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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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Ionic Specificity in pH Regulated Charged Interfaces: Fe[superscript 3+]versus La[superscript 3+]

We determine the distribution of two trivalent ions Fe{sup 3+} and La{sup 3+} next to two different amphiphilic charged interfaces as ions or complexes, consisting of the phosphate lipid dihexadecyl phosphate (DHDP) and the fatty acid arachidic acid (AA). These amphiphiles provide a wide range of pK{sub a} values, from 2.1 (DHDP) to 5.1 (AA), thus allowing manipulation of the surface charge over extremely low pH (pH {approx}1 or larger), and the two ions provide two limiting cases of specificity for the amphiphiles. We find that La{sup 3+} distribution is mostly sensitive to the surface charge, whereas the Fe{sup 3+} binding depends on its character in the solution and is highly specific, as indicated by the crucial role played by iron complexes (Fe(OH){sub 3} or Fe(OH){sup 2+}) forming covalent bonds even for an uncharged interface. The implications of the results to other ions and/or amphiphilic interfaces are also discussed.

36 MATERIALS SCIENCE↗

La 3+ and Y 3+ interactions with the carboxylic acid moiety at the liquid/vapor interface: Identification of binding complexes, charge reversal, and detection limits

Specific interactions of yttrium and lanthanum ions with a fatty acid Langmuir monolayer were investigated using vibrational sum frequency spectroscopy. The trivalent ions were shown to interact with the charged form of the carboxylic acid group from nanomolar concentrations (<300 nM). Analysis of the spectral features from both the symmetric and the asymmetric carboxylate modes reveals the presence of at least three distinct coordination structures linked to specific binding configurations. Although the same species were identified for both La 3+ and Y 3+ , they display a different concentration dependence, highlighting the ion-specificity of the interaction. From the analysis of the response of interfacial water molecules, the reversal of the surface charge, as well as the formation of yttrium hydroxide complexes, were detected upon increasing the amount of salt in solution. The binding interaction and kinetics of absorption are sensitive to the solution pH, showing a distinct ion speciation in the interfacial region when compared to the bulk. Changing the subphase pH or adding a monovalent background electrolyte that promotes deprotonation of the carboxylic acid headgroup could further improve the detection limit of La 3+ and Y 3+ to concentrations < 100 nM. These findings demonstrate that nM concentrations of trace metals contaminants, typically found on monovalent salts, can significantly influence the binding structure and kinetics in Langmuir monolayers.

01 COAL, LIGNITE, AND PEAT↗

Photocatalytic oxidation of the organic monolayers on TiO{sub 2} surface investigated by in-situ sum frequency generation spectroscopy

In-situ vibrational sum frequency generation (SFG) spectroscopy has been employed to investigate the photocatalytic oxidation of two types of well-ordered organic monolayers, namely, an arachidic acid (AA) monolayer prepared by the Langmuir-Blodgett method and an octadecyltrichlorosilane (OTS) monolayer prepared by the self-assembling method, on a TiO{sub 2} surface under ultraviolet (UV) irradiation. The extremely high sensitivity and unique selectivity of the SFG spectroscopy enabled us to directly probe the structural changes in these monolayers during the surface photocatalytic oxidation and further elucidate their reaction mechanisms at a molecular level. It was revealed that the ordering of the monolayers during the photocatalytic reaction is strongly dependent on their interaction with the substrate; the AA monolayer maintains its ordered conformation until the final oxidation stage, while the OTS monolayer shows a large increase in disordering during the initial oxidation stage, indicating a different photocatalytic reaction mechanism of the two monolayers on the TiO{sub 2} surface.

36 MATERIALS SCIENCE↗