An NH moiety is not required for anion binding to amides in aqueous solution

Langmuir : the ACS Journal of Surfaces and Colloids
Kelvin B RembertPaul S Cremer

Abstract

Herein, we use a combination of thermodynamic and spectroscopic measurements to investigate the interactions of Hofmeister anions with a thermoresponsive polymer, poly(N,N-diethylacrylamide) (PDEA). This amide-based polymer does not contain an NH moiety in its chemical structure and, thus, can serve as a model to test if anions bind to amides in the absence of an NH site. The lower critical solution temperature (LCST) of PDEA was measured as a function of the concentration for 11 sodium salts in aqueous solutions, and followed a direct Hofmeister series for the ability of anions to precipitate the polymer. More strongly hydrated anions (CO3(2-), SO4(2-), S2O3(2-), H2PO4(-), F(-), and Cl(-)) linearly decreased the LCST of the polymer with increasing the salt concentration. Weakly hydrated anions (SCN(-), ClO4(-), I(-), NO3(-), and Br(-)) increased the LCST at lower salt concentrations but salted the polymer out at higher salt concentrations. Proton nuclear magnetic resonance (NMR) was used to probe the mechanism of the salting-in effect and showed apparent binding between weakly hydrated anions (SCN(-) and I(-)) and the α protons of the polymer backbone. Additional experiments performed by attenuated total reflection Fourier tra...Continue Reading

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Citations

Dec 8, 2015·Journal of Colloid and Interface Science·Saeed Zajforoushan Moghaddam, Esben Thormann
Jan 6, 2017·Journal of the American Chemical Society·Jan HeydaPaul S Cremer
Jan 18, 2017·The Journal of Physical Chemistry. B·Halil I OkurPavel Jungwirth
Jan 21, 2017·The Journal of Physical Chemistry. B·Nicolas O JohnsonYanjie Zhang
Apr 28, 2017·Langmuir : the ACS Journal of Surfaces and Colloids·Saeed Zajforoushan Moghaddam, Esben Thormann
Nov 8, 2018·Angewandte Chemie·Vasileios BalosJohannes Hunger
Jan 26, 2018·Nihon Rinshō Men'eki Gakkai kaishi = Japanese journal of clinical immunology·Shigeru Oshima
Apr 16, 2020·Soft Matter·Haiyang Yuan, Guangming Liu
Jan 17, 2020·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Olga A FranciscoMazdak Khajehpour
Dec 3, 2016·Soft Matter·Lvdan LiuGuangming Liu
Oct 31, 2020·Journal of the American Chemical Society·Ellen E BrucePaul S Cremer
Dec 16, 2016·The Journal of Physical Chemistry. B·Bradley A RogersYanjie Zhang
Mar 20, 2019·The Journal of Physical Chemistry. B·Ki Chul Park, Takehiko Tsukahara
Mar 29, 2019·Journal of the American Chemical Society·Ellen E BruceNico F A van der Vegt
Dec 28, 2019·Langmuir : the ACS Journal of Surfaces and Colloids·Ki Chul Park, Takehiko Tsukahara
Oct 27, 2018·Langmuir : the ACS Journal of Surfaces and Colloids·Mitsuhiro MatsumotoYasuyuki Tsuboi
Jan 8, 2021·The Journal of Physical Chemistry. B·Ellen E BruceNico F A van der Vegt
Nov 3, 2021·Nature Chemistry·Bradley A RogersPaul S Cremer

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