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Title: Shape-Specific Patterning of Polymer-Functionalized Nanoparticles

Abstract

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]
+ Show Author Affiliations
  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:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1399669
Report Number(s):
BNL-114376-2017-JA
Journal ID: ISSN 1936-0851; KC0403020
Grant/Contract Number:  
SC0012704
Resource 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)
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

Citation Formats

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., 2017. Web. doi:10.1021/acsnano.7b01669.
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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. https://doi.org/10.1021/acsnano.7b01669
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Galati, Elizabeth, Tebbe, Moritz, Querejeta-Fernández, Ana, Xin, Huolin L., Gang, Oleg, Zhulina, Ekaterina B., and Kumacheva, Eugenia. Mon . "Shape-Specific Patterning of Polymer-Functionalized Nanoparticles". United States. https://doi.org/10.1021/acsnano.7b01669. https://www.osti.gov/servlets/purl/1399669.
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@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 = {Mon May 01 00:00:00 EDT 2017},
month = {Mon May 01 00:00:00 EDT 2017}
}
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https://doi.org/10.1021/acsnano.7b01669
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Works referenced in this record:

Fabrication, Assembly, and Application of Patchy Particles
journal, January 2010

  • Pawar, Amar B.; Kretzschmar, Ilona
  • Macromolecular Rapid Communications, Vol. 31, Issue 2, p. 150-168
  • DOI: 10.1002/marc.200900614

Synthesis, properties and applications of Janus nanoparticles
journal, June 2011

Properties and emerging applications of self-assembled structures made from inorganic nanoparticles
journal, December 2009

  • Nie, Zhihong; Petukhova, Alla; Kumacheva, Eugenia
  • Nature Nanotechnology, Vol. 5, Issue 1
  • DOI: 10.1038/nnano.2009.453

Particles as surfactants—similarities and differences
journal, March 2002

Scalable Routes to Janus Au−SiO 2 and Ternary Ag−Au−SiO 2 Nanoparticles
journal, July 2010

  • Chen, Tao; Chen, Gang; Xing, Shuangxi
  • Chemistry of Materials, Vol. 22, Issue 13
  • DOI: 10.1021/cm101155v

Anisotropic particles with patchy, multicompartment and Janus architectures: preparation and application
journal, January 2011

  • Du, Jianzhong; O'Reilly, Rachel K.
  • Chemical Society Reviews, Vol. 40, Issue 5
  • DOI: 10.1039/c0cs00216j

Multifunctional Patchy Particles by Glancing Angle Deposition
journal, August 2009

  • Pawar, Amar B.; Kretzschmar, Ilona
  • Langmuir, Vol. 25, Issue 16
  • DOI: 10.1021/la900809b

Janus and Ternary Particles Generated by Microfluidic Synthesis:  Design, Synthesis, and Self-Assembly
journal, July 2006

  • Nie, Zhihong; Li, Wei; Seo, Minseok
  • Journal of the American Chemical Society, Vol. 128, Issue 29
  • DOI: 10.1021/ja060882n

Colloids with valence and specific directional bonding
journal, October 2012

Precise hierarchical self-assembly of multicompartment micelles
journal, January 2012

  • Gröschel, André H.; Schacher, Felix H.; Schmalz, Holger
  • Nature Communications, Vol. 3, Issue 1
  • DOI: 10.1038/ncomms1707

Rational design of ABC triblock terpolymer solution nanostructures with controlled patch morphology
journal, June 2016

  • Löbling, Tina I.; Borisov, Oleg; Haataja, Johannes S.
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms12097

Template-Free Bottom-Up Method for Fabricating Diblock Copolymer Patchy Particles
journal, April 2016

Templated Synthesis of Amphiphilic Nanoparticles at the Liquid–Liquid Interface
journal, January 2012

  • Andala, Dickson M.; Shin, Sun Hae Ra; Lee, Hee-Young
  • ACS Nano, Vol. 6, Issue 2
  • DOI: 10.1021/nn202556b

Study of metal nanoparticles stabilised by mixed ligand shell: a striking blue shift of the surface-plasmon band evidencing the formation of Janus nanoparticles
journal, January 2007

  • Vilain, Claire; Goettmann, Frédéric; Moores, Audrey
  • Journal of Materials Chemistry, Vol. 17, Issue 33
  • DOI: 10.1039/b706613a

Spontaneous assembly of subnanometre-ordered domains in the ligand shell of monolayer-protected nanoparticles
journal, April 2004

  • Jackson, Alicia M.; Myerson, Jacob W.; Stellacci, Francesco
  • Nature Materials, Vol. 3, Issue 5
  • DOI: 10.1038/nmat1116

Effect of Molecular Weight on Lateral Microphase Separation of Mixed Homopolymer Brushes Grafted on Silica Particles
journal, September 2014

  • Bao, Chunhui; Tang, Saide; Wright, Roger A. E.
  • Macromolecules, Vol. 47, Issue 19
  • DOI: 10.1021/ma501474m

Preparation and Controlled Self-Assembly of Janus Magnetic Nanoparticles
journal, October 2007

  • Lattuada, Marco; Hatton, T. Alan
  • Journal of the American Chemical Society, Vol. 129, Issue 42
  • DOI: 10.1021/ja0740521

Amphiphilic Janus Gold Nanoparticles via Combining “Solid-State Grafting-to” and “Grafting-from” Methods
journal, September 2008

  • Wang, Bingbing; Li, Bing; Zhao, Bin
  • Journal of the American Chemical Society, Vol. 130, Issue 35
  • DOI: 10.1021/ja804192e

Stepwise surface encoding for high-throughput assembly of nanoclusters
journal, March 2009

  • Maye, Mathew M.; Nykypanchuk, Dmytro; Cuisinier, Marine
  • Nature Materials, Vol. 8, Issue 5
  • DOI: 10.1038/nmat2421

Surface patterning of nanoparticles with polymer patches
journal, August 2016

  • Choueiri, Rachelle M.; Galati, Elizabeth; Thérien-Aubin, Héloïse
  • Nature, Vol. 538, Issue 7623
  • DOI: 10.1038/nature19089

Inhomogeneous Structure of Collapsed Polymer Brushes Under Deformation
journal, December 1995

  • Zhulina, E. B.; Birshtein, T. M.; Priamitsyn, V. A.
  • Macromolecules, Vol. 28, Issue 25
  • DOI: 10.1021/ma00129a021

Grafted polymers in bad solvents: octopus surface micelles
journal, September 1993

Mesoflowers: A new class of highly efficient surface-enhanced Raman active and infrared-absorbing materials
journal, April 2009

  • Sajanlal, Panikkanvalappil Ravindranathan; Pradeep, Thalappil
  • Nano Research, Vol. 2, Issue 4
  • DOI: 10.1007/s12274-009-9028-5

Nanostars shine bright for you
journal, April 2011

  • Guerrero-Martínez, Andrés; Barbosa, Silvia; Pastoriza-Santos, Isabel
  • Current Opinion in Colloid & Interface Science, Vol. 16, Issue 2
  • DOI: 10.1016/j.cocis.2010.12.007

High-yield synthesis and optical response of gold nanostars
journal, November 2007

Influence of Iodide Ions on the Growth of Gold Nanorods: Tuning Tip Curvature and Surface Plasmon Resonance
journal, December 2008

  • Grzelczak, Marek; Sánchez-Iglesias, Ana; Rodríguez-González, Benito
  • Advanced Functional Materials, Vol. 18, Issue 23
  • DOI: 10.1002/adfm.200800706

The isoperimetric problem on some singular surfaces
journal, April 2005

  • Cotton, Andrew; Freeman, David; Gnepp, Andrei
  • Journal of the Australian Mathematical Society, Vol. 78, Issue 2
  • DOI: 10.1017/S1446788700008016

Nanoparticle Size and Surface Chemistry Determine Serum Protein Adsorption and Macrophage Uptake
journal, January 2012

  • Walkey, Carl D.; Olsen, Jonathan B.; Guo, Hongbo
  • Journal of the American Chemical Society, Vol. 134, Issue 4
  • DOI: 10.1021/ja2084338

The Role Radius of Curvature Plays in Thiolated Oligonucleotide Loading on Gold Nanoparticles
journal, January 2009

  • Hill, Haley D.; Millstone, Jill E.; Banholzer, Matthew J.
  • ACS Nano, Vol. 3, Issue 2
  • DOI: 10.1021/nn800726e

Curved polymer and polyelectrolyte brushes beyond the Daoud-Cotton model
journal, July 2006

  • Zhulina, E. B.; Birshtein, T. M.; Borisov, O. V.
  • The European Physical Journal E, Vol. 20, Issue 3
  • DOI: 10.1140/epje/i2006-10013-5

Electrostatic-Driven Ridge Formation on Nanoparticles Coated with Charged End-Group Ligands
journal, March 2011

  • Guo, Peijun; Sknepnek, Rastko; Olvera de la Cruz, Monica
  • The Journal of Physical Chemistry C, Vol. 115, Issue 14
  • DOI: 10.1021/jp201598k

Structural and Optical Properties of Self-Assembled Chains of Plasmonic Nanocubes
journal, October 2014

  • Klinkova, Anna; Thérien-Aubin, Héloïse; Ahmed, Aftab
  • Nano Letters, Vol. 14, Issue 11
  • DOI: 10.1021/nl502746h

Self-orienting nanocubes for the assembly of plasmonic nanojunctions
journal, June 2012

  • Gao, Bo; Arya, Gaurav; Tao, Andrea R.
  • Nature Nanotechnology, Vol. 7, Issue 7
  • DOI: 10.1038/nnano.2012.83

Reshaping and LSPR tuning of Au nanostars in the presence of CTAB
journal, January 2011

  • Rodríguez-Lorenzo, Laura; Romo-Herrera, José M.; Pérez-Juste, Jorge
  • Journal of Materials Chemistry, Vol. 21, Issue 31
  • DOI: 10.1039/c1jm10603a

Single-particle mapping of nonequilibrium nanocrystal transformations
journal, November 2016

Curvature-Directed Assembly of Gold Nanocubes, Nanobranches, and Nanospheres
journal, February 2009

  • Kou, Xiaoshan; Sun, Zhenhua; Yang, Zhi
  • Langmuir, Vol. 25, Issue 3
  • DOI: 10.1021/la802883p

Geometric curvature controls the chemical patchiness and self-assembly of nanoparticles
journal, August 2013

  • Walker, David A.; Leitsch, Emily K.; Nap, Rikkert J.
  • Nature Nanotechnology, Vol. 8, Issue 9, p. 676-681
  • DOI: 10.1038/nnano.2013.158

Epitaxial Growth of Heterogeneous Metal Nanocrystals: From Gold Nano-octahedra to Palladium and Silver Nanocubes
journal, June 2008

  • Fan, Feng-Ru; Liu, De-Yu; Wu, Yuan-Fei
  • Journal of the American Chemical Society, Vol. 130, Issue 22
  • DOI: 10.1021/ja801566d

Measured and calculated solubility of polymers in mixed solvents: Co‐nonsolvency
journal, September 1978

Self-assembly of metal–polymer analogues of amphiphilic triblock copolymers
journal, July 2007

  • Nie, Zhihong; Fava, Daniele; Kumacheva, Eugenia
  • Nature Materials, Vol. 6, Issue 8
  • DOI: 10.1038/nmat1954

Spatially-Directed Oxidation of Gold Nanoparticles by Au(III)−CTAB Complexes
journal, August 2005

  • Rodríguez-Fernández, Jessica; Pérez-Juste, Jorge; Mulvaney, Paul
  • The Journal of Physical Chemistry B, Vol. 109, Issue 30
  • DOI: 10.1021/jp052516g

Tuning of plasmon resonance of gold nanorods by controlled etching
journal, September 2015

N , N -Dimethylformamide as a Reaction Medium for Metal Nanoparticle Synthesis
journal, March 2009

  • Pastoriza-Santos, Isabel; Liz-Marzán, Luis M.
  • Advanced Functional Materials, Vol. 19, Issue 5
  • DOI: 10.1002/adfm.200801566

Matter of age: growing anisotropic gold nanocrystals in organic media
journal, January 2008

  • Gaikwad, Anil V.; Verschuren, Peter; Kinge, Sachin
  • Phys. Chem. Chem. Phys., Vol. 10, Issue 7
  • DOI: 10.1039/B715112H

Theory of the optical properties of ionic crystal cubes
journal, February 1975

Multimode Resonances in Silver Nanocuboids
journal, February 2012

  • Cortie, Michael B.; Liu, Fengguo; Arnold, Matthew D.
  • Langmuir, Vol. 28, Issue 24
  • DOI: 10.1021/la300407u

Polarisation charges and scattering behaviour of realistically rounded plasmonic nanostructures
journal, January 2013

Plasmon Coupling in Silver Nanocube Dimers: Resonance Splitting Induced by Edge Rounding
journal, November 2011

  • Grillet, Nadia; Manchon, Delphine; Bertorelle, Franck
  • ACS Nano, Vol. 5, Issue 12
  • DOI: 10.1021/nn2041329

Controlled Assembly of Eccentrically Encapsulated Gold Nanoparticles
journal, September 2008

  • Chen, Tao; Yang, Miaoxin; Wang, Xinjiao
  • Journal of the American Chemical Society, Vol. 130, Issue 36
  • DOI: 10.1021/ja8040288

Selective etching of gold nanorods by ferric chloride at room temperature
journal, January 2009

  • Zou, Renxian; Guo, Xia; Yang, Jian
  • CrystEngComm, Vol. 11, Issue 12
  • DOI: 10.1039/b911902g

NIH Image to ImageJ: 25 years of image analysis
journal, June 2012

  • Schneider, Caroline A.; Rasband, Wayne S.; Eliceiri, Kevin W.
  • Nature Methods, Vol. 9, Issue 7
  • DOI: 10.1038/nmeth.2089
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    • DOI: 10.1002/anie.201904430

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    • DOI: 10.1002/ange.201904430

    Reconfigurable Polymer Shells on Shape-Anisotropic Gold Nanoparticle Cores
    journal, May 2018

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    • DOI: 10.1002/marc.201800101

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    journal, January 2018

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    • DOI: 10.1039/c8sm00545a

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    journal, January 2019

    • Zanini, Michele; Cingolani, Alberto; Hsu, Chiao-Peng
    • Soft Matter, Vol. 15, Issue 39
    • DOI: 10.1039/c9sm01352k

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    journal, January 2019

    • Galati, Elizabeth; Tao, Huachen; Tebbe, Moritz
    • Angewandte Chemie, Vol. 131, Issue 10
    • DOI: 10.1002/ange.201812887

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    journal, January 2019

    • Yu, Linxiuzi; Shi, Rui; Qian, Hu-Jun
    • Physical Chemistry Chemical Physics, Vol. 21, Issue 3
    • DOI: 10.1039/c8cp06699j

    Homopolymer Nanolithography
    journal, July 2017

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    journal, January 2019

    • Sanchez-Rueda, Eddie G.; Rodriguez-Cristobal, Estefani; Moctezuma González, Claudia L.
    • Nanoscale, Vol. 11, Issue 40
    • DOI: 10.1039/c9nr05225a

    Patterning of polyoxometalate rings on gold nanorods
    journal, January 2020

    • Yang, Chenggong; Tao, Xingfu; Yang, Yang
    • Chemical Communications, Vol. 56, Issue 11
    • DOI: 10.1039/c9cc06968b

    Mechanical phase inversion of Pickering emulsions via metastable wetting of rough colloids
    text, January 2019

    Helicoidal Patterning of Nanorods with Polymer Ligands
    journal, January 2019

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    • Angewandte Chemie International Edition, Vol. 58, Issue 10
    • DOI: 10.1002/anie.201812887

    Janus particles: design, preparation, and biomedical applications
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