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Specific ion modulated thermoresponse of poly (N-isopropylacrylamide) brushes

Humphreys, Ben A LU ; Willott, Joshua D ; Murdoch, Timothy J ; Webber, Grant B and Wanless, Erica J (2016) In Physical Chemistry Chemical Physics 18(8). p.6037-6046
Abstract
The influence of specific anions on the equilibrium thermoresponse of poly(N-isopropylacrylamide) (pNIPAM) brushes has been studied using in situ ellipsometry, quartz crystal microbalance with dissipation (QCM-D) and static contact angle measurements between 20 and 45 °C in the presence of up to 250 mM acetate and thiocyanate anions in water. The thickness and changes in dissipation exhibited a broad swelling transition spanning approximately 15 °C from collapsed (high temperatures) to swollen conformation (low temperatures) while the brush surface wettability changed over approximately 2 °C. In the presence of the kosmotropic acetate anions, the measured lower critical solution temperature (LCST) by the three techniques was very similar... (More)
The influence of specific anions on the equilibrium thermoresponse of poly(N-isopropylacrylamide) (pNIPAM) brushes has been studied using in situ ellipsometry, quartz crystal microbalance with dissipation (QCM-D) and static contact angle measurements between 20 and 45 °C in the presence of up to 250 mM acetate and thiocyanate anions in water. The thickness and changes in dissipation exhibited a broad swelling transition spanning approximately 15 °C from collapsed (high temperatures) to swollen conformation (low temperatures) while the brush surface wettability changed over approximately 2 °C. In the presence of the kosmotropic acetate anions, the measured lower critical solution temperature (LCST) by the three techniques was very similar and decreased linearly as a function of ionic strength. Conversely, increasing the concentration of the chaotropic thiocyanate anions raised the LCST of the pNIPAM brushes with variation in the measured LCST between the three techniques increasing with ionic strength. The thickness of the pNIPAM brush was seen to progressively increase with increasing thiocyanate concentration at all temperatures. It is proposed that specific ion binding of the chaotropic thiocyanate anion with pNIPAM amide moieties increases the electrostatic intra- and intermolecular repulsion within and between pNIPAM chains. This allows the brush to begin to swell at higher temperatures and to an overall greater extent. (Less)
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author
; ; ; and
publishing date
type
Contribution to journal
publication status
published
subject
in
Physical Chemistry Chemical Physics
volume
18
issue
8
pages
10 pages
publisher
Royal Society of Chemistry
external identifiers
  • scopus:84959036996
ISSN
1463-9084
DOI
10.1039/C5CP07468A
language
English
LU publication?
no
id
49c67685-9471-4f0e-85bf-dca6e1eb5685
date added to LUP
2022-04-01 21:10:02
date last changed
2022-04-11 10:57:24
@article{49c67685-9471-4f0e-85bf-dca6e1eb5685,
  abstract     = {{The influence of specific anions on the equilibrium thermoresponse of poly(N-isopropylacrylamide) (pNIPAM) brushes has been studied using in situ ellipsometry, quartz crystal microbalance with dissipation (QCM-D) and static contact angle measurements between 20 and 45 °C in the presence of up to 250 mM acetate and thiocyanate anions in water. The thickness and changes in dissipation exhibited a broad swelling transition spanning approximately 15 °C from collapsed (high temperatures) to swollen conformation (low temperatures) while the brush surface wettability changed over approximately 2 °C. In the presence of the kosmotropic acetate anions, the measured lower critical solution temperature (LCST) by the three techniques was very similar and decreased linearly as a function of ionic strength. Conversely, increasing the concentration of the chaotropic thiocyanate anions raised the LCST of the pNIPAM brushes with variation in the measured LCST between the three techniques increasing with ionic strength. The thickness of the pNIPAM brush was seen to progressively increase with increasing thiocyanate concentration at all temperatures. It is proposed that specific ion binding of the chaotropic thiocyanate anion with pNIPAM amide moieties increases the electrostatic intra- and intermolecular repulsion within and between pNIPAM chains. This allows the brush to begin to swell at higher temperatures and to an overall greater extent.}},
  author       = {{Humphreys, Ben A and Willott, Joshua D and Murdoch, Timothy J and Webber, Grant B and Wanless, Erica J}},
  issn         = {{1463-9084}},
  language     = {{eng}},
  number       = {{8}},
  pages        = {{6037--6046}},
  publisher    = {{Royal Society of Chemistry}},
  series       = {{Physical Chemistry Chemical Physics}},
  title        = {{Specific ion modulated thermoresponse of poly (<i>N</i>-isopropylacrylamide) brushes}},
  url          = {{http://dx.doi.org/10.1039/C5CP07468A}},
  doi          = {{10.1039/C5CP07468A}},
  volume       = {{18}},
  year         = {{2016}},
}