skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Interfacial Self-Assembly of Polyelectrolyte-Capped Gold Nanoparticles

Abstract

Here, we report on pH- and salt-responsive assembly of nanoparticles capped with polyelectrolytes at vapor–liquid interfaces. Two types of alkylthiol-terminated poly(acrylic acid) (PAAs, varying in length) are synthesized and used to functionalize gold nanoparticles (AuNPs) to mimic similar assembly effects of single-stranded DNA-capped AuNPs using synthetic polyelectrolytes. Using surface-sensitive X-ray scattering techniques, including grazing incidence small-angle X-ray scattering (GISAXS) and X-ray reflectivity (XRR), we demonstrate that PAA-AuNPs spontaneously migrate to the vapor–liquid interfaces and form Gibbs monolayers by decreasing the pH of the suspension. The Gibbs monoalyers show chainlike structures of monoparticle thickness. The pH-induced self-assembly is attributed to the protonation of carboxyl groups and to hydrogen bonding between the neighboring PAA-AuNPs. In addition, we show that adding MgCl2 to PAA-AuNP suspensions also induces adsorption at the interface and that the high affinity between magnesium ions and carboxyl groups leads to two- and three-dimensional clusters that yield partial surface coverage and poorer ordering of NPs at the interface. We also examine the assembly of PAA-AuNPs in the presence of a positively charged Langmuir monolayer that promotes the attraction of the negatively charged capped NPs by electrostatic forces. Our results show that synthetic polyelectrolyte-functionalized nanoparticles exhibit interfacial self-assembly behavior similar tomore » that of DNA-functionalized nanoparticles, providing a pathway for nanoparticle assembly in general.« less

Authors:
 [1];  [1];  [2];  [1]; ORCiD logo [1]
  1. Ames Lab. and Iowa State Univ., Ames, IA (United States)
  2. Ames Lab., Ames, IA (United States)
Publication Date:
Research Org.:
Ames Lab., Ames, IA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1409368
Report Number(s):
IS-J-9499
Journal ID: ISSN 0743-7463
Grant/Contract Number:  
AC02-07CH11358
Resource Type:
Accepted Manuscript
Journal Name:
Langmuir
Additional Journal Information:
Journal Volume: 33; Journal Issue: 43; Journal ID: ISSN 0743-7463
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Zhang, Honghu, Nayak, Srikanth, Wang, Wenjie, Mallapragada, Surya, and Vaknin, David. Interfacial Self-Assembly of Polyelectrolyte-Capped Gold Nanoparticles. United States: N. p., 2017. Web. https://doi.org/10.1021/acs.langmuir.7b02359.
Zhang, Honghu, Nayak, Srikanth, Wang, Wenjie, Mallapragada, Surya, & Vaknin, David. Interfacial Self-Assembly of Polyelectrolyte-Capped Gold Nanoparticles. United States. https://doi.org/10.1021/acs.langmuir.7b02359
Zhang, Honghu, Nayak, Srikanth, Wang, Wenjie, Mallapragada, Surya, and Vaknin, David. Fri . "Interfacial Self-Assembly of Polyelectrolyte-Capped Gold Nanoparticles". United States. https://doi.org/10.1021/acs.langmuir.7b02359. https://www.osti.gov/servlets/purl/1409368.
@article{osti_1409368,
title = {Interfacial Self-Assembly of Polyelectrolyte-Capped Gold Nanoparticles},
author = {Zhang, Honghu and Nayak, Srikanth and Wang, Wenjie and Mallapragada, Surya and Vaknin, David},
abstractNote = {Here, we report on pH- and salt-responsive assembly of nanoparticles capped with polyelectrolytes at vapor–liquid interfaces. Two types of alkylthiol-terminated poly(acrylic acid) (PAAs, varying in length) are synthesized and used to functionalize gold nanoparticles (AuNPs) to mimic similar assembly effects of single-stranded DNA-capped AuNPs using synthetic polyelectrolytes. Using surface-sensitive X-ray scattering techniques, including grazing incidence small-angle X-ray scattering (GISAXS) and X-ray reflectivity (XRR), we demonstrate that PAA-AuNPs spontaneously migrate to the vapor–liquid interfaces and form Gibbs monolayers by decreasing the pH of the suspension. The Gibbs monoalyers show chainlike structures of monoparticle thickness. The pH-induced self-assembly is attributed to the protonation of carboxyl groups and to hydrogen bonding between the neighboring PAA-AuNPs. In addition, we show that adding MgCl2 to PAA-AuNP suspensions also induces adsorption at the interface and that the high affinity between magnesium ions and carboxyl groups leads to two- and three-dimensional clusters that yield partial surface coverage and poorer ordering of NPs at the interface. We also examine the assembly of PAA-AuNPs in the presence of a positively charged Langmuir monolayer that promotes the attraction of the negatively charged capped NPs by electrostatic forces. Our results show that synthetic polyelectrolyte-functionalized nanoparticles exhibit interfacial self-assembly behavior similar to that of DNA-functionalized nanoparticles, providing a pathway for nanoparticle assembly in general.},
doi = {10.1021/acs.langmuir.7b02359},
journal = {Langmuir},
number = 43,
volume = 33,
place = {United States},
year = {2017},
month = {10}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 5 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Fuzzy Nanoassemblies: Toward Layered Polymeric Multicomposites
journal, August 1997


Nanoengineering of Inorganic and Hybrid Hollow Spheres by Colloidal Templating
journal, November 1998


Technology-driven layer-by-layer assembly of nanofilms
journal, April 2015


Reversibly erasable nanoporous anti-reflection coatings from polyelectrolyte multilayers
journal, September 2002

  • Hiller, Jeri'Ann; Mendelsohn, Jonas D.; Rubner, Michael F.
  • Nature Materials, Vol. 1, Issue 1
  • DOI: 10.1038/nmat719

Catalytic Activity of Palladium Nanoparticles Encapsulated in Spherical Polyelectrolyte Brushes and Core−Shell Microgels
journal, March 2007

  • Mei, Yu; Lu, Yan; Polzer, Frank
  • Chemistry of Materials, Vol. 19, Issue 5
  • DOI: 10.1021/cm062554s

Nanocellulose Aerogels Functionalized by Rapid Layer-by-Layer Assembly for High Charge Storage and Beyond
journal, September 2013

  • Hamedi, Mahiar; Karabulut, Erdem; Marais, Andrew
  • Angewandte Chemie International Edition, Vol. 52, Issue 46
  • DOI: 10.1002/anie.201305137

Nanocoatings onto Arteries via Layer-by-Layer Deposition:  Toward the in Vivo Repair of Damaged Blood Vessels
journal, June 2003

  • Thierry, Benjamin; Winnik, Françoise M.; Merhi, Yahye
  • Journal of the American Chemical Society, Vol. 125, Issue 25
  • DOI: 10.1021/ja034321x

Cell Surface Engineering with Polyelectrolyte Multilayer Thin Films
journal, May 2011

  • Wilson, John T.; Cui, Wanxing; Kozlovskaya, Veronika
  • Journal of the American Chemical Society, Vol. 133, Issue 18
  • DOI: 10.1021/ja110926s

Multilayered Polymer Nanocapsules Derived from Gold Nanoparticle Templates
journal, December 2000


From Functional Core/Shell Nanoparticles Prepared via Layer-by-Layer Deposition to Empty Nanospheres
journal, September 2004

  • Schneider, Grégory; Decher, Gero
  • Nano Letters, Vol. 4, Issue 10
  • DOI: 10.1021/nl0490826

Reversible Tuning of Silver Quantum Dot Monolayers Through the Metal-Insulator Transition
journal, September 1997


Nanoparticle Assembly and Transport at Liquid-Liquid Interfaces
journal, January 2003


Large-Scale Synthesis of Nearly Monodisperse CdSe/CdS Core/Shell Nanocrystals Using Air-Stable Reagents via Successive Ion Layer Adsorption and Reaction
journal, October 2003

  • Li, J. Jack; Wang, Y. Andrew; Guo, Wenzhuo
  • Journal of the American Chemical Society, Vol. 125, Issue 41, p. 12567-12575
  • DOI: 10.1021/ja0363563

Tunable plasmonic lattices of silver nanocrystals
journal, July 2007

  • Tao, Andrea; Sinsermsuksakul, Prasert; Yang, Peidong
  • Nature Nanotechnology, Vol. 2, Issue 7
  • DOI: 10.1038/nnano.2007.189

On the origin of the remarkable stability of aqueous foams stabilised by nanoparticles: link with microscopic surface properties
journal, January 2008

  • Cervantes Martinez, A.; Rio, E.; Delon, G.
  • Soft Matter, Vol. 4, Issue 7
  • DOI: 10.1039/b804177f

Responsive Plasmonic Assemblies of Amphiphilic Nanocrystals at Oil−Water Interfaces
journal, September 2010

  • Cheng, Lin; Liu, Aiping; Peng, Shuo
  • ACS Nano, Vol. 4, Issue 10
  • DOI: 10.1021/nn101685q

Nanoparticles at fluid interfaces: Exploiting capping ligands to control adsorption, stability and dynamics
journal, December 2012

  • Garbin, Valeria; Crocker, John C.; Stebe, Kathleen J.
  • Journal of Colloid and Interface Science, Vol. 387, Issue 1
  • DOI: 10.1016/j.jcis.2012.07.047

A DNA-based method for rationally assembling nanoparticles into macroscopic materials
journal, August 1996

  • Mirkin, Chad A.; Letsinger, Robert L.; Mucic, Robert C.
  • Nature, Vol. 382, Issue 6592, p. 607-609
  • DOI: 10.1038/382607a0

Organization of 'nanocrystal molecules' using DNA
journal, August 1996

  • Alivisatos, A. Paul; Johnsson, Kai P.; Peng, Xiaogang
  • Nature, Vol. 382, Issue 6592
  • DOI: 10.1038/382609a0

A Simple Method for Kinetic Control of DNA-Induced Nanoparticle Assembly
journal, November 2006

  • Maye, Mathew M.; Nykypanchuk, Dmytro; van der Lelie, Daniel
  • Journal of the American Chemical Society, Vol. 128, Issue 43
  • DOI: 10.1021/ja0654229

Directed Self-Assembly of Nanoparticles into Macroscopic Materials Using Antibody-Antigen Recognition
journal, April 1999


Ordered nanoparticle arrays formed on engineered chaperonin protein templates
journal, November 2002

  • McMillan, R. Andrew; Paavola, Chad D.; Howard, Jeanie
  • Nature Materials, Vol. 1, Issue 4
  • DOI: 10.1038/nmat775

Core-controlled polymorphism in virus-like particles
journal, January 2007

  • Sun, J.; DuFort, C.; Daniel, M. -C.
  • Proceedings of the National Academy of Sciences, Vol. 104, Issue 4
  • DOI: 10.1073/pnas.0610542104

DNA-guided crystallization of colloidal nanoparticles
journal, January 2008

  • Nykypanchuk, Dmytro; Maye, Mathew M.; van der Lelie, Daniel
  • Nature, Vol. 451, Issue 7178, p. 549-552
  • DOI: 10.1038/nature06560

DNA-programmable nanoparticle crystallization
journal, January 2008

  • Park, Sung Yong; Lytton-Jean, Abigail K. R.; Lee, Byeongdu
  • Nature, Vol. 451, Issue 7178, p. 553-556
  • DOI: 10.1038/nature06508

Free-standing nanoparticle superlattice sheets controlled by DNA
journal, May 2009

  • Cheng, Wenlong; Campolongo, Michael J.; Cha, Judy J.
  • Nature Materials, Vol. 8, Issue 6
  • DOI: 10.1038/nmat2440

DNA-nanoparticle superlattices formed from anisotropic building blocks
journal, October 2010

  • Jones, Matthew R.; Macfarlane, Robert J.; Lee, Byeongdu
  • Nature Materials, Vol. 9, Issue 11, p. 913-917
  • DOI: 10.1038/nmat2870

Nanoparticle Superlattice Engineering with DNA
journal, October 2011


A general strategy for the DNA-mediated self-assembly of functional nanoparticles into heterogeneous systems
journal, October 2013

  • Zhang, Yugang; Lu, Fang; Yager, Kevin G.
  • Nature Nanotechnology, Vol. 8, Issue 11
  • DOI: 10.1038/nnano.2013.209

Importance of the DNA “bond” in programmable nanoparticle crystallization
journal, October 2014

  • Macfarlane, Robert J.; Thaner, Ryan V.; Brown, Keith A.
  • Proceedings of the National Academy of Sciences, Vol. 111, Issue 42
  • DOI: 10.1073/pnas.1416489111

Prescribed nanoparticle cluster architectures and low-dimensional arrays built using octahedral DNA origami frames
journal, May 2015


Self-organized architectures from assorted DNA-framed nanoparticles
journal, June 2016

  • Liu, Wenyan; Halverson, Jonathan; Tian, Ye
  • Nature Chemistry, Vol. 8, Issue 9
  • DOI: 10.1038/nchem.2540

Diamond family of nanoparticle superlattices
journal, February 2016


Lattice engineering through nanoparticle–DNA frameworks
journal, February 2016

  • Tian, Ye; Zhang, Yugang; Wang, Tong
  • Nature Materials, Vol. 15, Issue 6, p. 654-661
  • DOI: 10.1038/nmat4571

Crystalline Gibbs Monolayers of DNA-Capped Nanoparticles at the Air–Liquid Interface
journal, September 2011

  • Campolongo, Michael J.; Tan, Shawn J.; Smilgies, Detlef-M.
  • ACS Nano, Vol. 5, Issue 10
  • DOI: 10.1021/nn202383b

Crystallization of DNA-Capped Gold Nanoparticles in High-Concentration, Divalent Salt Environments
journal, December 2013

  • Tan, Shawn J.; Kahn, Jason S.; Derrien, Thomas L.
  • Angewandte Chemie International Edition, Vol. 53, Issue 5
  • DOI: 10.1002/anie.201307113

Self-Assembly of DNA Functionalized Gold Nanoparticles at the Liquid-Vapor Interface
journal, May 2016

  • Zhang, Honghu; Wang, Wenjie; Hagen, Noah
  • Advanced Materials Interfaces, Vol. 3, Issue 16
  • DOI: 10.1002/admi.201600180

Two-Dimensional DNA-Programmable Assembly of Nanoparticles at Liquid Interfaces
journal, May 2014

  • Srivastava, Sunita; Nykypanchuk, Dmytro; Fukuto, Masafumi
  • Journal of the American Chemical Society, Vol. 136, Issue 23
  • DOI: 10.1021/ja501749b

Tunable Nanoparticle Arrays at Charged Interfaces
journal, September 2014

  • Srivastava, Sunita; Nykypanchuk, Dmytro; Fukuto, Masafumi
  • ACS Nano, Vol. 8, Issue 10
  • DOI: 10.1021/nn5042416

Assembling Bare Au Nanoparticles at Positively Charged Templates
journal, May 2016

  • Wang, Wenjie; Zhang, Honghu; Kuzmenko, Ivan
  • Scientific Reports, Vol. 6, Issue 1
  • DOI: 10.1038/srep26462

Dynamical Self-Assembly of Nanocrystal Superlattices during Colloidal Droplet Evaporation by in situ Small Angle X-Ray Scattering
journal, September 2004


Kinetically driven self assembly of highly ordered nanoparticle monolayers
journal, March 2006

  • Bigioni, Terry P.; Lin, Xiao-Min; Nguyen, Toan T.
  • Nature Materials, Vol. 5, Issue 4
  • DOI: 10.1038/nmat1611

In situ study of the formation mechanism of two-dimensional superlattices from PbSe nanocrystals
journal, September 2016

  • Geuchies, Jaco J.; van Overbeek, Carlo; Evers, Wiel H.
  • Nature Materials, Vol. 15, Issue 12
  • DOI: 10.1038/nmat4746

Macroscopic and tunable nanoparticle superlattices
journal, January 2017

  • Zhang, Honghu; Wang, Wenjie; Mallapragada, Surya
  • Nanoscale, Vol. 9, Issue 1
  • DOI: 10.1039/C6NR07136H

Ion-Specific Interfacial Crystallization of Polymer-Grafted Nanoparticles
journal, July 2017

  • Zhang, Honghu; Wang, Wenjie; Mallapragada, Surya
  • The Journal of Physical Chemistry C, Vol. 121, Issue 28
  • DOI: 10.1021/acs.jpcc.7b02549

Synthesis and Characterization of Ionic Block Copolymer Templated Calcium Phosphate Nanocomposites
journal, August 2008

  • Kanapathipillai, M.; Yusufoglu, Y.; Rawal, A.
  • Chemistry of Materials, Vol. 20, Issue 18
  • DOI: 10.1021/cm703441n

Maximizing DNA Loading on a Range of Gold Nanoparticle Sizes
journal, December 2006

  • Hurst, Sarah J.; Lytton-Jean, Abigail K. R.; Mirkin, Chad A.
  • Analytical Chemistry, Vol. 78, Issue 24
  • DOI: 10.1021/ac0613582

Assembling and ordering polymer-grafted nanoparticles in three dimensions
journal, January 2017

  • Zhang, Honghu; Wang, Wenjie; Akinc, Mufit
  • Nanoscale, Vol. 9, Issue 25
  • DOI: 10.1039/C7NR00787F

How does the chain extension of poly (acrylic acid) scale in aqueous solution? A combined study with light scattering and computer simulation
journal, May 2002

  • Reith, Dirk; Müller, Beate; Müller-Plathe, Florian
  • The Journal of Chemical Physics, Vol. 116, Issue 20
  • DOI: 10.1063/1.1471901

Role of Hydrogen Bonding in the pH-Dependent Aggregation of Colloidal Gold Particles Bearing Solution-Facing Carboxylic Acid Groups
journal, July 2009

  • Preston, Thomas C.; Nuruzzaman, Mohammad; Jones, Nathan D.
  • The Journal of Physical Chemistry C, Vol. 113, Issue 32
  • DOI: 10.1021/jp903284h

pH-Controlled Reversible Assembly of Peptide-Functionalized Gold Nanoparticles
journal, January 2007


The pH-responsive behaviour of poly(acrylic acid) in aqueous solution is dependent on molar mass
journal, January 2016

  • Swift, Thomas; Swanson, Linda; Geoghegan, Mark
  • Soft Matter, Vol. 12, Issue 9
  • DOI: 10.1039/C5SM02693H

Novel Interparticle Spatial Properties of Hydrogen-Bonding Mediated Nanoparticle Assembly
journal, January 2003

  • Han, Li; Luo, Jin; Kariuki, Nancy N.
  • Chemistry of Materials, Vol. 15, Issue 1
  • DOI: 10.1021/cm0208051

Nanoparticle Shape Anisotropy Dictates the Collective Behavior of Surface-Bound Ligands
journal, November 2011

  • Jones, Matthew R.; Macfarlane, Robert J.; Prigodich, Andrew E.
  • Journal of the American Chemical Society, Vol. 133, Issue 46
  • DOI: 10.1021/ja206777k

Specificity and Variation of Length Scale over Which Monovalent Halide Ions Neutralize a Charged Interface
journal, March 2015

  • Sung, Woongmo; Wang, Wenjie; Lee, Jonggwan
  • The Journal of Physical Chemistry C, Vol. 119, Issue 13
  • DOI: 10.1021/jp512233g

Solubility of highly charged anionic polyelectrolytes in presence of multivalent cations: Specific interaction effect
journal, January 2000

  • Sabbagh, I.; Delsanti, M.
  • The European Physical Journal E - Soft Matter, Vol. 1, Issue 1
  • DOI: 10.1007/s101890050009

Understanding the self-assembly of charged nanoparticles at the water/oil interface
journal, January 2006

  • Reincke, François; Kegel, Willem K.; Zhang, Hao
  • Phys. Chem. Chem. Phys., Vol. 8, Issue 33
  • DOI: 10.1039/B604535A

Interfacial Localization and Voltage-Tunable Arrays of Charged Nanoparticles
journal, November 2014

  • Bera, Mrinal K.; Chan, Henry; Moyano, Daniel F.
  • Nano Letters, Vol. 14, Issue 12
  • DOI: 10.1021/nl502450j

Reversible Partitioning of Nanoparticles at an Oil–Water Interface
journal, September 2016


    Works referencing / citing this record:

    Gold-Aryl nanoparticles coated with polyelectrolytes for adsorption and protection of DNA against nuclease degradation: NANO-GOLD ORGANOMETALLICS FOR ADSORPTION AND PROTECTION OF DNA
    journal, January 2019

    • Panicker, Seema; Ahmady, Islam M.; Almehdi, Ahmed M.
    • Applied Organometallic Chemistry, Vol. 33, Issue 4
    • DOI: 10.1002/aoc.4803

    Self-Assembled Metal-Phenolic Networks on Emulsions as Low-Fouling and pH-Responsive Particles
    journal, August 2018


    Polyethylene-Glycol-Mediated Self-Assembly of Magnetite Nanoparticles at the Liquid/Vapor Interface
    journal, January 2018

    • Vaknin, David; Wang, Wenjie; Islam, Farhan
    • Advanced Materials Interfaces, Vol. 5, Issue 6
    • DOI: 10.1002/admi.201701149