Woongmo Sung

Halide ions effects on surface excess of long chain ionic liquids water solutions.

The interfacial structure and composition of water solutions with alkylimidazolium ionic liquids varying in their halide anions ([C12mim][X], X = Cl and I) were investigated by X-ray near-total-reflection fluorescence spectroscopy and X-ray reflectivity measurements. We demonstrate that X-ray fluorescence and reflectivity techniques provide a more direct measurement of surface adsorption. Furthermore, we show that for [C12mim][Cl] and [C12mim][I] solutions with mixed inorganic salts (NaI, NaCl), I(-) ions replace Cl(-) above the critical micelle concentration (CMC) of [C12mim][Cl] at much lower concentrations of NaI, whereas NaCl concentrations a hundred times higher than the CMC of [C12mim][I] only partially replace the I(-) at the interface. Our surface-sensitive X-ray diffraction and spectroscopy provide two independent tools to directly determine the surface adsorption of ionic surfactants and the interfacial composition of the surface films.

Origin of the Instability of Octadecylamine Langmuir Monolayer at Low pH

It has been reported that an octadecylamine (ODA) Langmuir monolayer becomes unstable at low pH values with no measurable surface pressure at around pH 3.5, suggesting significant dissolution of the ODA molecule into the subphase solution (Albrecht, Colloids Surf. A 2006, 284-285, 166-174). However, by lowering the pH further, ODA molecules reoccupy the surface, and a full monolayer is recovered at pH 2.5. Using surface sum-frequency spectroscopy and pressure-area isotherms, it is found that the recovered monolayer at very low pH has a larger area per molecule with many gauche defects in the ODA molecules as compared to that at high pH values. This structural change suggests that the reappearance of the monolayer is due to the adsorbed Cl(-) counterions to the protonated amine groups, leading to partial charge neutralization. This proposition is confirmed by intentionally adding monovalent salts (i.e., NaCl, NaBr, or NaI) to the subphase to recover the monolayer at pH 3.5, in which the detailed structure of the monolayer is confirmed by sum frequency spectra and the adsorbed anions by X-ray reflectivity.

Different Adsorption Behavior of Rare Earth and Metallic Ion Complexes on Langmuir Monolayers Probed by Sum-Frequency Generation Spectroscopy

Adsorption behavior of counterions under a Langmuir monolayer was investigated by sum-frequency generation (SFG) spectroscopy. By comparing SFG spectra of arachidic acid (AA) Langmuir monolayer/water interface with and without added salt, it was found that the simple trivalent cation La3+ adsorbed on AA monolayer only when the carboxylic headgroups are charged (deprotonated), implying that counterion adsorption is induced by Coulomb interaction. On the other hand, metal hydroxide complex Fe(OH)3 adsorbed even on a charge-neutral AA monolayer, indicating that the adsorption of iron hydroxide is due to chemical interaction such as covalent or hydrogen bonding to the headgroup of the molecules at the monolayer.

Binding of trivalent ions on fatty acid Langmuir monolayer: Fe3+ versus La3+

Langmuir monolayers consisting of fatty acid molecules were prepared on solutions of FeCl3 and LaCl3 to investigate adsorption of trivalent metal ions on carboxylic headgroups by using sum-frequency vibrational spectroscopy. Fe3+ ions bound to the fatty acid headgroups only in the form of hydroxide complexes (Fe(OH)x +3-x), and sum-frequency intensity of water stretch modes increased markedly upon adsorption of ion hydroxide. On the other hand, La3+ ions bound to the charged anionic headgroup as bare trivalent ions. Upon Fe(OH)x +3-x adsorption, the sum-frequency spectrum of carboxyl headgroups showed significant redshift which is opposite to the case of La3+ as well as those for alkali (Na+, K+) and alkali earth metal (Ca2+, Mg2+) ions, which also supports that Fe3+ binding is by covalent metal-ligand bonding, while La3+ binding is by Coulomb attraction.

Observation of isolated ionic liquid cations and water molecules in an inert solvent

1-Octyl-3-methyl imidazolium halides ([OMIM]I and [OMIM]Cl) were loaded on top of CCl4, and an in situ inclusion process was monitored from the CCl4 phase as time elapses by infrared absorption spectroscopy. Absorption from the bands corresponding to the C(2)-H and C(4,5)-H stretch modes in the imidazolium cation was reduced significantly compared to the bulk IL spectra. This indicates that (1) the [OMIM] cation exists in CCl4 as a monomer, dissociated from the anion and other cations, and (2) hydrogen bonding between the anion and the cation increases the dipole strength of the CH moieties in the imidazolium ring. [OMIM]I was found to transfer into the CCl4 phase much faster than [OMIM]Cl, and this instigated us to compare the transfer of aqueous solutions of ionic liquids, 1-butyl-3-methyl imidazolium halides ([BMIM]I and [BMIM]Cl) into the CCl4 matrix. Not only [BMIM]I but also water molecules transferred faster compared to those in the [BMIM]Cl aqueous solution. Water molecules in CCl4 were shown to form clusters in [BMIM]I; presumably, I- anions work as nucleation centers of water clusters.

Two-Dimensional Correlation Analysis of Sum-Frequency Vibrational Spectra of Langmuir Monolayers

Sum-frequency generation spectra of a Langmuir monolayer on water surface at varying surface areas were studied with two-dimensional correlation analysis. Upon enlarging the area/molecule of the Langmuir monolayer, the sum-frequency spectra changed reflecting the conformation change of the alkyl chains of the molecules in the monolayer. These changes stood out more clearly by employing two-dimensional correlation analysis of the above sum-frequency spectra. Features not very pronounced in the original spectra such as closely-spaced spectral bands can also be easily distinguished in the two-dimensional correlation spectra.

Structural change of interfacial water by adsorption of counterions on Langmuir monolayer

Langmuir monolayer of lipid molecules on LaCl<inf>3</inf> solutions was investigated by sum-frequency vibrational sepctroscopy. Adsorption of La³⁺ cation on lipid headgroups increased with higher LaCl<inf>3</inf> concentration, finally overcompensating negative charges of the lipid headgroups.

Sum-frequency spectra of Langmuir monolayers of lipid molecules having different headgroups

In infrared-visible sum-frequency spectra, interference between nearby bands is important in determining the spectral shape. Using Langmuir monolayers consisting of lipids having oppositely charged headgroups, we studied the influence of sum-frequency signal from interfacial water on the spectral shape in the CHx region.