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Title: Shape-Specific Patterning of Polymer-Functionalized Nanoparticles

Chemically and topographically patterned nanoparticles (NPs) with dimensions on the order of tens of nanometers have a diverse range of applications and are a valuable system for fundamental research. Recently, thermodynamically controlled segregation of a smooth layer of polymer ligands into pinned micelles (patches) offered an approach to nanopatterning of polymer-functionalized NPs. Control of the patch number, size, and spatial distribution on the surface of spherical NPs has been achieved, however, the role of NP shape remained elusive. Here, we report the role of NP shape, namely, the effect of the local surface curvature, on polymer segregation into surface patches. For polymer-functionalized metal nanocubes, we show experimentally and theoretically that the patches form preferentially on the high-curvature regions such as vertices and edges. An in situ transformation of the nanocubes into nanospheres leads to the change in the number and distribution of patches; a process that is dominated by the balance between the surface energy and the stretching energy of the polymer ligands. The experimental and theoretical results presented in this work are applicable to surface patterning of polymer-capped NPs with different shapes, which then enables the exploration of patch-directed self-assembly, as colloidal surfactants, and as templates for the synthesismore » of hybrid nanomaterials.« less
Authors:
 [1] ;  [1] ;  [1] ;  [2] ;  [3] ;  [4] ; ORCiD logo [5]
  1. Univ. of Toronto, ON (Canada). Dept. of Chemistry
  2. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials
  3. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials; Columbia Univ., New York, NY (United States). Dept. of Chemical Engineering, Dept. of Applied Physics and Applied Mathematics
  4. Russian Academy of Sciences (RAS) and St. Petersburg National Univ. of Informational Technologies, St. Petersburg (Russian Federation). Inst. of Macromolecular Compounds
  5. Univ. of Toronto, ON (Canada). Dept. of Chemistry, Inst. of Biomaterials and Biomedical Engineering, Dept. of Chemical Engineering and Applied Chemistry
Publication Date:
Report Number(s):
BNL-114376-2017-JA
Journal ID: ISSN 1936-0851; KC0403020
Grant/Contract Number:
SC0012704
Type:
Accepted Manuscript
Journal Name:
ACS Nano
Additional Journal Information:
Journal Volume: 11; Journal Issue: 5; Journal ID: ISSN 1936-0851
Publisher:
American Chemical Society (ACS)
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)
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY; 36 MATERIALS SCIENCE; Nanoparticles; nanocubes; surface patterning; surface curvature; pinned micelles; polymer patches; Center for Functional Nanomaterials
OSTI Identifier:
1399669

Galati, Elizabeth, Tebbe, Moritz, Querejeta-Fernández, Ana, Xin, Huolin L., Gang, Oleg, Zhulina, Ekaterina B., and Kumacheva, Eugenia. Shape-Specific Patterning of Polymer-Functionalized Nanoparticles. United States: N. p., Web. doi:10.1021/acsnano.7b01669.
Galati, Elizabeth, Tebbe, Moritz, Querejeta-Fernández, Ana, Xin, Huolin L., Gang, Oleg, Zhulina, Ekaterina B., & Kumacheva, Eugenia. Shape-Specific Patterning of Polymer-Functionalized Nanoparticles. United States. doi:10.1021/acsnano.7b01669.
Galati, Elizabeth, Tebbe, Moritz, Querejeta-Fernández, Ana, Xin, Huolin L., Gang, Oleg, Zhulina, Ekaterina B., and Kumacheva, Eugenia. 2017. "Shape-Specific Patterning of Polymer-Functionalized Nanoparticles". United States. doi:10.1021/acsnano.7b01669. https://www.osti.gov/servlets/purl/1399669.
@article{osti_1399669,
title = {Shape-Specific Patterning of Polymer-Functionalized Nanoparticles},
author = {Galati, Elizabeth and Tebbe, Moritz and Querejeta-Fernández, Ana and Xin, Huolin L. and Gang, Oleg and Zhulina, Ekaterina B. and Kumacheva, Eugenia},
abstractNote = {Chemically and topographically patterned nanoparticles (NPs) with dimensions on the order of tens of nanometers have a diverse range of applications and are a valuable system for fundamental research. Recently, thermodynamically controlled segregation of a smooth layer of polymer ligands into pinned micelles (patches) offered an approach to nanopatterning of polymer-functionalized NPs. Control of the patch number, size, and spatial distribution on the surface of spherical NPs has been achieved, however, the role of NP shape remained elusive. Here, we report the role of NP shape, namely, the effect of the local surface curvature, on polymer segregation into surface patches. For polymer-functionalized metal nanocubes, we show experimentally and theoretically that the patches form preferentially on the high-curvature regions such as vertices and edges. An in situ transformation of the nanocubes into nanospheres leads to the change in the number and distribution of patches; a process that is dominated by the balance between the surface energy and the stretching energy of the polymer ligands. The experimental and theoretical results presented in this work are applicable to surface patterning of polymer-capped NPs with different shapes, which then enables the exploration of patch-directed self-assembly, as colloidal surfactants, and as templates for the synthesis of hybrid nanomaterials.},
doi = {10.1021/acsnano.7b01669},
journal = {ACS Nano},
number = 5,
volume = 11,
place = {United States},
year = {2017},
month = {5}
}