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.; Bocharova, Vera; Thiele, Nikki A.; Doughty, Benjamin

doi:10.1016/j.jcis.2021.11.088

Cited by 20 publications

(34 citation statements)

References 37 publications

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“…The importance of similar tail-solvation interactions on assembly have recently been reported for organophosphorus amphiphiles, though the resulting assemblies differed from those observed here because of missing H-bonding interactions on the alkyl tails. 28 In conclusion, the study of the ODMS-MIM + decorated air− aqueous interface communicates new physical insights through coincident Langmuir trough measurements, SFG spectroscopy, and atomistic MD simulations. The findings shed newlight on an effect assumed to be negligible, that is, aqueous phase interactions with the hydrophobic tails.…”

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confidence: 76%

“…The unique inclusion of a Si–O backbone in ODMS provides an unexpected means to tune assembly through solvation interactions directly with the tail, despite the perceived hydrophobicity. The combination of physical and chemical handles capable of tuning the conformational aspects of ODMS-MIM + , and related species, opens new avenues for the design of soft-matter electronics and the fabrication of ultrathin polymer films for a range of applications, including antifouling, energy storage, and membrane separations. − …”

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confidence: 99%

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Squeezing Out Interfacial Solvation: The Role of Hydrogen-Bonding in the Structural and Orientational Freedom of Molecular Self-Assembly

Liu

et al. 2022

J. Phys. Chem. Lett.

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Bioinspired membrane molecules with improved physical properties and enhanced stability can serve as functional models for conventional lipid or amphiphilic species. Importantly, these molecules can also provide new insights into emergent phenomena that manifest during self-assembly at interfaces. Here, we elucidate the structural response and mechanistic steps underlying the self-assembly of the amphiphilic, charged oligodimethylsiloxane imidazolium cation (ODMS-MIM+) at the air–aqueous interface using Langmuir trough methods with coincident surface-specific vibrational sum-frequency generation (SFG) spectroscopy. We find evidence for a new compression-induced desolvation step that precedes commonly known disordered-to-ordered phase transitions to form nanoscopic assemblies. The experimental data was supported by atomistic molecular dynamics (MD) simulations to provide a detailed mechanistic picture underlying the assembly and the role of water in these phase transitions. The sensitivity of the hydrophobic ODMS tail conformations to compressionowing to distinct water–ODMS interactions and tail–tail solvation propertiesoffers new strategies for the design of interfaces that can be further used to develop soft-matter electronics and low-dimensional materials using physical and chemical controls.

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confidence: 76%

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confidence: 99%

Squeezing Out Interfacial Solvation: The Role of Hydrogen-Bonding in the Structural and Orientational Freedom of Molecular Self-Assembly

Liu

et al. 2022

J. Phys. Chem. Lett.

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“…Although these properties make SFG a versatile tool in surface/interface sciences, it has not been widely adopted in studies in probing liquid/liquid interfaces. In fact, only a few research groups have used SFG to study such interfaces, specifically in the context of amphiphile adsorption, − polymer assembly, − liquid extraction, droplet stabilization, and protein/surfactant interactions . Associated challenges in probing these buried interfaces typically limit available information, but their importance to chemical separations, self-assembly, and a range of applied sciences makes them extremely important.…”

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confidence: 99%

Ion Pairing and Molecular Orientation at Liquid/Liquid Interfaces: Self-Assembly and Function

Chowdhury

et al. 2022

J. Phys. Chem. B

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Molecular orientation plays a pivotal role in defining the functionality and chemistry of interfaces, yet accurate measurements probing this important feature are few, due, in part, to technical and analytical limitations in extracting information from molecular monolayers. For example, buried liquid/liquid interfaces, where a complex and poorly understood balance of inter- and intramolecular interactions impart structural constraints that facilitate the formation of supramolecular assemblies capable of new functions, are difficult to probe experimentally. Here, we use vibrational sum-frequency generation spectroscopy, numerical polarization analysis, and atomistic molecular dynamics simulations to probe molecular orientations at buried oil/aqueous interfaces decorated with amphiphilic oligomers. We show that the orientation of self-assembled oligomers changes upon the addition of salts in the aqueous phase. The evolution of these structures can be described by competitive ion effects in the aqueous phase altering the orientations of the tails extending into the oil phase. These specific anionic effects occur via interfacial ion pairing and associated changes in interfacial solvation and hydrogen-bonding networks. These findings provide more quantitative insight into orientational changes encountered during self-assembly and pave the way for the design of functional interfaces for chemical separations, neuromorphic computing applications, and related biomimetic systems.

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“… 23 Doughty and co-workers studied molecular ordering and self-assembly at the oil/water interface with HDEHP ligands through the CH and OH stretch vibrational signals observed by VSFG spectroscopy. 24 , 25 Uysal and co-workers 26 − 29 and our group 13 , 30 , 31 applied VSFG spectroscopy to the air/water interface covered with amphiphilic extractants as a model of oil/water liquid–liquid interface. Kikkawa et al conducted molecular dynamics (MD) simulation to dictate Cl – ion transport through a liquid–liquid interface.…”

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“…Miller et al studied rare earth adsorption at the air/water interface covered with surfactants by X-ray fluorescence measurements and implied that lanthanide extraction efficiency originates at the surfactant interface . Doughty and co-workers studied molecular ordering and self-assembly at the oil/water interface with HDEHP ligands through the CH and OH stretch vibrational signals observed by VSFG spectroscopy. , Uysal and co-workers − and our group ,, applied VSFG spectroscopy to the air/water interface covered with amphiphilic extractants as a model of oil/water liquid–liquid interface. Kikkawa et al conducted molecular dynamics (MD) simulation to dictate Cl – ion transport through a liquid–liquid interface …”

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Development of Heavy Element Chemistry at Interfaces: Observing Actinide Complexes at the Oil/Water Interface in Solvent Extraction by Nonlinear Vibrational Spectroscopy

Kusaka

Watanabe

2022

J. Phys. Chem. Lett.

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Understanding the chemistry of elements at the bottom of the periodic table is a challenging goal in chemistry. Observing actinide species at interfaces by using interface-selective second-order nonlinear optical spectroscopy, such as vibrational sum frequency generation (VSFG) spectroscopy, is a promising route for developing heavy element chemistry; however, such attempts are scarce. Here, we investigated the phase transfer mechanism of uranyl ions (UO 2 2+ ) in solvent extraction using the di(2-ethylhexyl)phosphoric acid (HDEHP) extractant dissolved in the dodecane organic phase by probing the oil/water liquid–liquid interface using VSFG spectroscopy. The POO – symmetric stretch vibrational signals of the HDEHP ligands clearly demonstrated that uranyl ions form interfacial complexes with HDEHP at the oil/water interface. The interfacial uranyl–HDEHP complexes were formed with uranyl ions coming from both the aqueous and oil phases, strongly suggesting that the interfacial complex is an intermediate to cross the oil/water interface. Density functional theory calculations proposed the molecular structure of the interfacial uranyl–HDEHP complex.

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Understanding Self-Assembly and the Stabilization of Liquid/Liquid Interfaces: The Importance of Ligand Tail Branching and Oil-Phase Solvation

Cited by 20 publications

References 37 publications

Squeezing Out Interfacial Solvation: The Role of Hydrogen-Bonding in the Structural and Orientational Freedom of Molecular Self-Assembly

Squeezing Out Interfacial Solvation: The Role of Hydrogen-Bonding in the Structural and Orientational Freedom of Molecular Self-Assembly

Ion Pairing and Molecular Orientation at Liquid/Liquid Interfaces: Self-Assembly and Function

Development of Heavy Element Chemistry at Interfaces: Observing Actinide Complexes at the Oil/Water Interface in Solvent Extraction by Nonlinear Vibrational Spectroscopy

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