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

Title: Dual-Responsive Reversible Plasmonic Behavior of Core–Shell Nanostructures with pH-Sensitive and Electroactive Polymer Shells

Journal Article · · Chemistry of Materials

In this paper, we report novel dual-responsive plasmonic core–shell anisotropic nanostructures composed of gold nanorod (AuNR) and responsive polyaniline (PANI) shells with plasmonic mode appearance reversibly modulated through orthogonal stimuli (i.e., electrical potential and pH change). In this system, the PANI shells provide AuNR cores with three different refractive index environments depending on stimuli (pH and electrical potential). Therefore, no additional secondary responsive component is necessary to induce the dual-responsive properties of AuNR cores. Furthermore, in this study, dual-responsive properties can be realized for nanostructures fixed on substrates, whereas previously reported dual-responsive plasmonic systems can only be controlled in solution. Here, the highest localized surface plasmonic resonance (LSPR) shift of the AuNR cores can be induced by changing both local pH and applying electric potential. Notably, a significant plasmon band shift by 107 nm is realized with only 8 nm thick PANI shell due to the large refractive index change at the gold–polymer interface. A maximum shift of the longitudinal plasmon mode of 149 nm is obtained by applying a modest electrical potential (below ±1 V), a large shift rarely reported in the literature for metal nanostructures. Moreover, our anisotropic core/shell nanostructures exhibit stable and reversible dual-responsive LSPR behavior over 100 cycles without degradation.

Research Organization:
Georgia Institute of Technology, Atlanta, GA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division; National Science Foundation (NSF)
Grant/Contract Number:
SC0002232; FG02-09ER46604
OSTI ID:
1534448
Journal Information:
Chemistry of Materials, Vol. 28, Issue 20; ISSN 0897-4756
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 42 works
Citation information provided by
Web of Science

References (73)

Controlling the Synthesis and Assembly of Silver Nanostructures for Plasmonic Applications journal June 2011
A Label-Free Immunoassay Based Upon Localized Surface Plasmon Resonance of Gold Nanorods journal February 2008
Plasmonic-metal nanostructures for efficient conversion of solar to chemical energy journal November 2011
Dual Plasmonic Nanostructures for High Performance Inverted Organic Solar Cells journal May 2012
Facile Synthesis of Sunlight-Driven AgCl:Ag Plasmonic Nanophotocatalyst journal May 2010
Cancer Cell Imaging and Photothermal Therapy in the Near-Infrared Region by Using Gold Nanorods journal February 2006
Rational Selection of Gold Nanorod Geometry for Label-Free Plasmonic Biosensors journal March 2009
Biosensing with plasmonic nanosensors journal June 2008
Real-time tunable lasing from plasmonic nanocavity arrays journal April 2015
Metallic Nanoparticle Arrays: A Common Substrate for Both Surface-Enhanced Raman Scattering and Surface-Enhanced Infrared Absorption journal March 2008
Distance and Wavelength Dependent Quenching of Molecular Fluorescence by Au@SiO 2 Core–Shell Nanoparticles journal June 2013
Tunability of Subradiant Dipolar and Fano-Type Plasmon Resonances in Metallic Ring/Disk Cavities: Implications for Nanoscale Optical Sensing journal February 2009
The State of Nanoparticle-Based Nanoscience and Biotechnology: Progress, Promises, and Challenges journal September 2012
Shape- and Size-Dependent Refractive Index Sensitivity of Gold Nanoparticles journal May 2008
Surface Plasmon Resonance in Bimetallic Core–Shell Nanoparticles journal July 2015
A Simple Millifluidic Benchtop Reactor System for the High-Throughput Synthesis and Functionalization of Gold Nanoparticles with Different Sizes and Shapes journal May 2013
Improved Size-Tunable Synthesis of Monodisperse Gold Nanorods through the Use of Aromatic Additives journal February 2012
Temperature-controlled surface plasmon resonance in VO_2 nanorods journal January 2002
Active molecular plasmonics: tuning surface plasmon resonances by exploiting molecular dimensions journal June 2015
Active Modulation of Nanorod Plasmons journal September 2011
PlasMOStor: A Metal−Oxide−Si Field Effect Plasmonic Modulator journal February 2009
Tunable Color Filters Based on Metal−Insulator−Metal Resonators journal July 2009
Light-Responsive Plasmonic Arrays Consisting of Silver Nanocubes and a Photoisomerizable Matrix journal February 2015
Novel pH-responsive nanoplasmonic sensor: controlling polymer structural change to modulate localized surface plasmon resonance response journal January 2014
Light-Driven Plasmonic Switches Based on Au Nanodisk Arrays and Photoresponsive Liquid Crystals journal August 2008
Reversible Strong Coupling in Silver Nanoparticle Arrays Using Photochromic Molecules journal December 2012
Nanorod-Coated PNIPAM Microgels: Thermoresponsive Optical Properties journal July 2007
Specific Biochemical-to-Optical Signal Transduction by Responsive Thin Hydrogel Films Loaded with Noble Metal Nanoparticles journal March 2010
(Gold Nanorod Core)/(Polyaniline Shell) Plasmonic Switches with Large Plasmon Shifts and Modulation Depths journal March 2014
Emerging applications of stimuli-responsive polymer materials journal January 2010
WO3 Sol–Gel Modified Ag Nanoparticle Arrays for Electrochemical Modulation of Surface Plasmon Resonance journal August 2003
Optical Properties of Ultrathin Poly(3,4-ethylenedioxythiophene) Films at Several Doping Levels Studied by In Situ Electrochemical Surface Plasmon Resonance Spectroscopy journal October 2003
Giant Plasmon Resonance Shift Using Poly(3,4-ethylenedioxythiophene) Electrochemical Switching journal August 2010
Active Plasmonic Devices with Anisotropic Optical Response: A Step Toward Active Polarizer journal May 2009
Conducting polymer/gold nanoparticle hybrid materials: A step toward electroactive plasmonic devices journal June 2007
Conducting Polymer Electrochemical Switching as an Easy Means for Designing Active Plasmonic Devices journal November 2005
Electrically Tunable Plasmonic Behavior of Nanocube–Polymer Nanomaterials Induced by a Redox-Active Electrochromic Polymer journal May 2014
Electrically Controlled Plasmonic Behavior of Gold Nanocube@Polyaniline Nanostructures: Transparent Plasmonic Aggregates journal April 2016
Design of Hybrid Electrochromic Materials with Large Electrical Modulation of Plasmonic Resonances journal May 2016
Electropolymerization and doping/dedoping properties of polyaniline thin films as studied by electrochemical-surface plasmon spectroscopy and by the quartz crystal microbalance journal January 2004
pH-Triggered SERS via Modulated Plasmonic Coupling in Individual Bimetallic Nanocobs journal April 2011
Gold Nanorod–pNIPAM Hybrids with Reversible Plasmon Coupling: Synthesis, Modeling, and SERS Properties journal March 2015
Multiresponsive Hybrid Colloids Based on Gold Nanorods and Poly(NIPAM-co-allylacetic acid) Microgels: Temperature- and pH-Tunable Plasmon Resonance journal March 2009
Gold Nanoparticles Functionalized by a Dextran-Based pH- and Temperature-Sensitive Polymer: Gold Nanoparticles Functionalized by a … journal December 2009
From multi-responsive tri- and diblock copolymers to diblock-copolymer-decorated gold nanoparticles: the effect of architecture on micellization behaviors in aqueous solutions journal January 2015
Light-Controllable Surface Plasmon Resonance Absorption of Gold Nanoparticles Covered with Photochromic Diarylethene Polymers journal September 2009
Localized Surface Plasmon Resonance Investigations of Photoswitching in Azobenzene-Functionalized Self-Assembled Monolayers on Au journal August 2013
Protein/Polymer-Based Dual-Responsive Gold Nanoparticles with pH-Dependent Thermal Sensitivity journal January 2012
Multiresponsive Block Copolymer-Modified “Hairy” Gold Nanoparticles for Remote Control of Interfaces journal October 2013
Thermo- and photoresponsive reversible changes in localized surface plasmon resonance of gold nanoparticles covered by poly(N-isopropylacrylamide) with photochromic diarylethene end group journal January 2013
Highly controlled core/shell structures: tunable conductive polymer shells on gold nanoparticles and nanochains journal January 2009
Multicompartmental Microcapsules from Star Copolymer Micelles journal February 2013
Polymer Acid Doped Polyaniline Is Electrochemically Stable Beyond pH 9 journal December 2008
Oxidatively stable polyaniline:polyacid electrodes for electrochemical energy storage journal January 2013
Carbon nanotubes: enhancing the polymer building blocks for intelligent materials journal January 2006
Charge Storage in Polymer Acid-Doped Polyaniline-Based Layer-by-Layer Electrodes journal October 2013
Optical properties of polyaniline journal May 1993
Polyaniline Exhibiting Stable and Reversible Switching in the Visible Extending into the Near-IR in Aqueous Media journal February 2010
Spectral response of ellipsometric sensors journal September 1994
Discourse on the utilization of polyaniline coatings for surface plasmon resonance sensing of ammonia vapor journal September 2011
Development and application of patterned conducting polymer thin films as chemoresponsive and electrochemically responsive optical diffraction gratings journal March 2001
Polyaniline/Vanadium Pentoxide Layer-by-Layer Electrodes for Energy Storage journal December 2011
Quantitative Evaluation of Sensitivity and Selectivity of Multiplex NanoSPR Biosensor Assays journal November 2007
Refractive Index of Thin Aqueous Films Confined between Two Hydrophobic Surfaces journal May 1994
Nanoscale Dimensional Changes and Optical Properties of Polyaniline Measured by In Situ Spectroscopic Ellipsometry journal April 1994
Large-area plasmonic electrodes and active plasmonic devices generated by electrochemical processes journal October 2015
Optical Sensitivity Comparison of Multiblock Gold–Silver Nanorods Toward Biomolecule Detection: Quadrupole Surface Plasmonic Detection of Dopamine journal March 2013
Plasmonic nanorod absorbers as orientation sensors journal February 2010
Optical detection of single non-absorbing molecules using the surface plasmon resonance of a gold nanorod journal April 2012
Plasmonic/Nonlinear Optical Material Core/Shell Nanorods as Nanoscale Plasmon Modulators and Optical Voltage Sensors journal November 2015
Localized Surface Plasmon Resonance Sensors journal June 2011
Polyaniline dispersions 4. Polymerization seeded by polyaniline particles journal October 1994
Anisotropic Plasmonic Sensing of Individual or Coupled Gold Nanorods journal October 2011

Cited By (6)

Actively Tunable Collective Localized Surface Plasmons by Responsive Hydrogel Membrane journal May 2019
Switching plasmonic Fano resonance in gold nanosphere–nanoplate heterodimers journal January 2019
A colorimetric/SERS dual-mode sensing method for the detection of mercury( ii ) based on rhodanine-stabilized gold nanobipyramids journal January 2018
Heterogeneous forward and backward scattering modulation by polymer-infused plasmonic nanohole arrays journal January 2019
A Tunable Polymer–Metal Based Anti‐Reflective Metasurface journal November 2019
Properties of quantum dots coupled to plasmons and optical cavities journal December 2019

Figures / Tables (10)