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

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

doi:10.1039/d3na00758h

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

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

Research output: Contribution to journal › Article › peer-review

Abstract

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.

Original language	English
Pages (from-to)	146-154
Number of pages	9
Journal	Nanoscale Advances
Volume	6
Issue number	1
DOIs	https://doi.org/10.1039/d3na00758h
State	Published - Nov 17 2023
Externally published	Yes

Funding

The authors would like to thank Dr Lin Yang and the beamtime of 16ID-LiX at the NSLS-II (Brookhaven National Laboratory) through a beamtime proposal (BAG-302208). The LiX beamline is part of the Center for BioMolecular Structure (CBMS), which is primarily supported by the National Institutes of Health, National Institute of General Medical Sciences (NIGMS) through a P30 Grant (P30GM133893), and by the DOE Office of Biological and Environmental Research (KP1605010). LiX also received additional support from NIH Grant S10 OD012331. As part of NSLS-II, a national user facility at Brookhaven National Laboratory, work performed at the CBMS is supported in part by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences Program under contract number DE-SC0012704. The Bruker Avance III used for NMR measurements was obtained with a National Science Foundation MRI grant (NSF-MRI CHE-0619275).

Funders	Funder number
NSF-MRI	CHE-0619275
Office of Basic Energy Sciences Program	DE-SC0012704
National Science Foundation
National Institutes of Health	S10 OD012331
U.S. Department of Energy
National Institute of General Medical Sciences	P30GM133893
Office of Science
Biological and Environmental Research	KP1605010

Access to Document

10.1039/d3na00758h

Cite this

@article{3a8f20816f574b62baa223595178b04a,

title = "Correlating structural changes in thermoresponsive hydrogels to the optical response of embedded plasmonic nanoparticles",

abstract = "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 (RH) and plasmon resonance, respectively. The new approach of contrasting plasmonic response (a measure of local surface hydrogel structure) with RH and relaxation times paves a new path to gain valuable insight for the design of plasmonic sensors based on stimuli-responsive hydrogels.",

author = "Kamila Zygadlo and Liu, {Chung Hao} and Bernardo, {Emmanuel Reynoso} and Huayue Ai and Nieh, {Mu Ping} and Hanson, {Lindsey A.}",

note = "Publisher Copyright: {\textcopyright} 2024 RSC",

year = "2023",

month = nov,

day = "17",

doi = "10.1039/d3na00758h",

language = "English",

volume = "6",

pages = "146--154",

journal = "Nanoscale Advances",

issn = "2516-0230",

publisher = "Royal Society of Chemistry",

number = "1",

}

TY - JOUR

T1 - Correlating structural changes in thermoresponsive hydrogels to the optical response of embedded plasmonic nanoparticles

AU - Zygadlo, Kamila

AU - Liu, Chung Hao

AU - Bernardo, Emmanuel Reynoso

AU - Ai, Huayue

AU - Nieh, Mu Ping

AU - Hanson, Lindsey A.

PY - 2023/11/17

Y1 - 2023/11/17

N2 - 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 (RH) and plasmon resonance, respectively. The new approach of contrasting plasmonic response (a measure of local surface hydrogel structure) with RH and relaxation times paves a new path to gain valuable insight for the design of plasmonic sensors based on stimuli-responsive hydrogels.

AB - 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 (RH) and plasmon resonance, respectively. The new approach of contrasting plasmonic response (a measure of local surface hydrogel structure) with RH and relaxation times paves a new path to gain valuable insight for the design of plasmonic sensors based on stimuli-responsive hydrogels.

UR - http://www.scopus.com/inward/record.url?scp=85178640648&partnerID=8YFLogxK

U2 - 10.1039/d3na00758h

DO - 10.1039/d3na00758h

M3 - Article

AN - SCOPUS:85178640648

SN - 2516-0230

VL - 6

SP - 146

EP - 154

JO - Nanoscale Advances

JF - Nanoscale Advances

IS - 1

ER -

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

Abstract

Funding

Access to Document

Other files and links

Fingerprint

Cite this