Self-oscillating vesicles: spontaneous cyclic structural changes of synthetic diblock copolymers.

A large variety of synthetic vesicles has been created for potential engineering applications and as model systems which mimic living organisms. In most cases, the structure is designed to be thermodynamically stable. However, mimicking dynamic behaviors of living vesicles still remains undeveloped. Herein, we present a synthetic vesicle which shows autonomous disintegration-reconstruction cycles without any external stimuli and which is similar to those in living organisms, such as in the nuclear envelope and synaptic vesicles. The vesicle is composed of a diblock copolymer which has a hydrophilic and a thermosensitive segment. The thermosensitive segment includes a redox moiety that acts as a catalyst for an oscillatory chemical reaction and also controls the aggregation temperature of vesicles. Furthermore, autonomous fusion of vesicles is also observed during the cycles.

[1]  D. Lasič,et al.  Liposomes: From Physics to Applications , 1993 .

[2]  M. Kozlov,et al.  Protein-lipid interplay in fusion and fission of biological membranes. , 2003, Annual review of biochemistry.

[3]  Mathias Winterhalter,et al.  Reconstitution of Channel Proteins in (Polymerized) ABA Triblock Copolymer Membranes , 2000 .

[4]  Dennis E. Discher,et al.  Temperature‐Controlled Assembly and Release from Polymer Vesicles of Poly(ethylene oxide)‐block‐ poly(N‐isopropylacrylamide) , 2006 .

[5]  Maïté Marguet,et al.  Polymersomes in polymersomes: multiple loading and permeability control. , 2012, Angewandte Chemie.

[6]  Kongchang Wei,et al.  Progressive Macromolecular Self‐Assembly: From Biomimetic Chemistry to Bio‐Inspired Materials , 2013, Advanced materials.

[7]  K. Ikeda,et al.  Disappearance and reformation of synaptic vesicle membrane upon transmitter release observed under reversible blockage of membrane retrieval , 1989, The Journal of neuroscience : the official journal of the Society for Neuroscience.

[8]  Thomas C. Südhof,et al.  The synaptic vesicle cycle: a cascade of protein–protein interactions , 1995, Nature.

[9]  K. Schulten,et al.  Molecular biomimetics: nanotechnology through biology , 2003, Nature materials.

[10]  Enzo Tiezzi,et al.  Dynamics of pattern formation in biomimetic systems. , 2008, Journal of theoretical biology.

[11]  Alberto Diaspro,et al.  Protein synthesis in liposomes with a minimal set of enzymes. , 2007, Biochemical and biophysical research communications.

[12]  W. Meier,et al.  Rekonstitution von Kanalproteinen in (polymerisierten) ABA-Triblockcopolymer-Membranen , 2000 .

[13]  Bartosz A Grzybowski,et al.  Vesicle-to-micelle oscillations and spatial patterns. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[14]  C. Palivan,et al.  Mimicking the cell membrane with block copolymer membranes , 2012 .

[15]  Holger Schönherr,et al.  Block-copolymer vesicles as nanoreactors for enzymatic reactions. , 2009, Small.

[16]  Wolfgang Meier,et al.  Polymeric vesicles: from drug carriers to nanoreactors and artificial organelles. , 2011, Accounts of chemical research.

[17]  J. Trevors Early assembly of cellular life. , 2003, Progress in biophysics and molecular biology.

[18]  R. Yoshida,et al.  Self-Oscillating Gel , 1996 .

[19]  R. Yoshida,et al.  In-Phase Synchronization of Chemical and Mechanical Oscillations in Self-Oscillating Gels , 2000 .

[20]  R. Foisner,et al.  Breaking and making of the nuclear envelope , 2005, Journal of cellular biochemistry.

[21]  D. Deamer,et al.  Membrane self‐assembly processes: Steps toward the first cellular life , 2002, The Anatomical record.

[22]  D. Deamer,et al.  The Lipid World , 2001, Origins of life and evolution of the biosphere.

[23]  Wolfgang Meier,et al.  Block copolymer vesicles—using concepts from polymer chemistry to mimic biomembranes , 2005 .

[24]  Ryo Yoshida,et al.  Self-oscillating micelles. , 2013, Chemical communications.

[25]  Zhiyong Tang,et al.  Biomedical Applications of Layer‐by‐Layer Assembly: From Biomimetics to Tissue Engineering , 2006 .

[26]  Vincent Noireaux,et al.  A vesicle bioreactor as a step toward an artificial cell assembly. , 2004, Proceedings of the National Academy of Sciences of the United States of America.

[27]  D. Hammer,et al.  Polymer vesicles in various media , 2000 .

[28]  J. Hubbell,et al.  A novel method for the encapsulation of biomolecules into polymersomes via direct hydration. , 2009, Langmuir : the ACS journal of surfaces and colloids.

[29]  Ho Cheung Shum,et al.  Multicompartment polymersomes from double emulsions. , 2011, Angewandte Chemie.