TY - JOUR
T1 - Classical Molecular Dynamics Simulation of Glyonic Liquids
T2 - Structural Insights and Relation to Conductive Properties
AU - Hei, Bai
AU - Pemberton, Jeanne E.
AU - Schwartz, Steven D.
N1 - Publisher Copyright:
© 2023 American Chemical Society.
PY - 2023/2/2
Y1 - 2023/2/2
N2 - Rhamnolipids are biosurfactants that have obtained wide industrial and environmental interests with their biodegradability and great surface activity. Besides their important roles as surfactants, they are found to function as a new type of glycolipid-based protic ionic liquids (ILs)─glyonic liquids (GLs). GLs are reported to have impressive physicochemical properties, especially superionic conductivity, and it was reported in experiments that specific ion selections and the fraction of water content have a strong effect on the conductivity. Also, the shape of the conductivity curve as a function of water fraction in GLs is interesting with a sharp increase first and a long plateau. We related the conductivities to the three-dimensional (3D) networks composed of −OH inside the GLs utilizing classical molecular dynamics (MD) simulations. The amount and size of these networks vary with both ion species and water fractions. Before reaching the first hydration layer, the −OH networks with higher projection/box length ratios indicate better conductivity; after reaching the first hydration layer and forming continuous structures, the conductivity retains with more water molecules participating in the continuous networks. Therefore, networks are found to be a qualitative predictor of actual conductivity. This is explained by the analysis of the atomic structures, including radial distribution function, fraction free volume, anion conformations, and hydrogen bond occupancies, of GLs and their water mixtures under different chemical conditions.
AB - Rhamnolipids are biosurfactants that have obtained wide industrial and environmental interests with their biodegradability and great surface activity. Besides their important roles as surfactants, they are found to function as a new type of glycolipid-based protic ionic liquids (ILs)─glyonic liquids (GLs). GLs are reported to have impressive physicochemical properties, especially superionic conductivity, and it was reported in experiments that specific ion selections and the fraction of water content have a strong effect on the conductivity. Also, the shape of the conductivity curve as a function of water fraction in GLs is interesting with a sharp increase first and a long plateau. We related the conductivities to the three-dimensional (3D) networks composed of −OH inside the GLs utilizing classical molecular dynamics (MD) simulations. The amount and size of these networks vary with both ion species and water fractions. Before reaching the first hydration layer, the −OH networks with higher projection/box length ratios indicate better conductivity; after reaching the first hydration layer and forming continuous structures, the conductivity retains with more water molecules participating in the continuous networks. Therefore, networks are found to be a qualitative predictor of actual conductivity. This is explained by the analysis of the atomic structures, including radial distribution function, fraction free volume, anion conformations, and hydrogen bond occupancies, of GLs and their water mixtures under different chemical conditions.
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U2 - 10.1021/acs.jpcb.2c07264
DO - 10.1021/acs.jpcb.2c07264
M3 - Article
C2 - 36652632
AN - SCOPUS:85146610370
SN - 1520-6106
VL - 127
SP - 921
EP - 931
JO - Journal of Physical Chemistry B
JF - Journal of Physical Chemistry B
IS - 4
ER -