Physicochemical control of solvation and molecular assembly of charged amphiphilic oligomers at air-aqueous interfaces

Liu, Zening; Lin, Lu; Li, Tianyu; Premadasa, Uvinduni I.; Hong, Kunlun; Ma, Ying-Zhong; Sacci, Robert L.; Katsaras, John; Carrillo, Jan-Michael; Doughty, Benjamin; Collier, C. Patrick

doi:10.1016/j.jcis.2024.05.008

Physicochemical control of solvation and molecular assembly of charged amphiphilic oligomers at air-aqueous interfaces

Journal Article · Tue May 07 00:00:00 EDT 2024 · Journal of Colloid and Interface Science

DOI:https://doi.org/10.1016/j.jcis.2024.05.008· OSTI ID:2376326

Liu, Zening ^[1]; ^[2]; ^[3]; ^[2]; ^[1]; ^[2]; ^[2]; ^[4]; ^[1]; ^[2]; ^[1]

Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Univ. of Tennessee, Knoxville, TN (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Shull Wollan Center

Hypothesis: Understanding the rules that control the assembly of nanostructured soft materials at interfaces is central to many applications. We hypothesize that electrolytes can be used to alter the hydration shell of amphiphilic oligomers at the air-aqueous interface of Langmuir films, thereby providing a means to control the formation of emergent nanostructures. Experiments: Three representative salts – (NaF, NaCl, NaSCN) were studied for mediating the self-assembly of oligodimethylsiloxane methylimidazolium (ODMS-MIM⁺) amphiphiles in Langmuir films. The effects of the different salts on the nanostructure assembly of these films were probed using vibrational sum frequency generation (SFG) spectroscopy and Langmuir trough techniques. Experimental data were supported by atomistic molecular dynamic simulations. Findings: Langmuir trough surface pressure – area isotherms suggested a surprising effect on oligomer assembly, whereby the presence of anions affects the stability of the interfacial layer irrespective of their surface propensities. In contrast, SFG results implied a strong anion effect that parallels the surface activity of anions. These seemingly contradictory trends are explained by anion driven tail dehydration resulting in increasingly heterogeneous systems with entangled ODMS tails and appreciable anion penetration into the complex interfacial layer comprised of headgroups, tails, and interfacial water molecules. These findings provide physical and chemical insight for tuning a wide range of interfacial assemblies.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 2376326

Alternate ID(s):: OSTI ID: 2348966

Journal Information:: Journal of Colloid and Interface Science, Journal Name: Journal of Colloid and Interface Science Vol. 669; ISSN 0021-9797

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Langmuir films
Nanostructure assembly
Solvation
Specific ion effects
Sum frequency generation spectroscopy
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Physicochemical control of solvation and molecular assembly of charged amphiphilic oligomers at air-aqueous interfaces

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References (62)

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