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Spectroscopic Characterization and Modeling of Methyl- and Hydrogen-Terminated Oligo (ethylene glycol) Self-Assembled Monolayers
Bogolyubov Institute for Theoretical Physics, 03680, Kiev, Ukraine.
Bogolyubov Institute for Theoretical Physics, 03680, Kiev, Ukraine.
Linköping University, Department of Physics, Chemistry and Biology, Chemistry. Linköping University, Faculty of Science & Engineering.
Linköping University, Department of Physics, Chemistry and Biology, Molecular Physics. Linköping University, Faculty of Science & Engineering.
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2012 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 116, no 22, 12008-12016 p.Article in journal (Refereed) Published
Abstract [en]

Two series of oligo (ethylene glycol) (OEG) thiol compounds HS-(CH2CH2O)nR with R = CH3, H and n = 5, 6, 7, have been synthesized and used to form self-assembled monolayers (SAMs) on gold. The data from null ellipsometry, infrared reflection-absorption spectroscopy and ab initio calculations of this type of OH- and CH3-terminated OEG SAMs are used to examine the rarely addressed in-SAM orientation of oligo (ethylene glycols) and to provide detailed assignments of infrared bands in the fingerprint and CH-stretching regions. Based on these results, a new spectral band has been observed at 2947 cm-1 and identified by the firstprinciple calculations as localized vibrations that are specific for hydrogen-terminated OEG thiolate SAMs. This band can be used as an indicator of a high crystalline like ordering. It is further more stressed that theory agrees with the experimentally obtained CH-stretching spectra remarkably well if, and only if, the OEG helix axis within studied SAMs is tilted by about 20o with respect to the surface normal.

Place, publisher, year, edition, pages
2012. Vol. 116, no 22, 12008-12016 p.
Keyword [en]
Oligo(ethylene glycol) self-assembled monolayers, infrared reflection absorption spectroscopy, first-principle calculations
National Category
Natural Sciences
Identifiers
URN: urn:nbn:se:liu:diva-77052DOI: 10.1021/jp212400zISI: 000304888700021OAI: oai:DiVA.org:liu-77052DiVA: diva2:524725
Available from: 2012-05-03 Created: 2012-05-03 Last updated: 2017-12-07Bibliographically 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.
Series
Linköping Studies in Science and Technology. Dissertations, ISSN 0345-7524 ; 1446
National Category
Natural Sciences
Identifiers
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)
Opponent
Supervisors
Available from: 2012-05-03 Created: 2012-05-03 Last updated: 2012-06-29Bibliographically approved
2. Synthesis of Orthogonally Functionalized Oligosaccharides for Self-assembled Monolayers and as Multimodal Tools in Chemical Biology
Open this publication in new window or tab >>Synthesis of Orthogonally Functionalized Oligosaccharides for Self-assembled Monolayers and as Multimodal Tools in Chemical Biology
2012 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis covers different topics in the field of synthetic organic chemistry combined with the field of surface science and glycobiology.

First, the text presents a series of orthogonally protected oligosaccharides (tri-, penta-, and heptasaccharides) of varying length and structures, which are synthesized with the aim of developing novel heterobifunctional biocompatible cross-linkers. Successful conjugation with different chemical handles is also described and used to illustrate the potential implementation of defined carbohydrate based compounds have potential use in biosensing applications. The results of incubation experiments using living cells indicate that the linker is incorporated into cell surfaces and enriched in microdomains.

Second, synthesis of various saccharide-terminated alkane thiols immobilized on gold surfaces is reported. The protein adsorption and antifouling characteristics of these surfaces were investigated using model proteins and the common fouling organisms, Ulva linza and Balanus amphitrite.

Further, oligo(lactose)-based thiols (di-, tetra-, and hexasaccharides) were synthesized and immobilized on gold nanoparticles to investigate how well these rigid, rod-like oligosaccharides can stabilize such nanoparticles for future use in constructing hybrid nanoparticles.

Finally, the thesis describes synthesis of a systematic series of oligo(ethylene) glycols possessing either hydrogen- or methyl-terminated groups. Investigation of the fundamental characteristics of self-assembled monolayers, will give important insights into the design of protein repellant surfaces.

Place, publisher, year, edition, pages
Linköping: Linköping University Electronic Press, 2012. 65 p.
Series
Linköping Studies in Science and Technology. Dissertations, ISSN 0345-7524 ; 1442
Keyword
Oligosaccharide synthesis, glycosylation, thioglycosides, orthogonally protected, oligo(lactosides), spacer molecule, heterobifunctional, surface plasmon resonance, lipid anchor, self-assembled monolayers, glyconanoparticles
National Category
Natural Sciences
Identifiers
urn:nbn:se:liu:diva-76733 (URN)978-91-7519-906-1 (ISBN)
Public defence
2012-05-11, Planck, Fysikhuset, Campus Valla, Linköpings universitet, Linköping, 10:15 (English)
Opponent
Supervisors
Available from: 2012-04-18 Created: 2012-04-18 Last updated: 2017-01-11Bibliographically approved

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Fyrner, TimmyLee, Hung-HsunKonradsson, PeterLiedberg, Bo

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