liu.seSearch for publications in DiVA
Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • harvard1
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • oxford
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
Noradrenaline and a Thiol Analogue on Gold Surfaces: An Infrared Reflection-Absorption Spectroscopy, X-ray Photoelectron Spectroscopy, and Near-Edge X-ray Absorption Fine Structure Spectroscopy Study
Linköping University, Department of Physics, Chemistry and Biology, Molecular Surface Physics and Nano Science. Linköping University, Faculty of Science & Engineering.
Linköping University, Department of Physics, Chemistry and Biology, Computational Physics. Linköping University, The Institute of Technology.
Linköping University, Department of Physics, Chemistry and Biology, Computational Physics. Linköping University, The Institute of Technology.
Linköping University, Department of Physics, Chemistry and Biology, Computational Physics. Linköping University, The Institute of Technology.
Show others and affiliations
2011 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 115, no 1, 165-175 p.Article in journal (Refereed) Published
Abstract [en]

Self-assembled monolayers and multilayers of a noradrenaline analogue (Nor-Pt) on gold substrates as well as multilayers of noradrenaline have been investigated by means of the molecular orientation, the molecule surface interaction, the molecular composition and the functional group availability for further biointeraction processes, using X-ray photoelectron spectroscopy (XPS), infrared reflection absorption spectroscopy (IRAS), and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. A chemical shift (1.7 eV) of the S 2p peak to lower binding energies is observed, in the XPS spectrum, indicating that the Nor-Pt molecules are chemisorbed onto the gold substrate. The IR results show that Nor-Pt adsorbate has the C=O stretching vibration modes parallel oriented relative to the gold substrate. The average tilt angle of the aromatic ring relative to the gold surface normal is determined to be approximately 51 degrees, based on the NEXAFS measurements on Nor-Pt monolayers. The experimental results and assignments are supported with theoretical studies where we use the building block principle in the spectral analysis and compare with the measurements of noradrenaline and Nor-Pt. The theoretical calculations are shown to be useful; for angle dependence NEXAFS studies as resonances with fully pi* or sigma* character are preferred for correct analysis.

Place, publisher, year, edition, pages
American Chemical Society , 2011. Vol. 115, no 1, 165-175 p.
National Category
Engineering and Technology
Identifiers
URN: urn:nbn:se:liu:diva-66293DOI: 10.1021/jp105696jISI: 000285818200024OAI: oai:DiVA.org:liu-66293DiVA: diva2:403130
Available from: 2011-03-11 Created: 2011-03-11 Last updated: 2015-05-29Bibliographically approved
In thesis
1. Structure analysis and molecular recognition studies of bio-functionalized surfaces
Open this publication in new window or tab >>Structure analysis and molecular recognition studies of bio-functionalized surfaces
2011 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Biological and chemical reactions involved in physiological processes are often complex and very sophisticated. Such processes can be mimicked in the laboratory to obtain important knowledge, valuable for the  development of new diagnostic methods, drugs and biosensors. This  thesis includes investigations of bio-functionalized surfaces that can be used as model systems to mimic naturally existing biomolecular recognition processes.

In this thesis, three different peptides, of our own design, that mimic parts of the second and third intracellular loops of the α2A-adrenergic receptor, are studied. The peptides were immobilized onto gold substrates, through thiol chemistry. The interaction between the peptides and the G-protein was investigated using surface plasmon resonance (SPR). The G-protein showed the highest binding capability for surfaces functionalized with a peptide mimicking the n-terminal of the third intracellular loop (GPR-i3n). The binding was enhanced when the pure GPR-i3n peptide was mixed with a short oligopeptide (3GC). A tentative explanation for the obtained results is that the presence of the 3GC molecule enables conformational changes of the GPR-i3n monolayer which affect the interaction with the G-protein. The results from the SPR measurements also indicated that the conformation of the G-protein was kept intact during the interaction with a peptide mimicking the c-terminal of the third intracellular loop (GPR-i3c). Multilayers were formed on the surfaces functionalized with a peptide mimicking the second intracellular loop (GPR-i2c) and the GPR-i3n peptide. We suggest that conformational changes of the G-protein are induced during the interaction with the surfaces functionalized with the GPR-i3n and GPR-i2c peptides.

Comprehensive surface characterizations of four biomolecular systems, based upon the functional groups: noradrenaline, phenylboronic-ester, phenylboronic-acid and benzenesulfonamide, are presented in the thesis. The aim is to develop a platform for detailed molecular recognition studies on surfaces. The molecular systems were characterized using infrared spectroscopy, X-ray photoelectron spectroscopy, near edge X-ray absorption fine structure spectroscopy, ellipsometry and contact angle goniometry. Noradrenaline was chosen as it is a neurotransmitter that interacts with the extracellular loops of adrenergic receptors. In this work, the noradrenaline analogue (Nor-Pt) of our own design, was equipped with a -SH handle to be linked to surfaces and with the free noradrenaline group available for interaction studies. The Nor-Pt molecules were organized on the surfaces with the sulfur atom close to the gold substrate and the aromatic ring available for possible interactions with other biomolecules in the ambient media. The main component of the C=O vibrational mode present in the amide moiety had a parallel orientation relative to the plane of the gold surface, based on the infrared spectroscopy results. The phenylboronic system was designed as a simple mimicry of an  adrenergic receptor as the boronic acid functional group binds to diol containing molecules such as noradrenaline. The boronic  esterterminated alkane thiol (BOR-Capped) was chemisorbed onto gold substrates. We showed that BOR-Capped was linked to the gold substrate via thiolate bond formation and formed a well-organized monolayer. The pinacolyl protection group was removed directly from the BOR-Capped monolayer on the surfaces, which resulted in an unprotected monolayer terminated with the boronic acid functional group (BOR-Uncapped). The strong chemical bond to the gold substrate was retained during the deprotection procedure as only thiolate sulfur species were observed for the BOR-Uncapped molecular system. The benzenesulfonamide based molecule was designed as a model system for bioselective surfaces. An amine-terminated alkane thiol was adsorbed onto a gold substrate. In a second step, a benzenesulfonamide derivative was linked to the amine-terminated monolayer by the formation of an amide bond. We showed that the resulting benzenesulfonamide-terminated alkane thiol (AUT-C6) formed a well-organized and semi-thick monolayer on the gold substrate. The polarization dependence of NEXAFS was used to determine the average tilt angle of the aromatic ring structures of Nor-Pt, BOR-Capped, BOR-Uncapped and AUT-C6. The results indicate that the aromatic ring planes of BOR-Capped and AUT-C6 have a preferential orientation toward the surface normal. The aromatic ring structures of Nor-Pt and BOR-Uncapped were determined to have a more tilted orientation relative to the gold surface normal.

Finally, the interaction between carbonic anhydrase and the AUT-C6 molecule was investigated using surface plasmon resonance and ellipsometry. The surface immobilized benzenesulfonamide was shown to bind to carbonic anhydrase and the results indicated that the interaction is specific.

Place, publisher, year, edition, pages
Linköping: Linköping University Electronic Press, 2011. 56 p.
Series
Linköping Studies in Science and Technology. Dissertations, ISSN 0345-7524 ; 1404
National Category
Natural Sciences
Identifiers
urn:nbn:se:liu:diva-71457 (URN)978–91–7393–050–5 (ISBN)
Public defence
2011-11-11, Planck, Fysikhuset, Campus Valla, Linköpings universitet, Linköping, 10:15 (Swedish)
Opponent
Supervisors
Available from: 2011-10-19 Created: 2011-10-19 Last updated: 2015-06-03Bibliographically approved

Open Access in DiVA

No full text

Other links

Publisher's full text

Authority records BETA

Vahlberg, CeciliaLinares, MathieuVillaume, SebastienNorman, PatrickUvdal, Kajsa

Search in DiVA

By author/editor
Vahlberg, CeciliaLinares, MathieuVillaume, SebastienNorman, PatrickUvdal, Kajsa
By organisation
Molecular Surface Physics and Nano ScienceFaculty of Science & EngineeringComputational PhysicsThe Institute of Technology
In the same journal
The Journal of Physical Chemistry C
Engineering and Technology

Search outside of DiVA

GoogleGoogle Scholar

doi
urn-nbn

Altmetric score

doi
urn-nbn
Total: 250 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • harvard1
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • oxford
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf