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Molecular Insights into the Interactions of Monovalent Cations with Highly charged Fatty Acid Monolayers
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemistry.
2023 (English)Independent thesis Advanced level (degree of Master (Two Years)), 20 credits / 30 HE creditsStudent thesisAlternative title
Molekylära insikter inom interaktionerna mellan monovalenta katjoner och laddade fettsyramonolager (Swedish)
Abstract [sv]

Vibrational sum frequency spectroscopy har använts för att studera interaktionerna mellan monovalenta joner och laddade fettsyramonolager. Subfasen bestod av utvalda alkalihydroxidsaltlösningar med pH12, med huvudfokus på cesiumjonen. Molekylär information erhölls genom att rikta in sig på vibrationerna hos karboxylsyragruppen, alkylkedjor, och vattenmolekyler i kontakt med monolagret, samt i det diffusa dubbellagret. Ytans laddning uppskattades genom att observera sträckningsvibrationerna hos hydratiserade karboxylat och protonerade karboxylsyror. Ytans potential beräknades utifrån signalresponsen hos vattenmolekylerna i det diffusa dubbellagret. Beteendet hos ytans laddning och potential överensstämmer väl med Gouy-Chapman-teorin för stora områden per molekyl, men avviker avsevärt vid kompression av monolagret. Vid små områden per molekyl, eller hög laddningsdensitet, stämmer resultaten bättre överens med en storleksmodifierad version av Poisson-Boltzmann-teorin. Resultaten från experiment med en cesiumhydroxidsubfas jämfördes med motsvarande experiment med natrium och litium, vilket beskriver cesiumjonen i relation till de andra alkalijonerna vad gäller jonspecifika effekter. Resultaten som har samlats in här ger insikt i hur effektiv jonstorlek kan användas för att modellera och förutsäga jonspecifika effekter med karboxylsyragruppen i ett Langmuir-monolager.

Abstract [en]

Vibrational sum frequency spectroscopy has been used to study the interactions of monovalent ions with highly charged fatty acid monolayers. The subphase consisted of selected alkali hydroxide salt solutions of pH 12, primarily focusing on the cesium ion. Molecular information was obtained by targeting the vibrational modes of the carboxylic acid headgroups, alkyl chains, and water molecules in the immediate surface and diffuse double layers. The surface charge was estimated by monitoring the stretching modes of the hydrated carboxylate and protonated carboxylic acid. The surface potential was estimated from the signal response of the water molecules in the diffuse double layer. The behaviour of the surface charge and surface potential agrees well with Gouy-Chapman theory for large areas per molecule, but deviates significantly upon monolayer compression. At small areas per molecule or high surface charge density, the results better align with a size-modified version of the Poisson-Boltzmann theory. The results obtained with a cesium hydroxide subphase were compared to equivalent experiments with sodium and lithium, which puts the cesium ion into context with the other alkali ions in terms ion specific effects. The results collected here provide insight into how effective ion size can be used in modelling and predicting ion specific effects with the carboxylic acid moiety in a Langmuir monolayer.

Place, publisher, year, edition, pages
2023.
Series
TRITA-CBH-GRU ; 2023:281
Keywords [en]
VSFS, Langmuir monolayer, ion specific effects, modified Poisson Boltzmann, carboxylic acid
Keywords [sv]
VSFS, Langmuir monolager, jonspecifika effekter, modifierad Poisson Boltzmann, karboxylsyra
National Category
Physical Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-340552OAI: oai:DiVA.org:kth-340552DiVA, id: diva2:1817966
Subject / course
Chemical Science and Engineering
Educational program
Degree of Master - Molecular Science and Engineering
Examiners
Available from: 2023-12-08 Created: 2023-12-08

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