Correlating structural changes in thermoresponsive hydrogels to the optical response of embedded plasmonic nanoparticles

Zygadlo, Kamila; Liu, Chung-Hao; Bernardo, Emmanuel Reynoso; Ai, Huayue; Nieh, Mu-Ping; Hanson, Lindsey A.

doi:10.1039/d3na00758h

Title: Correlating structural changes in thermoresponsive hydrogels to the optical response of embedded plasmonic nanoparticles

Journal Article · Fri Nov 17 00:00:00 UTC 2023 · Nanoscale Advances

DOI: https://doi.org/10.1039/d3na00758h · OSTI ID:2470327

Zygadlo, Kamila ^[1];

^[2]; Bernardo, Emmanuel Reynoso ^[1];

^[1];

^[2];

^[1]

Trinity College, Hartford, CT (United States)
University of Connecticut, Storrs, CT (United States)

Stimuli-responsive microgels, composed of small beads with soft, deformable polymer networks swollen through a combination of synthetic control over the polymer and its interaction with water, form a versatile platform for development of multifunctional and biocompatible sensors. The interfacial structural variation of such materials at a nanometer length scale is essential to their function, but not yet fully comprehended. Here, we take advantage of the plasmonic response of a gold nanorod embedded in a thermoresponsive microgel (AuNR@PNIPMAm) to monitor structural changes in the hydrogel directly near the nanorod surface. By direct comparison of the plasmon response against measurements of the hydrogel structure from dynamic light scattering and nuclear magnetic resonance, we find that the microgel shell of batch-polymerized AuNR@PNIPMAm exhibits a heterogeneous volume phase transition reflected by different onset temperatures for changes in the hydrodyanmic radius (R_H) and plasmon resonance, respectively. The new approach of contrasting plasmonic response (a measure of local surface hydrogel structure) with R_H and relaxation times paves a new path to gain valuable insight for the design of plasmonic sensors based on stimuli-responsive hydrogels.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)

Sponsoring Organization:: National Institutes of Health (NIH); National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: SC0012704

OSTI ID:: 2470327

Journal Information:: Nanoscale Advances, Journal Name: Nanoscale Advances Journal Issue: 1 Vol. 6; ISSN 2516-0230

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (40)

Exploiting Advanced Hydrogel Technologies to Address Key Challenges in Regenerative Medicine Foyt, Daniel A.; Norman, Michael D. A.; Yu, Tracy T. L. Advanced Healthcare Materials, Vol. 7, Issue 8 https://doi.org/10.1002/adhm.201700939	journal	January 2018
Sequestering Gold Nanorods by Polymer Microgels Das, Mallika; Mordoukhovski, Leo; Kumacheva, Eugenia Advanced Materials, Vol. 20, Issue 12 https://doi.org/10.1002/adma.200702860	journal	June 2008
Encapsulation and Growth of Gold Nanoparticles in Thermoresponsive Microgels Contreras-Cáceres, Rafael; Sánchez-Iglesias, Ana; Karg, Matthias Advanced Materials, Vol. 20, Issue 9 https://doi.org/10.1002/adma.200800064	journal	May 2008
Unresolved issues in the preparation and characterization of thermoresponsive microgels Pelton, Robert Macromolecular Symposia, Vol. 207, Issue 1 https://doi.org/10.1002/masy.200450306	journal	February 2004
Nanorod-Coated PNIPAM Microgels: Thermoresponsive Optical Properties Karg, Matthias; Pastoriza-Santos, Isabel; Pérez-Juste, Jorge Small, Vol. 3, Issue 7 https://doi.org/10.1002/smll.200700078	journal	July 2007
Volume phase transition and structure of poly(N-isopropylacrylamide) microgels studied with 1H-NMR spectroscopy in D2O Andersson, Mirja; Maunu, Sirkka Liisa Colloid and Polymer Science, Vol. 285, Issue 3 https://doi.org/10.1007/s00396-006-1563-y	journal	October 2006
Structure and polymer dynamics within PNIPAM-based microgel particles Sierra-Martin, Benjamin; Retama, Jorge Rubio; Laurenti, Marco Advances in Colloid and Interface Science, Vol. 205 https://doi.org/10.1016/j.cis.2013.11.001	journal	March 2014
New “smart” poly(NIPAM) microgels and nanoparticle microgel hybrids: Properties and advances in characterisation Karg, Matthias; Hellweg, Thomas Current Opinion in Colloid & Interface Science, Vol. 14, Issue 6 https://doi.org/10.1016/j.cocis.2009.08.002	journal	December 2009
Temperature-tunable plasmonic property and SERS activity of the monodisperse thermo-responsive composite microgels with core–shell structure based on gold nanorod as core Dong, Xu; Zou, Xianbo; Liu, Xiaoyun Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 452 https://doi.org/10.1016/j.colsurfa.2014.03.090	journal	June 2014
Morphology and opto-thermal properties of the thermo-responsive PNIPAAm-protected gold nanorods Lee, Chia-Fen; Zhang, Geng-Ming; Nieh, Mu-Ping Polymer, Vol. 84 https://doi.org/10.1016/j.polymer.2015.12.047	journal	February 2016
Stimuli-responsive materials in additive manufacturing Shafranek, Ryan T.; Millik, S. Cem; Smith, Patrick T. Progress in Polymer Science, Vol. 93 https://doi.org/10.1016/j.progpolymsci.2019.03.002	journal	June 2019
Hydrophobic Collapse Initiates the Poly(N-isopropylacrylamide) Volume Phase Transition Reaction Coordinate Wu, Tsung-Yu; Zrimsek, Alyssa B.; Bykov, Sergei V. The Journal of Physical Chemistry B, Vol. 122, Issue 11 https://doi.org/10.1021/acs.jpcb.8b00740	journal	February 2018
Grazing Incidence Neutron Spin Echo Study of Poly(N-isopropylacrylamide) Brushes Witte, Judith; Krause, Patrick; Kyrey, Tetyana Macromolecules, Vol. 53, Issue 5 https://doi.org/10.1021/acs.macromol.9b01247	journal	February 2020
A Dual-Responsive Nanocomposite toward Climate-Adaptable Solar Modulation for Energy-Saving Smart Windows Lee, Heng Yeong; Cai, Yufeng; Bi, Shuguang ACS Applied Materials & Interfaces, Vol. 9, Issue 7 https://doi.org/10.1021/acsami.6b15065	journal	February 2017
Enhancement of Thermosensitivity of Gel-Immobilized Tunable Colloidal Photonic Crystals with Anisotropic Contraction Kanai, Toshimitsu; Yano, Hiroki; Kobayashi, Naoto ACS Macro Letters, Vol. 6, Issue 11 https://doi.org/10.1021/acsmacrolett.7b00780	journal	October 2017
Localized Nanoscale Heating Leads to Ultrafast Hydrogel Volume-Phase Transition Zhao, Jing; Su, Hanquan; Vansuch, Gregory E. ACS Nano, Vol. 13, Issue 1 https://doi.org/10.1021/acsnano.8b07150	journal	December 2018
Microgel Mechanics in Biomaterial Design Saxena, Shalini; Hansen, Caroline E.; Lyon, L. Andrew Accounts of Chemical Research, Vol. 47, Issue 8 https://doi.org/10.1021/ar500131v	journal	May 2014
Tunable Swelling Kinetics in Core−Shell Hydrogel Nanoparticles Gan, Daoji; Lyon, L. Andrew Journal of the American Chemical Society, Vol. 123, Issue 31 https://doi.org/10.1021/ja010609f	journal	July 2001
Temperature-Controlled Reversible Localized Surface Plasmon Resonance Response of Polymer-Functionalized Gold Nanoprisms in the Solid State Joshi, Gayatri K.; Smith, Kimberly A.; Johnson, Merrell A. The Journal of Physical Chemistry C, Vol. 117, Issue 49 https://doi.org/10.1021/jp409264w	journal	December 2013
Thermo-, pH-, and Light-Responsive Poly(N-isopropylacrylamide-co-methacrylic acid)–Au Hybrid Microgels Prepared by the in Situ Reduction Method Based on Au-Thiol Chemistry Shi, Shan; Wang, Qianman; Wang, Tao The Journal of Physical Chemistry B, Vol. 118, Issue 25 https://doi.org/10.1021/jp5027477	journal	June 2014
Microgels Loaded with Gold Nanorods: Photothermally Triggered Volume Transitions under Physiological Conditions ^† Das, Mallika; Sanson, Nicolas; Fava, Daniele Langmuir, Vol. 23, Issue 1 https://doi.org/10.1021/la061596s	journal	January 2007
Control of Poly(N-isopropylacrylamide) Microgel Network Structure by Precipitation Polymerization near the Lower Critical Solution Temperature Hu, Xiaobo; Tong, Zhen; Lyon, L. Andrew Langmuir, Vol. 27, Issue 7 https://doi.org/10.1021/la200114s	journal	March 2011
Shape- and Size-Dependent Refractive Index Sensitivity of Gold Nanoparticles Chen, Huanjun; Kou, Xiaoshan; Yang, Zhi Langmuir, Vol. 24, Issue 10 https://doi.org/10.1021/la800305j	journal	May 2008
Multiresponsive Hybrid Colloids Based on Gold Nanorods and Poly(NIPAM-co-allylacetic acid) Microgels: Temperature- and pH-Tunable Plasmon Resonance Karg, Matthias; Lu, Yan; Carbó-Argibay, Enrique Langmuir, Vol. 25, Issue 5 https://doi.org/10.1021/la803458j	journal	March 2009
"Domain" Coil-Globule Transition in Homopolymers Tiktopulo, Elizaveta I.; Uversky, Vladimir N.; Lushchik, Vanda B. Macromolecules, Vol. 28, Issue 22 https://doi.org/10.1021/ma00126a032	journal	October 1995
Synthesis and Characterization of Multiresponsive Core−Shell Microgels Jones, Clinton D.; Lyon, L. Andrew Macromolecules, Vol. 33, Issue 22 https://doi.org/10.1021/ma001398m	journal	October 2000
Application of ¹ H DOSY for Facile Measurement of Polymer Molecular Weights Li, Weibin; Chung, Hoyong; Daeffler, Chris Macromolecules, Vol. 45, Issue 24 https://doi.org/10.1021/ma301666x	journal	December 2012
Seeded Growth of Monodisperse Gold Nanorods Using Bromide-Free Surfactant Mixtures Ye, Xingchen; Gao, Yuzhi; Chen, Jun Nano Letters, Vol. 13, Issue 5 https://doi.org/10.1021/nl400653s	journal	April 2013
Optical Properties of Responsive Hybrid Au@Polymer Nanoparticles Tagliazucchi, Mario; Blaber, Martin G.; Schatz, George C. ACS Nano, Vol. 6, Issue 9 https://doi.org/10.1021/nn303221y	journal	August 2012
The design of reversible hydrogels to capture extracellular matrix dynamics Rosales, Adrianne M.; Anseth, Kristi S. Nature Reviews Materials, Vol. 1, Issue 2 https://doi.org/10.1038/natrevmats.2015.12	journal	February 2016
Nanoscale optomechanical actuators for controlling mechanotransduction in living cells Liu, Zheng; Liu, Yang; Chang, Yuan Nature Methods, Vol. 13, Issue 2 https://doi.org/10.1038/nmeth.3689	journal	December 2015
A comparison of the network structure and inner dynamics of homogeneously and heterogeneously crosslinked PNIPAM microgels with high crosslinker content Witte, Judith; Kyrey, Tetyana; Lutzki, Jana Soft Matter, Vol. 15, Issue 5 https://doi.org/10.1039/C8SM02141D	journal	January 2019
Hybrid conjugated polymer-Ag@PNIPAM fluorescent nanoparticles with metal-enhanced fluorescence Tang, Fu; Ma, Ning; Wang, Xiaoyu Journal of Materials Chemistry, Vol. 21, Issue 42 https://doi.org/10.1039/c1jm11395j	journal	January 2011
Interaction of gold nanoparticles with thermoresponsive microgels: influence of the cross-linker density on optical properties Gawlitza, Kornelia; Turner, Sarah T.; Polzer, Frank Physical Chemistry Chemical Physics, Vol. 15, Issue 37 https://doi.org/10.1039/c3cp51578h	journal	January 2013
Stimuli-responsive nanogel composites and their application in nanomedicine Molina, Maria; Asadian-Birjand, Mazdak; Balach, Juan Chemical Society Reviews, Vol. 44, Issue 17 https://doi.org/10.1039/c5cs00199d	journal	January 2015
Triggering the volume phase transition of core–shell Au nanorod–microgel nanocomposites with light Rodríguez-Fernández, Jessica; Fedoruk, Michael; Hrelescu, Calin Nanotechnology, Vol. 22, Issue 24 https://doi.org/10.1088/0957-4484/22/24/245708	journal	May 2011
Temperature-sensitive poly(N-Isopropyl-Acrylamide) microgel particles: A light scattering study Reufer, M.; Dıaz-Leyva, P.; Lynch, I. The European Physical Journal E, Vol. 28, Issue 2 https://doi.org/10.1140/epje/i2008-10387-2	journal	November 2008
Refractive Index Change Due to Volume-Phase Transition in Polyacrylamide Gel Nanospheres for Optoelectronics and Bio-photonics Garner, Brett W.; Cai, Tong; Ghosh, Santaneel Applied Physics Express, Vol. 2 https://doi.org/10.1143/APEX.2.057001	journal	April 2009
Localized Surface Plasmon Resonance Spectroscopy and Sensing Willets, Katherine A.; Van Duyne, Richard P. Annual Review of Physical Chemistry, Vol. 58, Issue 1 https://doi.org/10.1146/annurev.physchem.58.032806.104607	journal	May 2007
Plasmonic Materials for Surface-Enhanced Sensing and Spectroscopy Haes, Amanda J.; Haynes, Christy L.; McFarland, Adam D. MRS Bulletin, Vol. 30, Issue 5 https://doi.org/10.1557/mrs2005.100	journal	May 2005

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Title: Correlating structural changes in thermoresponsive hydrogels to the optical response of embedded plasmonic nanoparticles

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