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Title: Surface patterning of nanoparticles with polymer patches

Abstract

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 withmore » 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.« less

Authors:
 [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
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1336122
Report Number(s):
BNL-112583-2016-JA
Journal ID: ISSN 0028-0836; R&D Project: 16060; 16060; KC0403020
Grant/Contract Number:  
SC00112704
Resource Type:
Accepted Manuscript
Journal Name:
Nature (London)
Additional Journal Information:
Journal Name: Nature (London); Journal Volume: 538; Journal Issue: 7623; Journal ID: ISSN 0028-0836
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Soft/hard interfaces; Center for Functional Nanomaterials

Citation Formats

Choueiri, Rachelle M., Galati, Elizabeth, Thérien-Aubin, Héloïse, Klinkova, Anna, Larin, Egor M., Querejeta-Fernández, Ana, Han, Lili, Xin, Huolin L., Gang, Oleg, Zhulina, Ekaterina B., Rubinstein, Michael, and Kumacheva, Eugenia. Surface patterning of nanoparticles with polymer patches. United States: N. p., 2016. Web. doi:10.1038/nature19089.
Choueiri, Rachelle M., Galati, Elizabeth, Thérien-Aubin, Héloïse, Klinkova, Anna, Larin, Egor M., Querejeta-Fernández, Ana, Han, Lili, Xin, Huolin L., Gang, Oleg, Zhulina, Ekaterina B., Rubinstein, Michael, & Kumacheva, Eugenia. Surface patterning of nanoparticles with polymer patches. United States. doi:10.1038/nature19089.
Choueiri, Rachelle M., Galati, Elizabeth, Thérien-Aubin, Héloïse, Klinkova, Anna, Larin, Egor M., Querejeta-Fernández, Ana, Han, Lili, Xin, Huolin L., Gang, Oleg, Zhulina, Ekaterina B., Rubinstein, Michael, and Kumacheva, Eugenia. Wed . "Surface patterning of nanoparticles with polymer patches". United States. doi:10.1038/nature19089. https://www.osti.gov/servlets/purl/1336122.
@article{osti_1336122,
title = {Surface patterning of nanoparticles with polymer patches},
author = {Choueiri, Rachelle M. and Galati, Elizabeth and Thérien-Aubin, Héloïse and Klinkova, Anna and Larin, Egor M. and Querejeta-Fernández, Ana and Han, Lili and Xin, Huolin L. and Gang, Oleg and Zhulina, Ekaterina B. and Rubinstein, Michael and Kumacheva, Eugenia},
abstractNote = {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.},
doi = {10.1038/nature19089},
journal = {Nature (London)},
number = 7623,
volume = 538,
place = {United States},
year = {2016},
month = {8}
}

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Works referenced in this record:

Particles as surfactants—similarities and differences
journal, March 2002


Anisotropy of building blocks and their assembly into complex structures
journal, August 2007

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