Highly ordered arrays of magnetic nanoparticles prepared via block copolymer assembly

In the present study we report a simple and reproducible method to prepare highly ordered arrays of Fe3O4 superparamagnetic nanoparticles (MNPs) via block copolymer (BCP) self assembly. Pre-synthesized MNPs with a mean diameter of 6.1 nm are selectively segregated within the lamellae or hexagonally packed cylinders composed of PVP blocks in poly(styrene-b-vinylpyridine) (PS-b-PVP) block copolymers without any additional surface modification. The density of the stabilizing shell in the MNPs as well as the position of pyridine nitrogen in the PVP block of the BCPs are found to be crucial for selective incorporation of MNPs into the PVP domains. The obtained results suggest a key importance of a mutual affinity between active blocks and the nanoparticles which should be maximized in order to attain high nanoparticles loadings and long-range structural orders.

[1]  Bumjoon J. Kim,et al.  Nanoparticle‐Induced Phase Transitions in Diblock‐Copolymer Films , 2005 .

[2]  Anna C. Balazs,et al.  Nanoparticle Polymer Composites: Where Two Small Worlds Meet , 2006, Science.

[3]  Bumjoon J. Kim,et al.  Effect of Areal Chain Density on the Location of Polymer-Modified Gold Nanoparticles in a Block Copolymer Template , 2006 .

[4]  S. Minko,et al.  Microphase Separation in Thin Films of Poly(styrene-block-4-vinylpyridine) Copolymer−2-(4‘-Hydroxybenzeneazo)benzoic Acid Assembly , 2005 .

[5]  G. Chumanov,et al.  Poly(Vinyl Pyridine) as a Universal Surface Modifier for Immobilization of Nanoparticles , 2002 .

[6]  S. Gruner,et al.  Metal Nanoparticle/Block Copolymer Composite Assembly and Disassembly. , 2009, Chemistry of materials : a publication of the American Chemical Society.

[7]  Soojin Park,et al.  A simple route to highly oriented and ordered nanoporous block copolymer templates. , 2008, ACS nano.

[8]  Todd Emrick,et al.  Self-directed self-assembly of nanoparticle/copolymer mixtures , 2005, Nature.

[9]  Jillian M. Buriak,et al.  Assembly of aligned linear metallic patterns on silicon , 2007, Nature Nanotechnology.

[10]  T. Hayakawa,et al.  Three-Dimensional Nanoscale Alignment of Metal Nanoparticles Using Block Copolymer Films as Nanoreactors , 2003 .

[11]  E. Thomas,et al.  Size-selective organization of enthalpic compatibilized nanocrystals in ternary block copolymer/particle mixtures. , 2003, Journal of the American Chemical Society.

[12]  Sergiy Minko,et al.  Ordered reactive nanomembranes/nanotemplates from thin films of block copolymer supramolecular assembly. , 2003, Journal of the American Chemical Society.

[13]  Ian W. Hamley,et al.  Ordering in thin films of block copolymers: Fundamentals to potential applications , 2009 .

[14]  Hao Zeng,et al.  Monodisperse MFe2O4 (M = Fe, Co, Mn) nanoparticles. , 2004, Journal of the American Chemical Society.

[15]  I. Mondragon,et al.  Self‐Assembling Nanomaterials using Magnetic Nanoparticles Modified with Polystyrene Brushes , 2007 .

[16]  H. Gu,et al.  Oleic acid coating on the monodisperse magnetite nanoparticles , 2006 .

[17]  E. Thomas,et al.  Metallodielectric Photonic Crystals Based on Diblock Copolymers , 2001 .

[18]  S. Minko,et al.  Metallic nickel nanorod arrays embedded into ordered block copolymer templates , 2007 .

[19]  K. Das,et al.  Monolayer Exchange Chemistry of γ-Fe2O3 Nanoparticles , 2002 .

[20]  T. Emrick,et al.  Responsive Assemblies: Gold Nanoparticles with Mixed Ligands in Microphase Separated Block Copolymers , 2008 .

[21]  Hao Zeng,et al.  Size-controlled synthesis of magnetite nanoparticles. , 2002, Journal of the American Chemical Society.

[22]  J. Jung,et al.  Tunable magnetic arrangement of iron oxide nanoparticles in situ synthesized on the solid substrate from diblock copolymer micelles. , 2005, Langmuir : the ACS journal of surfaces and colloids.

[23]  S. Krishnamoorthy,et al.  Nanoscale patterning with block copolymers , 2006 .

[24]  Jin Xie,et al.  One-pot synthesis of monodisperse iron oxide nanoparticles for potential biomedical applications , 2006 .

[25]  E. Thomas,et al.  Block Copolymer Nanocomposites: Perspectives for Tailored Functional Materials , 2005, Advanced materials.

[26]  M. A. Kashem,et al.  Array of Magnetic Nanoparticles via Particle Co-operated Self-Assembly in Block Copolymer Thin Film , 2009 .

[27]  Agus Haryono,et al.  Controlled arrangement of nanoparticle arrays in block-copolymer domains. , 2006, Small.

[28]  G. Craig,et al.  Synthesis of palladium and platinum nanoclusters within microphase-separated diblock copolymers , 1992 .

[29]  C. Ross,et al.  Selective Growth of Cobalt Nanoclusters in Domains of Block Copolymer Films , 2003 .

[30]  C. O'connor,et al.  Magnetic properties of variable-sized Fe3O4 nanoparticles synthesized from non-aqueous homogeneous solutions of polyols , 2007 .

[31]  S. Krishnamoorthy,et al.  Tuning the Dimensions and Periodicities of Nanostructures Starting from the Same Polystyrene‐block‐poly(2‐vinylpyridine) Diblock Copolymer , 2006 .

[32]  Moon Jeong Park,et al.  Effect of the casting solvent on the morphology of poly(styrene-b-isoprene) diblock copolymer/magnetic nanoparticle mixtures. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[33]  Jinan Chai,et al.  Using cylindrical domains of block copolymers to self-assemble and align metallic nanowires. , 2008, ACS nano.

[34]  Bumjoon J. Kim,et al.  Control of nanoparticle location in block copolymers. , 2005, Journal of the American Chemical Society.

[35]  I. Hamley.  Nanostructure fabrication using block copolymers , 2003 .

[36]  B. Erné,et al.  Surface analysis of magnetite nanoparticles in cyclohexane solutions of oleic acid and oleylamine , 2007 .

[37]  R. Schrock,et al.  Synthesis of silver and gold nanoclusters within microphase-separated diblock copolymers , 1992 .

[38]  Markus Antonietti,et al.  Amphiphilic Block Copolymers in Structure-Controlled Nanomaterial Hybrids , 1998 .

[39]  R. Composto,et al.  Dispersion of polymer-grafted magnetic nanoparticles in homopolymers and block copolymers , 2008 .

[40]  Alexander Eychmüller,et al.  Arrays of Inorganic Nanodots and Nanowires Using Nanotemplates Based on Switchable Block Copolymer Supramolecular Assemblies , 2009 .

[41]  Ting Xu,et al.  Small-molecule-directed nanoparticle assembly towards stimuli-responsive nanocomposites. , 2009, Nature materials.

[42]  Todd Emrick,et al.  Self‐Assembly of Nanoparticle–Copolymer Mixtures: A Kinetic Point of View , 2007 .

[43]  I. Mondragon,et al.  Structural and ordering behavior of lamellar polystyrene‐block‐polybutadiene‐block‐polystyrene triblock copolymer containing layered silicates , 2008 .