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Long-Chain Alkylthiol Assemblies Containing Buried In-Plane Stabilizing Architectures
Linköping University, Department of Physics, Chemistry and Biology, Molecular Physics. Linköping University, Faculty of Science & Engineering.
Institute Phys, Department Funct Nanomat, LT-02300 Vilnius, Lithuania .
Bogolyubov Institute Theoret Phys, UA-03143 Kiev, Ukraine .
Bogolyubov Institute Theoret Phys, UA-03143 Kiev, Ukraine .
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2009 (English)In: Langmuir, ISSN 0743-7463, E-ISSN 1520-5827, Vol. 25, no 24, 13959-13971 p.Article in journal (Refereed) Published
Abstract [en]

A series of alkylthiol compounds were synthesized to study the formation and structure of complex self-assembled monolayers (SAMs) consisting of interchanging structural modules stabilized by intermolecular hydrogen bonds. The chemical structure of the synthesized compounds, HS(CH2)(15)CONH(CH2CH2O)(6)CH2CONH-X, where X refers to the extended chains of either -(CH2)(n)CH3 or -(CD2)(n)CD3, with n = 0, 1, 7, 8, 15, was confirmed by NMR and elemental analysis. The formation of highly ordered, methyl-terminated SAMs oil gold from diluted ethanolic solutions of these compounds was revealed using contact angle goniometry, mill ellipsometry, cyclic voltammetry, and infrared reflection absorption spectroscopy. The experimental work was complemented with extensive DFT modeling of infrared spectra and molecular orientation. New assignments were introduced for both nondeuterated and deuterated Compounds. The latter set of compounds also served as a convenient tool to resolve the packing, conformation, and orientation of the buried and extended modules within the SAM. Thus, it was shown that the lower alkyl portion together with the hexa(ethylene glycol) portion is stabilized by the two layers of lateral hydrogen bonding networks between the amide groups, and they provide it Structurally robust support for the extended alkyls, The presented system can be considered to be an extension of the well-known alkyl SAM platform, enabling precise engineering of nanoscopic architectures oil the length scale from a Few to similar to 60 angstrom for applications such as cell membrane mimetics, molecular nanolithography, and so forth.

Place, publisher, year, edition, pages
2009. Vol. 25, no 24, 13959-13971 p.
National Category
Engineering and Technology
URN: urn:nbn:se:liu:diva-52826DOI: 10.1021/la901668uOAI: diva2:285609
Available from: 2010-01-12 Created: 2010-01-12 Last updated: 2015-05-29Bibliographically approved
In thesis
1. Structural Studies of Oligo(ethylene glycol)-Containing Assemblies on Gold
Open this publication in new window or tab >>Structural Studies of Oligo(ethylene glycol)-Containing Assemblies on Gold
2012 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The work presents in this thesis has been focused on structural  characterization of a series of selected well-defined molecular architectures for the application as biomimetic membranes. The molecular architectures were prepared by self-assembly from dilute solution onto gold substrates, so called self-assembled monolayers (SAMs).

Biological membranes are essential components for all living systems; their molecular organizations and interactions with intra- and extracellular networks are key factors of cell functions. Many important biological processes are regulated at membrane interfaces via interactions between membrane proteins. Therefore, identification of the cell structures and understanding of the processes associated with membranes are crucial. However, the intrinsic complexity of the cell membrane systems makes direct investigation extra difficult. Based on this reason, artificial model membranes have become a useful strategy. Especially, solid supported tethered lipid membranes on SAMs allow for controlling the composition and geometry of biomimetic assemblies on molecular scale. However, the underlying mechanisms of lipid vesicle fusion on SAMs remain unclear. In this thesis, a series of thiolate SAMs containing alkyl chains and oligo(ethylene glycol) (OEG) portions of different length as well as amide linking groups were prepared and characterized in detail by employing a number of surface analyzing methods. In parallel, a set of ab initio modeling was undertaken for the best interpretation of the experimental infrared spectra. Investigation of small unilamellar vesicles interact with such SAMs is included as well.

The results show this type of assemblies forms highly ordered and oriented SAMs regardless of the length of the extended alkyl chains. The two layers of lateral hydrogen bonding networks through the two amide linking groups improve further the structural robustness of the assemblies. Furthermore, the use of deuterated terminal alkyl chains enables a direct relation between the surface density of the anchor molecules and the properties of the lipidbilayers. IRRAS data and ab initio modeling confirm that orientation of the helical OEG is affected by the second hydrogen bonding layer rather than the extended alkyl tails. Nanopatterns consisting of such SAMs with different extended alkyl chains can be employed as supports for the assembly of artificial cell membranes.

Place, publisher, year, edition, pages
Linköping: Linköping University Electronic Press, 2012. 62 p.
Linköping Studies in Science and Technology. Dissertations, ISSN 0345-7524 ; 1446
National Category
Natural Sciences
urn:nbn:se:liu:diva-77056 (URN)978-91-7519-898-9 (ISBN)
Public defence
2012-05-31, Planck, Fysikhuset, Campus Valla, Linköpings universitet, Linköping, 10:15 (Swedish)
Available from: 2012-05-03 Created: 2012-05-03 Last updated: 2012-06-29Bibliographically approved

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