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Self-assembly of long chain fatty acids: effect of a methyl branch
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Surface and Corrosion Science.ORCID iD: 0000-0003-2734-2847
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Surface and Corrosion Science.
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Surface and Corrosion Science. Department of Chemistry, Technical University of Denmark, Kemitorvet 207, DK-2800 Kgs. Lyngby, Denmark.
L’Oréal Research and Innovation, Aulnay-sous-Bois, France.
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2014 (English)In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 16, no 33, 17869-17882 p.Article in journal (Refereed) Published
Abstract [en]

The morphology and molecular conformation of Langmuir Blodgett deposited and floating monolayers of a selection of straight chain (eicosanoic acid, EA), iso (19-methyl eicosanoic acid, 19-MEA), and anteiso (18-methyl eicosanoic acid, 18-MEA) fatty acids have been investigated by Vibrational Sum Frequency Spectroscopy (VSFS), AFM imaging, and the Langmuir trough. While the straight chain fatty acid forms smooth, featureless monolayers, all the branched chain fatty acids display 10-50 nm sized domains (larger for 19-MEA than the 18-MEA) with a homogeneous size distribution. A model is suggested to explain the domain formation and size in terms of the branched fatty acid packing properties and the formation of hemispherical caps at the liquid air interface. No difference between the chiral (S) form and the racemic mixture of the 18-MEA is observed with any of the utilized techniques. The aliphatic chains of the straight chain fatty acids appear to be oriented perpendicular to the sample surface, based on an orientational analysis of VSFS data and the odd/even effect. In addition, the selection of the subphase (neat water or CdCl2 containing water buffered to pH 6.0) used for the LB-deposition has a profound influence on the monolayer morphology, packing density, compressibility, and conformational order. Finally, the orientation of the 19-MEA dimethyl moiety is estimated, and a strategy for performing an orientational analysis to determine the complete molecular orientation of the aliphatic chains of 19-MEA and 18-MEA is outlined and discussed.

Place, publisher, year, edition, pages
Royal Society of Chemistry, 2014. Vol. 16, no 33, 17869-17882 p.
Keyword [en]
Sum-Frequency Spectroscopy, Air-Water-Interface, Generation Vibrational Spectroscopy, Normal-Alkyl Chains, H Stretching Modes, Molecular-Structure, 18-Methyleicosanoic Acid, Air/Water Interface, Eicosanoic Acid, Lipid-Bilayer
National Category
Physical Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-98091DOI: 10.1039/C4CP00512KISI: 000341064800058Scopus ID: 2-s2.0-84905453377ISBN: 978-91-7501-436-4 (print)OAI: oai:DiVA.org:kth-98091DiVA: diva2:546301
Funder
Swedish Foundation for Strategic Research Swedish Research Council
Note

QC 20140929

Manuscript in Thesis. QS 2012 with title "Domain Formation and Molecular Conformation in Monolayers of Branched Long Chain Fatty Acids: The Influence of ω-1 and ω-2 Methylation"

Available from: 2012-08-23 Created: 2012-06-19 Last updated: 2017-12-07Bibliographically approved
In thesis
1. A Spectroscopic Study of Interfacial Films: Internal Structuring, Stability, and Hydration
Open this publication in new window or tab >>A Spectroscopic Study of Interfacial Films: Internal Structuring, Stability, and Hydration
2012 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Monolayers of molecules are capable of completely changing the nature of surfaces and their interactions with the surroundings despite their almost negligible thickness. In the research presented in this doctoral thesis the surface specific technique Vibrational Sum Frequency Spectroscopy (VSFS) was combined with the Langmuir trough to investigate various manifestations of monolayers, such as biomimetic membranes, mono methyl branched long chain fatty acids in contact with air, and hydrophobic silane monolayers in contact with water.

VSFS was applied to in situ studies of the oxidative degradation of Langmuir monolayers of 1,2-diacylphosphocholines with identical C-18 chains featuring various degrees of unsaturation. The monolayer area and vinyl CH signal intensity were probed at constant surface pressure to monitor the degradation. The rapid degradation of the unsaturated lipids in contact with the ambient air is attributed to oxidation of the C=C bonds mediated by reactive species in the air and can be inhibited by purging the compartment surrounding the monolayer with nitrogen.

The molecular structure and order of Langmuir monolayers of 1,2-distearoyl-phosphocholine (18:0 PC) and their hydrating water were investigated at different surface pressures using VSFS. The monolayers are conformationally well ordered at all surface pressures and the signal intensity increases due to larger molecular number density at increasing surface pressures. Also, water signals with different vibrational frequencies are observed in different polarization combinations.

Additionally, a selection of common phospholipids (18:0 PC, 18:0 PC-D83 and 18:0 PS) were Langmuir-Blodgett (LB) deposited on CaF2 substrates and the CH- and OH-stretching regions as well as lower wavenumber regions were probed using VSFS. The orientation of the conformationally well ordered aliphatic chains was determined to be approximately perpendicular to the sample surface.

Monolayers of eicosanoic acid, its iso (19-MEA), and anteiso (18-MEA) analogues were investigated with VSFS, AFM imaging, and the Langmuir trough. The EA forms smooth, featureless monolayers when deposited on silica, while 19-MEA and 18-MEA form 10 -50 nm large domains with homogeneous size distribution. It was not possible to discriminate between the monolayers of racemic and chiral 18-MEA using any of the techniques employed

The influence of the experimental geometry on the SF spectral shape and en-hancement at and near total internal reflection conditions (TIR) were systematically investigated by comparing simulations with recorded data from a hydrophobized silica / water interface. The data agree qualitatively, but not quantitatively, with the simulations, and the reasons were critically discussed.

The water structure next to ordered and disordered hydrophobic silane monolayers on silica was investigated using VSFS. The results indicate that the structure of water next to a well ordered hydrophobic monolayer, with the exception of the first layer of water molecules, is not much different from that in the isotropic bulk. This is in contrast to the previous notion where such monolayers were assumed to induce a more ordered interfacial water structure.

Abstract [sv]

Trots sin begränsade tjocklek har monolager förmågan att totalt kunna förändra en ytas egenskaper och dess växelverkan med omgivningen. I forskningen som beskrivs i denna doktorsavhandling har den ytspecifika tekniken vibrationssumfrekvensspektroskopi (VSFS) kombinerats med Langmuir-tråget för att undersöka olika varianter av monolager, såsom biomimetiska membran, monometylgrenade långkedjiga fettsyror och hydrofoba silanmonolager i kontakt med vatten.

VSFS användes för att genomföra in situ undersökningar av den oxidativa nedbrytningen av Langmuir-monolager av 1,2-diacylfosfokoliner med identiska 18 kolatomer långa kedjor med varierande grader av omättnad. Monolagerarean och vinylCH-signalens intensitet mättes vid konstant yttryck för att övervaka nedbrytningen. Den snabba nedbrytningen av de omättade lipiderna i kontakt med den omgivande luften tillskrivs oxidation orsakad av reaktiva ämnen i luften och kan inhiberas fullständigt genom att genomblåsa utrymmet som omger monolagret med kvävgas.

Den molekylära strukturen och ordningen hos Langmuir-monolager av 1,2-distearoylfosfokolin (18:0 PC) och deras hydratiseringsvatten undersöktes vid olika yttryck med VSFS. Monolagerna har en välordnad konformation vid alla yttryck och signalintensiteten ökar vid ökande yttryck på grund av den större numerära molekyltätheten. Dessutom observeras vattensignaler med olika vibrationsfrekvenser i olika polarisationskombinationer.

Vidare LB-deponerades ett urval av vanligt förekommande fosfolipider (18:0 PC, 18:0 PC-D83 och 18:0 PS) på ett substrat av CaF2 varefter CH- och vattenregionen såväl som lågvågtalsområdet undersöktes med hjälp av VSFS. Orienteringen hos kolvätekedjorna, som hade en välordnad konformation, befanns vara ungefär vinkelrät mot provytan.

Monolager av eicosansyra, samt dess iso (19-MEA), och anteiso (18-MEA) analoger undersöktes med VSFS, AFM avbildning och Langmuirtråget. Eicosanssyran bildar jämna, strukturlösa monolager då den deponeras på kiseldioxid medan 19-MEA och 18-MEA formar 10 – 50 nm stora domäner med homogen storleksfördelning. Ingen av de använda teknikerna kunde särskilja racemisk och kiral 18-MEA.

Inverkan av försöksuppställningens geometri på SF-spektrumets form och förstärkning vid och i närheten av total internreflektion (TIR) undersöktes systematiskt genom att jämföra simuleringar med mätdata från en gränsyta mellan hydro-foberad kiseldioxid och vatten. Mätdata överensstämmer kvalitativt, men inte kvantitativt, med simuleringarna och orsakerna till detta diskuterades kritiskt.

Vattenstrukturen intill ordnade och oordnade hydrofoba silanmonolager undersöktes med VSFS. Resultaten visar att vattenstrukturen nära ett välordnat hydrofobt monolager, med undantag av det första lagret av vattenmolekyler, inte är särskilt olik den isotropa bulkfasens. Detta är i motsats till den tidigare uppfattningen att sådana monolager ansågs orsaka en mera välordnad vattenstruktur.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2012. viii, 80 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2012:35
National Category
Physical Chemistry
Identifiers
urn:nbn:se:kth:diva-101081 (URN)978-91-7501-436-4 (ISBN)
Public defence
2012-09-21, KTH, Hörsal F3, Lindstedtsvägen 26, KTH, Stockholm, 13:30 (English)
Opponent
Supervisors
Note

QC 20120824

Available from: 2012-08-24 Created: 2012-08-23 Last updated: 2012-08-24Bibliographically approved

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Liljeblad, Jonathan F. D.

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