Surface structure and chemical switching of thioctic acid adsorbed on Au(111) as observed using near-edge X-ray absorption fine structure

Thioctic acid (alpha-lipoic acid) is a molecule with a large disulfide-containing base, a short alkyl chain with four CH2 units, and a carboxyl termination. Self-assembled monolayer (SAM) films ofthioctic acid adsorbed on Au(111) have been investigated with near-edge X-ray absorption fine structure...

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Veröffentlicht in:Langmuir : the ACS journal of surfaces and colloids. - 1985. - 20(2004), 12 vom: 08. Juni, Seite 4939-44
1. Verfasser: Willey, Trevor M (VerfasserIn)
Weitere Verfasser: Vance, Andrew L, Bostedt, Christoph, van Buuren, Tony, Meulenberg, Robert W, Terminello, Louis J, Fadley, Charles S
Format: Aufsatz
Sprache:English
Veröffentlicht: 2004
Zugriff auf das übergeordnete Werk:Langmuir : the ACS journal of surfaces and colloids
Schlagworte:Journal Article
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245 1 0 |a Surface structure and chemical switching of thioctic acid adsorbed on Au(111) as observed using near-edge X-ray absorption fine structure 
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520 |a Thioctic acid (alpha-lipoic acid) is a molecule with a large disulfide-containing base, a short alkyl chain with four CH2 units, and a carboxyl termination. Self-assembled monolayer (SAM) films ofthioctic acid adsorbed on Au(111) have been investigated with near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and X-ray photoelectron spectroscopy (XPS) to determine film quality, bonding, and morphology. Using standard preparation protocols for SAMs, that is, dissolving thioctic acid in ethanol and exposing gold to the solution, results in poor films. These films are highly disordered, contain a mixture of carboxyl and carboxylate terminations, have more than monolayer coverage, and exhibit unbound disulfide. Conversely, forming films by dissolving 1 mmol thioctic acid into 5% acetic acid in ethanol (as previously reported with carboxyl-terminated alkanethiols) forms ordered monolayers with small amounts of unbound sulfur. NEXAFS indicates tilted over endgroups with the carboxyl group normal on average 38 degrees from the surface normal. Slight angle-dependent intensity modulations in other features indicate alkyl chains statistically more upright than prostrate on the surface. Reflection-absorption Fourier transform infrared (RA-FTIR) spectra indicate hydrogen bonding between neighboring molecules. In such well-formed monolayers, a stark reorientation occurs upon deprotonation of the endgroup by rinsing in a KOH solution. The carboxylate plane normal is now about 66 degrees from sample normal, a much more upright orientation. Data indicate this reorientation may also cause a more upright orientation to the alkyl portion of the molecules 
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700 1 |a Vance, Andrew L  |e verfasserin  |4 aut 
700 1 |a Bostedt, Christoph  |e verfasserin  |4 aut 
700 1 |a van Buuren, Tony  |e verfasserin  |4 aut 
700 1 |a Meulenberg, Robert W  |e verfasserin  |4 aut 
700 1 |a Terminello, Louis J  |e verfasserin  |4 aut 
700 1 |a Fadley, Charles S  |e verfasserin  |4 aut 
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