Adsorption of n-butyl-substituted tetrathiafulvalene dodecanethiol on gold

Petoral, Rodrigo; Wermelin, Karin; Dahlstedt, Emma; Hellberg, Jonas

doi:10.1016/j.jcis.2005.02.046

Cited by 8 publications

(7 citation statements)

References 28 publications

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“…These results lead to important conclusion the observed specific chemical state representing large chemical shift is inherent to sulfur-gold interface. As to the S 2p XPS, Petoral Jr. et al reported that the energy of the S 2p peak in XPS is lower by about 2 eV than as a result of a strong molecule-surface interaction in the S 2p XPS spectra for thiol-Au bond [25]. Similar results were reported by the other groups [26][27][28][29].…”

Section: Resultssupporting

confidence: 57%

Observation of Au-S Interface of L-Cysteine on Gold Surface

Honda

Baba

Hirao

et al. 2009

e-J. Surf. Sci. Nanotechnol.

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We studied the metal-molecular interface of Au-S bonds at the L-cysteine modified gold surface using X-ray photoelectron spectroscopy (XPS) and near-edge x-ray absorption fine structure (NEXAFS). Two kinds of Lcysteine layers, i.e., multi-layer and two-layers, were prepared on gold substrate. The formation of unique chemical bond was found at the sulfur-gold interface. The sulfur 1s core-level energy of two-layered L-cysteine on gold is higher by 8.2 eV than that of multi-layered sample. The large chemical shift was also observed in S K-edge NEXAFS spectra. Such remarkably large chemical shift in the case of two-layers has never been reported for any sulfur compounds. The direction of the S 1s energy shift for Au-S bond is opposite to that for the normal metal sulfides. This means that the electrons are donated from the sulfur atom to the gold substrate, and most likely the sulfur atoms are positively charged at likely [δ + ] states. We conclude that the strong Au-S bonds that are recently used for the immobilization of molecules are due to the observed specific Au-S bond.

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Section: Resultssupporting

confidence: 57%

Observation of Au-S Interface of L-Cysteine on Gold Surface

Honda

Baba

Hirao

et al. 2009

e-J. Surf. Sci. Nanotechnol.

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“…Many authors have reported the electrochemical properties of TTF derivative SAMs. Such studies include the redox activity of TTF derivatives on gold, 18,25,26 electrochemical polymerization, 27 double-layer capacitance, 28 metal ion recognition, [29][30][31][32] and host-guest complexation. 33,34 However, a microscopic understanding of the electrochemical processes of TTFterminated SAMs has not yet been developed.…”

Section: Introductionmentioning

confidence: 99%

Dynamic and Collective Electrochemical Responses of Tetrathiafulvalene Derivative Self-Assembled Monolayers

et al. 2006

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Electroactive tetrathiafulvalene (TTF)-containing alkanethiol self-assembled monolayers (SAMs) were designed and synthesized to elucidate the relationship between electrochemical responses and film structures. Two TTF derivative molecules having one alkanethiol chain (1) and two alkanethiol chains (2) were utilized to modulate the molecular packing arrangements in the SAMs, and the formation and structure of the SAMs were characterized by surface plasmon resonance spectroscopy (SPR). SPR measurements in various contacting media demonstrated loose packing of SAM 1 and close packing of SAM 2 due to the different space fillings of the molecules. Two successive one-electron redox waves were observed for both SAMs by cyclic voltammetry. The peak widths of the redox waves were strongly dependent on the oxidation states of the TTF moieties, the packing arrangement of the SAMs, and the contacting medium. We found that TTF-based SAMs exhibited collective electrochemical responses induced by dynamic structural changes, depending on the degree of freedom for the component molecules in the SAMs. These results imply that the molecular design, taking into account the electrochemical responses, extends the available range of molecular-based functionalities in TTF-based SAMs.

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“…23 This may be because the sample was oxidized during the recrystallization process. In contrast, for the structure of L-cysteine in water, as previously discussed with respect to Figure 3, the resonance peaks of SO 4 2− (peaks D and E) are not observed although the resonance absorption peak from the S 1s orbital to the 2e − orbital is seen as peak C at the lower energy side. These results confirm that the sulfur atoms are not oxidized to SO 4 2− in water at pH 7.…”

Section: Resultsmentioning

confidence: 61%

“…In contrast, for the structure of L-cysteine in water, as previously discussed with respect to Figure 3, the resonance peaks of SO 4 2− (peaks D and E) are not observed although the resonance absorption peak from the S 1s orbital to the 2e − orbital is seen as peak C at the lower energy side. These results confirm that the sulfur atoms are not oxidized to SO 4 2− in water at pH 7. We expect that L-cysteine molecules in pH 7 water are surrounded by H 2 O, and the -SH group should form a hydrate with the water molecules without dissociating.…”

Section: Resultsmentioning

confidence: 61%

A fluorescence XAFS measurement instrument in the soft x-ray region toward observation under operando conditions

Honda

Baba

Shimoyama

et al. 2015

Review of Scientific Instruments

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X-ray absorption fine structure (XAFS) measurements are widely used for the analysis of electronic structure. Generally, XAFS in the soft X-ray region is measured under vacuum, but chemical structures under vacuum are typically different from those under operando conditions, where chemical species exhibit their function. Here, we developed an XAFS measurement instrument, as a step toward operando fluorescent, which yields XAFS measurement using synchrotron radiation in the soft X-ray region. We applied this method to analyze the local electronic structure of the sulfur atoms in L-cysteine in different pH solutions. In water at pH 7, the hydrogen atom does not dissociate from the thiol (-SH) group in L-cysteine, which forms a structure surrounded by and interacting with water molecules. The XAFS spectrum of L-cysteine in solution was altered by changing the pH. At pH 9, the hydrogen atom dissociated and a thiolate anion was formed. Although the -SH group was oxidized to SO4 (2-) when L-cysteine was adsorbed on a metal surface and dried, no oxidation was observed in solution. This may be because the water molecules were densely packed and protected the -SH group from oxidation. Our results show that this instrument aimed toward operando fluorescence XAFS measurements in the soft X-ray region is useful for structural analysis of sulfur atoms in organic molecules in air and in solution. The instrument will be applied to the structural analysis of materials containing elements that have absorption edges in soft X-ray region, such as phosphorus and alkali metals (potassium and cesium). It will be also particularly useful for the analysis of samples that are difficult to handle under vacuum and materials that have specific functions in solution.

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Adsorption of n-butyl-substituted tetrathiafulvalene dodecanethiol on gold

Cited by 8 publications

References 28 publications

Observation of Au-S Interface of L-Cysteine on Gold Surface

Observation of Au-S Interface of L-Cysteine on Gold Surface

Dynamic and Collective Electrochemical Responses of Tetrathiafulvalene Derivative Self-Assembled Monolayers

A fluorescence XAFS measurement instrument in the soft x-ray region toward observation under operando conditions

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