The Unexpected Role of Cations in the Self-Assembly of Positively Charged Amphiphiles at Liquid/Liquid Interfaces

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

doi:10.1021/acs.jpclett.2c02921

The Unexpected Role of Cations in the Self-Assembly of Positively Charged Amphiphiles at Liquid/Liquid Interfaces

Journal Article · Thu Nov 17 00:00:00 EST 2022 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.2c02921· OSTI ID:1922306

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

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

Conventional wisdom suggests that cations play a minimal role in the assembly of cationic amphiphiles. Here, we show that at liquid/liquid (L/L) interfaces, specific cation effects can modulate the assemblies of hydrophobic tails in an oil phase despite being attached to cationic headgroups in the aqueous phase. In this work, we used oligo-dimethylsiloxane (ODMS) methyl imidazolium amphiphiles to identify these specific interactions at hexadecane/aqueous interfaces. Small cations, such as Li⁺, bind to the O atoms in the ODMS tail and pin it to the interface, thereby imposing a kinked conformation-as evidenced by vibrational sum frequency generation spectroscopy and molecular dynamics simulations. While larger Cs⁺ ions more readily partition to the interface, they do not form analogous complexes. Our data not only point to ways for controlling amphiphile structure at L/L interfaces but also suggest a means for the separation of Li⁺, or related applications, in soft-matter electronics.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1922306

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 46 Vol. 13; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (62)

Understanding Self-Assembly and the Stabilization of Liquid/Liquid Interfaces: The Importance of Ligand Tail Branching and Oil-Phase Solvation Premadasa, Uvinduni I.; Ma, Ying-Zhong; Sacci, Robert L. Journal of Colloid and Interface Science, Vol. 609 https://doi.org/10.1016/j.jcis.2021.11.088	journal	March 2022
The structure of aqueous lithium chloride solutions at high concentrations as revealed by a comparison of classical interatomic potential models Pethes, Ildikó Journal of Molecular Liquids, Vol. 264 https://doi.org/10.1016/j.molliq.2018.05.044	journal	August 2018
Amphiphile conformation impacts aggregate morphology and solution structure across multiple lengthscales Servis, Michael J.; Sadhu, Biswajit; Soderholm, L. Journal of Molecular Liquids, Vol. 345 https://doi.org/10.1016/j.molliq.2021.117743	journal	January 2022
Establishing a unified framework for ion solvation and transport in liquid and solid electrolytes Siegel, Donald J.; Nazar, Linda; Chiang, Yet-Ming Trends in Chemistry, Vol. 3, Issue 10 https://doi.org/10.1016/j.trechm.2021.06.004	journal	October 2021
Amphiphile Organization in Organic Solutions: An Alternative Explanation for Small-Angle X-ray Scattering Features in Malonamide/Alkane Mixtures Servis, Michael J.; Piechowicz, Marek; Shkrob, Ilya A. The Journal of Physical Chemistry B, Vol. 124, Issue 47 https://doi.org/10.1021/acs.jpcb.0c07080	journal	November 2020
Ion Pairing and Molecular Orientation at Liquid/Liquid Interfaces: Self-Assembly and Function Lin, Lu; Chowdhury, Azhad U.; Ma, Ying-Zhong The Journal of Physical Chemistry B, Vol. 126, Issue 11 https://doi.org/10.1021/acs.jpcb.2c01148	journal	March 2022
Neutron Diffraction Study on the Structure of Hydrated Li ⁺ in Dilute Aqueous Solutions Kameda, Yasuo; Maeda, Shunya; Amo, Yuko The Journal of Physical Chemistry B, Vol. 122, Issue 5 https://doi.org/10.1021/acs.jpcb.7b12218	journal	January 2018
Come Together: Molecular Details into the Synergistic Effects of Polymer–Surfactant Adsorption at the Oil/Water Interface Schabes, Brandon K.; Altman, Rebecca M.; Richmond, Geraldine L. The Journal of Physical Chemistry B, Vol. 122, Issue 36 https://doi.org/10.1021/acs.jpcb.8b05432	journal	August 2018
Helping Strands: Polyelectrolyte Assists in Surfactant Assembly below Critical Micelle Concentration Schabes, Brandon K.; Richmond, Geraldine L. The Journal of Physical Chemistry B, Vol. 124, Issue 1 https://doi.org/10.1021/acs.jpcb.9b08692	journal	December 2019
Coordination Effects in Polymer Electrolytes: Fast Li⁺ Transport by Weak Ion Binding Rosenwinkel, Mark P.; Andersson, Rassmus; Mindemark, Jonas The Journal of Physical Chemistry C, Vol. 124, Issue 43 https://doi.org/10.1021/acs.jpcc.0c08369	journal	October 2020
Intermolecular Interactions at the Interface Quantified by Surface-Sensitive Second-Order Fermi Resonant Signals Tian, Kangzhen; Zhang, Baixiong; Ye, Shuji The Journal of Physical Chemistry C, Vol. 119, Issue 29 https://doi.org/10.1021/acs.jpcc.5b03204	journal	July 2015
Fermi Resonant Interaction of the Tailed Methyl Groups of Langmuir Monolayer at the Air/Water Interface during Phase Transition Tian, Kangzhen; Ye, Shuji The Journal of Physical Chemistry C, Vol. 119, Issue 45 https://doi.org/10.1021/acs.jpcc.5b07347	journal	October 2015
Selective Probing of Thin-Film Interfaces Using Internal Reflection Sum-Frequency Spectroscopy Azam, Md. Shafiul; Cai, Canyu; Hore, Dennis K. The Journal of Physical Chemistry C, Vol. 123, Issue 38 https://doi.org/10.1021/acs.jpcc.9b06761	journal	August 2019
Molecular Insights into the Role of Electronic Substituents on the Chemical Environment of the −CH ₃ and >C═O Groups of Neat Liquid Monomers Using Sum Frequency Generation Spectroscopy Premadasa, Uvinduni I.; Adhikari, Narendra M.; Cimatu, Katherine Leslee A. The Journal of Physical Chemistry C, Vol. 123, Issue 46 https://doi.org/10.1021/acs.jpcc.9b07816	journal	October 2019
Intermolecular Interactions at the Silica–Liquid Interface Modulate the Fermi Resonance Coupling in Surface Methanol Bui, Thomas T.; Colón, Luis A.; Velarde, Luis The Journal of Physical Chemistry Letters, Vol. 12, Issue 24 https://doi.org/10.1021/acs.jpclett.1c01015	journal	June 2021
Probing Orientations and Conformations of Peptides and Proteins at Buried Interfaces Guo, Wen; Lu, Tieyi; Gandhi, Zahra The Journal of Physical Chemistry Letters, Vol. 12, Issue 41 https://doi.org/10.1021/acs.jpclett.1c02956	journal	October 2021
Contact Ion Pair Formation Is Not Necessarily Stronger than Solvent Shared Ion Pairing Judd, Kenneth D.; Gonzalez, Nicole M.; Yang, Tinglu The Journal of Physical Chemistry Letters, Vol. 13, Issue 3 https://doi.org/10.1021/acs.jpclett.1c03576	journal	January 2022
Squeezing Out Interfacial Solvation: The Role of Hydrogen-Bonding in the Structural and Orientational Freedom of Molecular Self-Assembly Liu, Zening; Lin, Lu; Li, Tianyu The Journal of Physical Chemistry Letters, Vol. 13, Issue 10 https://doi.org/10.1021/acs.jpclett.1c03941	journal	March 2022
Development of Heavy Element Chemistry at Interfaces: Observing Actinide Complexes at the Oil/Water Interface in Solvent Extraction by Nonlinear Vibrational Spectroscopy Kusaka, Ryoji; Watanabe, Masayuki The Journal of Physical Chemistry Letters, Vol. 13, Issue 30 https://doi.org/10.1021/acs.jpclett.2c01550	journal	July 2022
Corn Oil–Water Separation: Interactions of Proteins and Surfactants at Corn Oil/Water Interfaces Zhang, Chengcheng; Gao, Jinpeng; Hankett, Jeanne Langmuir, Vol. 36, Issue 15 https://doi.org/10.1021/acs.langmuir.0c00338	journal	March 2020
Molecular Forces in Liquid–Liquid Extraction Špadina, Mario; Dufrêche, Jean-François; Pellet-Rostaing, Stephane Langmuir, Vol. 37, Issue 36 https://doi.org/10.1021/acs.langmuir.1c00673	journal	July 2021
Orientation and Conformation of Hydrophobin at the Oil–Water Interface: Insights from Molecular Dynamics Simulations Yu, Hai; Yang, Shengjiang; Chen, Zheng Langmuir, Vol. 38, Issue 19 https://doi.org/10.1021/acs.langmuir.2c00614	journal	May 2022
Effect of Added Salt on Disordered Poly(ethylene oxide)-Block-Poly(methyl methacrylate) Copolymer Electrolytes Shah, Neel J.; Dadashi-Silab, Sajjad; Galluzzo, Michael D. Macromolecules, Vol. 54, Issue 3 https://doi.org/10.1021/acs.macromol.0c02493	journal	January 2021
Free Thiols Regulate the Interactions and Self-Assembly of Thiol-Passivated Metal Nanoparticles Sun, Pan; Nowack, Linsey M.; Bu, Wei Nano Letters, Vol. 21, Issue 4 https://doi.org/10.1021/acs.nanolett.0c04147	journal	February 2021
Hydrogen-Bond-Driven Chemical Separations: Elucidating the Interfacial Steps of Self-Assembly in Solvent Extraction Chowdhury, Azhad U.; Lin, Lu; Doughty, Benjamin ACS Applied Materials & Interfaces, Vol. 12, Issue 28 https://doi.org/10.1021/acsami.0c06176	journal	June 2020
Ion Pairing Mediates Molecular Organization Across Liquid/Liquid Interfaces Lin, Lu; Chowdhury, Azhad U.; Ma, Ying-Zhong ACS Applied Materials & Interfaces, Vol. 13, Issue 28 https://doi.org/10.1021/acsami.1c09763	journal	July 2021
Ionic Conductivity Enhancement of Polymer Electrolytes by Directed Crystallization Liu, Changhao; Tang, Xiaomin; Wang, Yangyang ACS Macro Letters, Vol. 11, Issue 4 https://doi.org/10.1021/acsmacrolett.2c00040	journal	April 2022
Nanoparticle-Induced Disorder at Complex Liquid–Liquid Interfaces: Effects of Curvature and Compositional Synergy on Functional Surfaces Basham, Colin M.; Premadasa, Uvinduni I.; Ma, Ying-Zhong ACS Nano, Vol. 15, Issue 9 https://doi.org/10.1021/acsnano.1c02663	journal	September 2021
Memristive Ion Channel-Doped Biomembranes as Synaptic Mimics Najem, Joseph S.; Taylor, Graham J.; Weiss, Ryan J. ACS Nano, Vol. 12, Issue 5 https://doi.org/10.1021/acsnano.8b01282	journal	March 2018
Electrolyte Solvation Structure at Solid–Liquid Interface Probed by Nanogap Surface-Enhanced Raman Spectroscopy Yang, Guang; Ivanov, Ilia N.; Ruther, Rose E. ACS Nano, Vol. 12, Issue 10 https://doi.org/10.1021/acsnano.8b05038	journal	September 2018
Synergistic Solvent Extraction Is Driven by Entropy Špadina, Mario; Bohinc, Klemen; Zemb, Thomas ACS Nano, Vol. 13, Issue 12 https://doi.org/10.1021/acsnano.9b07605	journal	November 2019
Hofmeister Series: Insights of Ion Specificity from Amphiphilic Assembly and Interface Property Kang, Beibei; Tang, Huicheng; Zhao, Zengdian ACS Omega, Vol. 5, Issue 12 https://doi.org/10.1021/acsomega.0c00237	journal	March 2020
Cations Bind Only Weakly to Amides in Aqueous Solutions Okur, Halil I.; Kherb, Jaibir; Cremer, Paul S. Journal of the American Chemical Society, Vol. 135, Issue 13 https://doi.org/10.1021/ja3119256	journal	March 2013
Slow Oil, Slow Water: Long-Range Dynamic Coupling across a Liquid–Liquid Interface Baryiames, Christopher P.; Baiz, Carlos R. Journal of the American Chemical Society, Vol. 142, Issue 18 https://doi.org/10.1021/jacs.0c00817	journal	April 2020
Photoresponsive Structured Liquids Enabled by Molecular Recognition at Liquid–Liquid Interfaces Sun, Huilou; Li, Lianshun; Russell, Thomas P. Journal of the American Chemical Society, Vol. 142, Issue 19 https://doi.org/10.1021/jacs.0c02555	journal	April 2020
Insight into the Mechanisms Driving the Self-Assembly of Functional Interfaces: Moving from Lipids to Charged Amphiphilic Oligomers Chowdhury, Azhad U.; Taylor, Graham J.; Bocharova, Vera Journal of the American Chemical Society, Vol. 142, Issue 1 https://doi.org/10.1021/jacs.9b10536	journal	December 2019
A Unified Treatment of Selection Rules and Symmetry Relations for Sum-Frequency and Second Harmonic Spectroscopies Moad, Andrew J.; Simpson, Garth J. The Journal of Physical Chemistry B, Vol. 108, Issue 11 https://doi.org/10.1021/jp035362i	journal	March 2004
Structure of Butanol and Hexanol at Aqueous, Ammonium Bisulfate, and Sulfuric Acid Solution Surfaces Investigated by Vibrational Sum Frequency Generation Spectroscopy ^† Van Loon, Lisa L.; Minor, Rena N.; Allen, Heather C. The Journal of Physical Chemistry A, Vol. 111, Issue 31 https://doi.org/10.1021/jp070625k	journal	August 2007
Cation Effects on Interfacial Water Organization of Aqueous Chloride Solutions. I. Monovalent Cations: Li ⁺ , Na ⁺ , K ⁺ , and NH ₄ ⁺ Hua, Wei; Verreault, Dominique; Huang, Zishuai The Journal of Physical Chemistry B, Vol. 118, Issue 28 https://doi.org/10.1021/jp503132m	journal	May 2014
Toward Understanding the Mechanism of Phase Transfer Catalysis with Surface Second Harmonic Generation Fita, Piotr The Journal of Physical Chemistry C, Vol. 118, Issue 40 https://doi.org/10.1021/jp5071314	journal	September 2014
Molecular Structure and Ordering of Phospholipids at a Liquid−Liquid Interface Walker, Robert A.; Conboy, John C.; Richmond, Geraldine L. Langmuir, Vol. 13, Issue 12 https://doi.org/10.1021/la961007q	journal	June 1997
Seven chemical separations to change the world Sholl, David S.; Lively, Ryan P. Nature, Vol. 532, Issue 7600 https://doi.org/10.1038/532435a	journal	April 2016
Collaborative routes to clarifying the murky waters of aqueous supramolecular chemistry Cremer, Paul S.; Flood, Amar H.; Gibb, Bruce C. Nature Chemistry, Vol. 10, Issue 1 https://doi.org/10.1038/nchem.2894	journal	December 2017
The interfacial structure of water droplets in a hydrophobic liquid Smolentsev, Nikolay; Smit, Wilbert J.; Bakker, Huib J. Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms15548	journal	May 2017
Dynamical nonlinear memory capacitance in biomimetic membranes Najem, Joseph S.; Hasan, Md Sakib; Williams, R. Stanley Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-11223-8	journal	July 2019
Weakly hydrated anions bind to polymers but not monomers in aqueous solutions Rogers, Bradley A.; Okur, Halil I.; Yan, Chuanyu Nature Chemistry, Vol. 14, Issue 1 https://doi.org/10.1038/s41557-021-00805-z	journal	November 2021
Origin of ion selectivity at the air/water interface Sun, Lu; Li, Xin; Tu, Yaoquan Physical Chemistry Chemical Physics, Vol. 17, Issue 6 https://doi.org/10.1039/C4CP03338H	journal	January 2015
Structure of a liquid/liquid interface during solvent extraction combining X-ray and neutron reflectivity measurements Scoppola, E.; Watkins, E.; Li Destri, G. Physical Chemistry Chemical Physics, Vol. 17, Issue 23 https://doi.org/10.1039/C5CP01809A	journal	January 2015
Spontaneous aggregation of lithium ion coordination polymers in fluorinated electrolytes for high-voltage batteries Malliakas, Christos D.; Leung, Kevin; Pupek, Krzysztof Z. Physical Chemistry Chemical Physics, Vol. 18, Issue 16 https://doi.org/10.1039/C6CP01157H	journal	January 2016
Molecular interactions of organic molecules at the air/water interface investigated by sum frequency generation vibrational spectroscopy Wang, Wenting; Ye, Shuji Physical Chemistry Chemical Physics, Vol. 19, Issue 6 https://doi.org/10.1039/C6CP07827C	journal	January 2017
Dynamic effect of polymers at the surfactant–water interface: an ultrafast study Garrett, Paul; Baiz, Carlos R. Soft Matter, Vol. 18, Issue 9 https://doi.org/10.1039/D1SM01651B	journal	January 2022
Understanding specific ion effects and the Hofmeister series Gregory, Kasimir P.; Elliott, Gareth R.; Robertson, Hayden Physical Chemistry Chemical Physics, Vol. 24, Issue 21 https://doi.org/10.1039/D2CP00847E	journal	January 2022
Simulated vibrational sum frequency generation from a multilayer thin film system with two active interfaces O'Brien, Daniel B.; Massari, Aaron M. The Journal of Chemical Physics, Vol. 138, Issue 15 https://doi.org/10.1063/1.4799921	journal	April 2013
Sensitivity of sum frequency generation experimental conditions to thin film interference effects Cotton, Daniel E.; Roberts, Sean T. The Journal of Chemical Physics, Vol. 154, Issue 11 https://doi.org/10.1063/5.0039897	journal	March 2021
Bursting the bubble: A molecular understanding of surfactant-water interfaces Baryiames, Christopher P.; Garrett, Paul; Baiz, Carlos R. The Journal of Chemical Physics, Vol. 154, Issue 17 https://doi.org/10.1063/5.0047377	journal	May 2021
Sum frequency generation as a proxy for ellipsometry: Not just a phase Dramstad, Thorn A.; Wu, Zhihao; Massari, Aaron M. The Journal of Chemical Physics, Vol. 156, Issue 11 https://doi.org/10.1063/5.0076252	journal	March 2022
Ordered polyelectrolyte assembly at the oil-water interface Beaman, D. K.; Robertson, E. J.; Richmond, G. L. Proceedings of the National Academy of Sciences, Vol. 109, Issue 9 https://doi.org/10.1073/pnas.1200244109	journal	February 2012
Nanoscale view of assisted ion transport across the liquid–liquid interface Liang, Zhu; Bu, Wei; Schweighofer, Karl J. Proceedings of the National Academy of Sciences, Vol. 116, Issue 37 https://doi.org/10.1073/pnas.1701389115	journal	March 2018
Specific cation effects at aqueous solution−vapor interfaces: Surfactant-like behavior of Li ⁺ revealed by experiments and simulations Perrine, Kathryn A.; Parry, Krista M.; Stern, Abraham C. Proceedings of the National Academy of Sciences, Vol. 114, Issue 51 https://doi.org/10.1073/pnas.1707540114	journal	October 2017
Quantitative spectral and orientational analysis in surface sum frequency generation vibrational spectroscopy (SFG-VS) Wang *, Hong-Fei; Gan † ‡, Wei; Lu † ‡ §, Rong International Reviews in Physical Chemistry, Vol. 24, Issue 2 https://doi.org/10.1080/01442350500225894	journal	April 2005
Implementing the Theory of Sum Frequency Generation Vibrational Spectroscopy: A Tutorial Review Lambert, Alex G.; Davies, Paul B.; Neivandt, David J. Applied Spectroscopy Reviews, Vol. 40, Issue 2 https://doi.org/10.1081/ASR-200038326	journal	May 2005
Nanoparticle Assembly and Transport at Liquid-Liquid Interfaces Lin, Y.; Skaff, H.; Emrick, T. Science, Vol. 299, Issue 5604, p. 226-229 https://doi.org/10.1126/science.1078616	journal	January 2003

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Alkyls
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The Unexpected Role of Cations in the Self-Assembly of Positively Charged Amphiphiles at Liquid/Liquid Interfaces

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