through to the Other Side—Biophysics and Cell Biology Shed Light on Cell‐Penetrating Peptides , 2005, Chembiochem : a European journal of chemical biology.

[26]  E. Giralt,et al.  Synthetic Ligands Able to Interact with the P53 Tetramerization Domain. Towards Understanding a Protein Surface Recognition Event , 2006, Chembiochem : a European journal of chemical biology.

[27]  V. Torchilin,et al.  Design, synthesis, and characterization of pH-sensitive PEG-PE conjugates for stimuli-sensitive pharmaceutical nanocarriers: the effect of substitutes at the hydrazone linkage on the ph stability of PEG-PE conjugates. , 2007, Bioconjugate chemistry.

[28]  Yan Zhao,et al.  Environmental effects dominate the folding of oligocholates in solution, surfactant micelles, and lipid membranes. , 2010, Journal of the American Chemical Society.

[29]  Hidekazu Hiroaki,et al.  High-resolution multi-dimensional NMR spectroscopy of proteins in human cells , 2009, Nature.

[30]  T. Takeuchi,et al.  Amphiphilic Counterion Activators for DNA: Stimuli‐Responsive Cation Transporters and Biosensors in Bulk and Lipid Bilayer Membranes , 2009, Chembiochem : a European journal of chemical biology.

[31]  C. Palivan,et al.  Biocompatible functionalization of polymersome surfaces: a new approach to surface immobilization and cell targeting using polymersomes. , 2011, Journal of the American Chemical Society.

[32]  N. Voyer,et al.  How far can a sodium ion travel within a lipid bilayer? , 2011, Journal of the American Chemical Society.

[33]  P. Wender,et al.  The design of guanidinium-rich transporters and their internalization mechanisms. , 2008, Advanced drug delivery reviews.

[34]  S. Matile,et al.  Comprehensive screening of octopus amphiphiles as DNA activators in lipid bilayers: implications on transport, sensing and cellular uptake. , 2011, Organic & biomolecular chemistry.

[35]  George W. Gokel,et al.  Transport of chloride ion through phospholipid bilayers mediated by synthetic ionophores , 2009 .

[36]  Pavel Bucek,et al.  A practical approach to optical cross-reactive sensor arrays. , 2010, Chemical Society reviews.

[37]  B. Le Droumaguet,et al.  In situ ATRP-mediated hierarchical formation of giant amphiphile bionanoreactors. , 2008, Angewandte Chemie.

[38]  Wolfgang Meier,et al.  Immobilized protein-polymer nanoreactors. , 2009, Small.

[39]  W. Meier,et al.  Calcein Release from Polymeric Vesicles in Blood Plasma and PVA Hydrogel , 2009, Pharmaceutical Research.

[40]  S. Matile,et al.  Anionic activators for differential sensing with cell-penetrating peptides. , 2011, Chemistry, an Asian journal.

[41]  S. Futaki,et al.  Direct and rapid cytosolic delivery using cell-penetrating peptides mediated by pyrenebutyrate. , 2006, ACS chemical biology.

[42]  B. Shen,et al.  Synthetic chloride channel regulates cell membrane potentials and voltage-gated calcium channels. , 2009, Journal of the American Chemical Society.

[43]  Jiahua Zhu,et al.  Polymersome stomatocytes: controlled shape transformation in polymer vesicles. , 2010, Journal of the American Chemical Society.

[44]  Mark E. Davis,et al.  Evidence of RNAi in humans from systemically administered siRNA via targeted nanoparticles , 2010, Nature.

[45]  S. Bhattacharya,et al.  Advances in gene delivery through molecular design of cationic lipids. , 2009, Chemical communications.

[46]  Leo A. Joyce,et al.  The uses of supramolecular chemistry in synthetic methodology development: examples of anion and neutral molecular recognition. , 2010, Chemical Society reviews.

[47]  C. Chern,et al.  Polymer vesicles containing small vesicles within interior aqueous compartments and pH-responsive transmembrane channels. , 2008, Angewandte Chemie.

[48]  Neal A. Rakow,et al.  A colorimetric sensor array for odour visualization , 2000, Nature.

[49]  Seokmin Shin,et al.  Designer nanorings with functional cavities from self-assembling β-sheet peptides. , 2011, Chemistry, an Asian journal.

[50]  S. Matile,et al.  Anion-mediated transfer of polyarginine across liquid and bilayer membranes. , 2003, Journal of the American Chemical Society.

[51]  Carlo Montemagno,et al.  Photo-induced proton gradients and ATP biosynthesis produced by vesicles encapsulated in a silica matrix , 2005, Nature materials.

[52]  Adam Blanazs,et al.  Self-Assembled Block Copolymer Aggregates: From Micelles to Vesicles and their Biological Applications. , 2009, Macromolecular rapid communications.

[53]  W. Meier,et al.  Stimuli-responsive polymersomes as nanocarriers for drug and gene delivery. , 2009, Macromolecular bioscience.

[54]  T. Takeuchi,et al.  Counterion-activated polyions as soft sensing systems in lipid bilayer membranes: from cell-penetrating peptides to DNA. , 2009, Faraday discussions.

[55]  Philip A. Gale.  Anion receptor chemistry: highlights from 2008 and 2009. , 2010, Chemical Society reviews.

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

[57]  Eric V Anslyn,et al.  Sensing A Paradigm Shift in the Field of Molecular Recognition: From Selective to Differential Receptors. , 2001, Angewandte Chemie.

[58]  T. Takeuchi,et al.  Dynamic octopus amphiphiles as powerful activators of DNA transporters: differential fragrance sensing and beyond. , 2010, Chemistry.

[59]  A. Schmitzer,et al.  Uncovering new properties of imidazolium salts: Cl- transport and supramolecular regulation of their transmembrane activity. , 2011, Chemical communications.

[60]  T. Fyles,et al.  Synthetic ion channels in bilayer membranes. , 2007, Chemical Society reviews.

[61]  Roger Y Tsien,et al.  Tumor imaging by means of proteolytic activation of cell-penetrating peptides. , 2004, Proceedings of the National Academy of Sciences of the United States of America.

[62]  Sheshanath V. Bhosale,et al.  Photoproduction of Proton Gradients with π-Stacked Fluorophore Scaffolds in Lipid Bilayers , 2006, Science.