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Title: Surface patterning of nanoparticles with polymer patches

Journal Article · · Nature (London)
DOI:https://doi.org/10.1038/nature19089· OSTI ID:1336122
 [1];  [1];  [1];  [1];  [1];  [1];  [2];  [3];  [3];  [4];  [5];  [6]
  1. Univ. of Toronto, ON (Canada). Dept. of Chemistry
  2. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials; Tianjin Univ. (China). Inst. for New Energy Materials
  3. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials
  4. Russian Academy of Sciences, Saint Petersburg (Russia). Int. of Macromolecular Compounds; St. Petersburg National Univ. of Informational Technologies, St. Petersburg (Russia). Mechanics and Optics
  5. Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry
  6. Univ. of Toronto, ON (Canada). Dept. of Chemistry and Inst. of Biomaterials and Biomedical Engineering and Dept. of Chemical Engineering and Applied Chemistry

Patterning of colloidal particles with chemically or topographically distinct surface domains (patches) has attracted intense research interest. Surface-patterned particles act as colloidal analogues of atoms and molecules serve as model systems in studies of phase transitions in liquid systems, behave as ‘colloidal surfactants’ and function as templates for the synthesis of hybrid particles. The generation of micrometre- and submicrometre-sized patchy colloids is now efficient but surface patterning of inorganic colloidal nanoparticles with dimensions of the order of tens of nanometres is uncommon. Such nanoparticles exhibit size- and shape-dependent optical, electronic and magnetic properties, and their assemblies show new collective properties. At present, nanoparticle patterning is limited to the generation of two-patch nanoparticles and nanoparticles with surface ripples or a ‘raspberry’ surface morphology. We demonstrate nanoparticle surface patterning, which utilizes thermodynamically driven segregation of polymer ligands from a uniform polymer brush into surface-pinned micelles following a change in solvent quality. Patch formation is reversible but can be permanently preserved using a photocrosslinking step. The methodology offers the ability to control the dimensions of patches, their spatial distribution and the number of patches per nanoparticle, in agreement with a theoretical model. The versatility of the strategy is demonstrated by patterning nanoparticles with different dimensions, shapes and compositions, tethered with various types of polymers and subjected to different external stimuli. Furthermore, these patchy nanocolloids have potential applications in fundamental research, the self-assembly of nanomaterials, diagnostics, sensing and colloidal stabilization.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC00112704
OSTI ID:
1336122
Report Number(s):
BNL-112583-2016-JA; R&D Project: 16060; 16060; KC0403020
Journal Information:
Nature (London), Vol. 538, Issue 7623; ISSN 0028-0836
Publisher:
Nature Publishing GroupCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 215 works
Citation information provided by
Web of Science

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Multiscale Nanoparticle Assembly: From Particulate Precise Manufacturing to Colloidal Processing journal October 2017
Nanostructured Architectures for Biomolecular Detection inside and outside the Cell journal December 2019
Artificial Microbial Arenas: Materials for Observing and Manipulating Microbial Consortia journal April 2019
Thin, Porous, and Conductive Networks of Metal Nanoparticles through Electrochemical Welding on a Liquid Metal Template journal May 2018
Programmable Supra-Assembly of a DNA Surface Adapter for Tunable Chiral Directional Self-Assembly of Gold Nanorods journal October 2017
Faceted-Charge Patchy LnF 3 Nanocrystals with a Selective Solvent Interaction journal October 2018
Helicoidal Patterning of Nanorods with Polymer Ligands journal January 2019
Staged Surface Patterning and Self‐Assembly of Nanoparticles Functionalized with End‐Grafted Block Copolymer Ligands journal May 2019
Programmable Supra-Assembly of a DNA Surface Adapter for Tunable Chiral Directional Self-Assembly of Gold Nanorods journal October 2017
Faceted-Charge Patchy LnF 3 Nanocrystals with a Selective Solvent Interaction journal October 2018
Staged Surface Patterning and Self‐Assembly of Nanoparticles Functionalized with End‐Grafted Block Copolymer Ligands journal May 2019
Self-Assembly and Surface Patterning of Polyferrocenylsilane-Functionalized Gold Nanoparticles journal November 2017
Reconfigurable Polymer Shells on Shape-Anisotropic Gold Nanoparticle Cores journal May 2018
Directed Self‐Assembly of Patchy Microgels into Anisotropic Nanostructures journal December 2019
Homopolymer Nanolithography journal July 2017
Fluorescent Diarylethene Photoswitches-A Universal Tool for Super-Resolution Microscopy in Nanostructured Materials journal January 2018
Engineering Microstructure with Evaporation-Induced Self-Assembly of Microdroplets journal May 2018
Surface Patterns of a Tetrahedral Polyelectrolyte Brush Induced by Grafting Density and Charge Fraction journal November 2019
Transformable masks for colloidal nanosynthesis journal February 2018
Hierarchical self-assembly of 3D lattices from polydisperse anisometric colloids journal April 2019
Programming nanoparticle valence bonds with single-stranded DNA encoders journal December 2019
Surface Interactions between Gold Nanoparticles and Biochar journal July 2017
Surface morphologies of spherical polyelectrolyte brushes induced by trivalent salt ions journal January 2018
Versatile fabrication of patchy nanoparticles via patterning of grafted diblock copolymers on NP surface journal January 2019
A detour strategy for colloidally stable block-copolymer grafted MAPbBr 3 quantum dots in water with long photoluminescence lifetime journal January 2018
Circular assembly of colloidal nanoparticles at the liquid–air interface mediated by block copolymers journal January 2018
Enabling the synthesis of homogeneous or Janus hairy nanoparticles through surface photoactivation journal January 2018
Nanoparticle heterogeneity: an emerging structural parameter influencing particle fate in biological media? journal January 2019
Co-initiated hyperbranched-polydendron building blocks for the direct nanoprecipitation of dendron-directed patchy particles with heterogeneous surface functionality journal January 2018
Gelation of patchy ligand shell nanoparticles decorated by liquid-crystalline ligands: computer simulation study journal January 2018
Phase separation in mixed polymer brushes on nanoparticle surfaces enables the generation of anisotropic nanoarchitectures journal January 2018
Patterning of polyoxometalate rings on gold nanorods journal January 2020
General criteria for evaluating suitable polymer ligands for the synthesis of aluminum nanocrystals journal January 2020
Tailoring the interparticle distance in Langmuir nanoparticle films journal January 2019
Morphologies of a polyelectrolyte brush grafted onto a cubic colloid in the presence of trivalent ions journal January 2019
Self-organization of gel networks formed by block copolymer stars journal January 2019
Slowing down supercooled liquids by manipulating their local structure journal January 2019
N-Heterocyclic carbene-ended polymers as surface ligands of plasmonic metal nanoparticles journal January 2020
Free energy of metal-organic framework self-assembly journal March 2019
Single-component quasicrystalline nanocrystal superlattices through flexible polygon tiling rule journal December 2018
Directed Self‐Assembly of Patchy Microgels into Anisotropic Nanostructures journal January 2020
Helicoidal Patterning of Nanorods with Polymer Ligands journal January 2019
Surface Fluctuations Dominate the Slow Glassy Dynamics of Polymer-Grafted Colloid Assemblies journal August 2018
Quantitative Nanoplasmonics journal August 2018
Vector assembly of colloids on monolayer substrates journal June 2017
Multivalent ions induce lateral structural inhomogeneities in polyelectrolyte brushes journal December 2017
Inverse patchy colloids: synthesis, modeling and self-organization text January 2021

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