Polymersome magneto-valves for reversible capture and release of nanoparticles

Stomatocytes are polymersomes with an infolded bowl-shaped architecture. This internal cavity is connected to the outside environment via a small ‘mouth’ region. Stomatocytes are assembled from diamagnetic amphiphilic block-copolymers with a highly anisotropic magnetic susceptibility, which permits to magnetically align and deform the polymeric self-assemblies. Here we show the reversible opening and closing of the mouth region of stomatocytes in homogeneous magnetic fields. The control over the size of the opening yields magneto-responsive supramolecular valves that are able to reversibly capture and release cargo. Furthermore, the increase in the size of the opening is gradual and starts at fields below 10 T, which opens the possibility of using these structures for delivery and nanoreactor applications.

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

[2]  K. Caldemeyer,et al.  The basic principles of computed tomography and magnetic resonance imaging. , 1999, Journal of the American Academy of Dermatology.

[3]  Fei Peng,et al.  Micro- and nano-motors for biomedical applications. , 2014, Journal of materials chemistry. B.

[4]  Q. Pankhurst,et al.  Applications of magnetic nanoparticles in biomedicine , 2003 .

[5]  Zhiyuan Zhong,et al.  Stimuli-responsive polymersomes for programmed drug delivery. , 2009, Biomacromolecules.

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

[7]  N. Boukos,et al.  Nanodesigned magnetic polymer containers for dual stimuli actuated drug controlled release and magnetic hyperthermia mediation , 2012 .

[8]  Sébastien Lecommandoux,et al.  Magnetic field triggered drug release from polymersomes for cancer therapeutics. , 2013, Journal of controlled release : official journal of the Controlled Release Society.

[9]  A. Eisenberg,et al.  Control of Morphology through Polymer−Solvent Interactions in Crew-Cut Aggregates of Amphiphilic Block Copolymers , 1997 .

[10]  H. Hofmann,et al.  Superparamagnetic nanoparticles for biomedical applications: Possibilities and limitations of a new drug delivery system , 2005 .

[11]  Lixin Dong,et al.  Artificial bacterial flagella: Fabrication and magnetic control , 2009 .

[12]  S. Nie,et al.  In vivo cancer targeting and imaging with semiconductor quantum dots , 2004, Nature Biotechnology.

[13]  M. R. Imam,et al.  Dendron-mediated self-assembly, disassembly, and self-organization of complex systems. , 2009, Chemical reviews.

[14]  Wei Gao,et al.  Nanomotor-based biocatalytic patterning of helical metal microstructures. , 2013, Nanoscale.

[15]  P. Fischer,et al.  Magnetically actuated propulsion at low Reynolds numbers: towards nanoscale control. , 2011, Nanoscale.

[16]  Y. Yamauchi,et al.  Block copolymer mediated synthesis of dendritic platinum nanoparticles. , 2009, Journal of the American Chemical Society.

[17]  Daniela A Wilson,et al.  Fuel concentration dependent movement of supramolecular catalytic nanomotors. , 2013, Nanoscale.

[18]  Roberto Cingolani,et al.  Subnanometer local temperature probing and remotely controlled drug release based on azo-functionalized iron oxide nanoparticles. , 2013, Nano letters.

[19]  Gyoujin Cho,et al.  Phospholipid bicelles that align with their normals parallel to the magnetic field. , 2002, Journal of the American Chemical Society.

[20]  Daniela A Wilson,et al.  Autonomous movement of platinum-loaded stomatocytes. , 2012, Nature chemistry.

[21]  A. Hamasaki,et al.  Colloid and Interface Chemistry under Magnetic Fields , 2012 .

[22]  Younan Xia,et al.  Pulsatile drug release from PLGA hollow microspheres by controlling the permeability of their walls with a magnetic field. , 2012, Small.

[23]  E. W. Meijer,et al.  Magnetic deformation of self-assembled sexithiophene spherical nanocapsules. , 2005, Journal of the American Chemical Society.

[24]  Daniela A Wilson,et al.  Manipulation of micro- and nanostructure motion with magnetic fields. , 2014, Soft matter.

[25]  D. Wilson,et al.  Probing morphological changes in polymersomes with magnetic birefringence. , 2014, Chemical communications.

[26]  Sébastien Lecommandoux,et al.  Magnetic responsive polymer composite materials. , 2013, Chemical Society reviews.

[27]  Gerald Küstler,et al.  DIAMAGNETIC LEVITATION - HISTORICAL MILESTONES , 2007 .

[28]  J. V. van Hest,et al.  Controlled shape transformation of polymersome stomatocytes. , 2011, Angewandte Chemie.

[29]  J. Kohlbrecher,et al.  Alignment of bicelles studied with high-field magnetic birefringence and small-angle neutron scattering measurements. , 2013, Langmuir : the ACS journal of surfaces and colloids.

[30]  P. Fischer,et al.  Controlled propulsion of artificial magnetic nanostructured propellers. , 2009, Nano letters.

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

[32]  D. Wilson,et al.  Entrapment of metal nanoparticles in polymer stomatocytes. , 2012, Journal of the American Chemical Society.

[33]  Jeff W M Bulte,et al.  Iron oxide MR contrast agents for molecular and cellular imaging , 2004, NMR in biomedicine.

[34]  Dennis E. Discher,et al.  Polymer Vesicles , 2022 .

[35]  H. Iseki,et al.  A Study of Magnetic Drug Delivery System Using Bulk High Temperature Superconducting Magnet , 2008, IEEE Transactions on Applied Superconductivity.

[36]  M. Motwani,et al.  MR imaging of cardiac tumors and masses: a review of methods and clinical applications. , 2013, Radiology.

[37]  J. Giddings,et al.  Field-flow fractionation: analysis of macromolecular, colloidal, and particulate materials. , 1993, Science.

[38]  R. Liburdy,et al.  Magnetic deformation of phospholipid bilayers: Effects on liposome shape and solute permeability at prephase transition temperatures , 1988 .

[39]  C. Breathnach.  Magnetism in medicine. , 1983, Irish medical journal.

[40]  Seyda Bucak,et al.  Protein Separations Using Colloidal Magnetic Nanoparticles , 2003, Biotechnology progress.

[41]  Nicole Pamme,et al.  Magnetism and microfluidics. , 2006, Lab on a chip.

[42]  Richard Bowtell,et al.  Safety Implications of High-Field MRI: Actuation of Endogenous Magnetic Iron Oxides in the Human Body , 2009, PloS one.

[43]  Wei Wang,et al.  Steering acoustically propelled nanowire motors toward cells in a biologically compatible environment using magnetic fields. , 2013, Langmuir : the ACS journal of surfaces and colloids.

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

[45]  J. Fraser Stoddart,et al.  Noninvasive remote-controlled release of drug molecules in vitro using magnetic actuation of mechanized nanoparticles. , 2010, Journal of the American Chemical Society.

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

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