Mercury Segregation and Diselenide Self-Assembly on Gold

Prato, Mirko; Toccafondi, Chiara; Maidecchi, Giulia; Chaudhari, Vijay R.; Kotresh, Harish Makri Nimbegondi; Sampath, S.; Parodi, R.; Esaulov, Vladimir A.; Canepa, M.

doi:10.1021/jp207157m

Cited by 15 publications

(22 citation statements)

References 62 publications

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“…Clear peaks are observed in the Se 3d region (54–56 eV, Figure S2). These signatures are distinct from the neighboring gold feature (57 eV, Au 5p) and are in good agreement with literature reports for related selenium systems –. No appreciable difference is visible in the Au 4 f region (84 eV) when the spectra of treated and bare substrates are compared.…”

Section: Resultssupporting

confidence: 92%

Electrochemical Study of Selenocystine Reactivity and Reduction at Metallic Surfaces

et al. 2017

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The reduction of seleno-L-cystine is examined on gold and platinum electrodes in aqueous solution. The voltammetric behavior is indicative of a two-step process, in which the metallic substrate is modified by the diselenide analyte prior to observation of diffusionally controlled, proton-coupled electron transfer. X-ray photoelectron spectroscopy confirms the presence of selenium on gold foil samples that have been reductively cycled in selenocystine solution. The selenium-based surface modification, which is accessible through multiple preparation routes, can be removed by anodic stripping and fully restored through subsequent cycling. The described electrochemical approach allows for the analysis of redox-active chalcogen-containing species under physiologically relevant conditions. Results and Discussion Voltammetric Behavior of Seleno-L-cystine on GoldThe voltammetric response of selenocystine on gold features a quasi-reversible redox couple centered at À486 mV vs. Ag/ AgCl. [10] Figure 1 shows a comparison of cyclic voltammograms recorded for increasing selenocystine concentrations (0.2-2 mM) in phosphate buffered saline (PBS, pH 7). For each concentration, the electrode has been reductively cycled (À0.2 to À0.7 V vs. Ag/AgCl) for 100 consecutive scans in the selenium-containing solution to reach a steady signal. [10] The dependence of peak current on concentration is linear (Figure S1), consistent with the measured redox process corre- [a]

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Section: Resultssupporting

confidence: 92%

Electrochemical Study of Selenocystine Reactivity and Reduction at Metallic Surfaces

et al. 2017

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“…This behavior is consistent with a two-step mechanism in which the diselenide is first cleaved to yield a selenium-gold adsorbate (1) and then bulk selenocystine is reduced at the modified substrate (2). Formation of gold-selenium monolayers and films via Se-Se bond cleavage is well documented in the literature [33][34][35][36][37][38][39][40][41][42][43].…”

Section: Resultsmentioning

confidence: 88%

Voltammetric behavior of selenocystine at modified gold substrates

Walker

Karnaukh

Dewan

et al. 2016

Electrochemistry Communications

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The voltammetric response of seleno-L-cystine has been studied at gold substrates under physiological conditions. The reactivity of diselenides is utilized to generate a modified electrode surface, which in turn allows for electroanalysis of solution-based selenium species. Stable and reproducible voltammetry is observed for selenocystine reduction at pH 7 on selenium-modified gold substrates (E mid =-486 mV vs. Ag/AgCl) and is consistent with a diffusionally controlled process. Modification of the gold surface is readily achieved via electrochemical cycling in the presence of a diselenide source at conventional scan rates. These studies afford voltammetric characterization of the selenocystine / selenocysteine redox couple under physiologically relevant conditions and highlight the potential utility of selenium-modified substrates for electroanalysis of chalcogen-containing species.

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“…The experimental procedure has been outlined in detail in previous publications [ 22 – 24 26 – 27 43 , 48 , 69 ] and here we provide only essential points about new experiments relevant to this report.…”

Section: Methodsmentioning

confidence: 99%

“…Much work on various aspects of assembly and its uses has been performed with sulfur head group (thiol) molecules [ 1 – 27 ], but interest in other head group atoms such as C [ 28 – 29 ], N [ 30 ] and other chalcogenides has also received increased attention. In particular, selenium head group SAMs have attracted much attention and significant research has resulted [ 31 – 43 ] for substrates such as Au and Ag. There is considerable discussion in the literature about the strength of the head group substrate bond [ 14 , 34 , 41 ] and whether or not it provides a better conductance pathway than sulfur.…”

Section: Introductionmentioning

confidence: 99%

Case studies on the formation of chalcogenide self-assembled monolayers on surfaces and dissociative processes

Tong¹,

Jiang²,

Bendounan³

et al. 2016

Beilstein J. Nanotechnol.

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SummaryThis report examines the assembly of chalcogenide organic molecules on various surfaces, focusing on cases when chemisorption is accompanied by carbon–chalcogen atom-bond scission. In the case of alkane and benzyl chalcogenides, this induces formation of a chalcogenized interface layer. This process can occur during the initial stages of adsorption and then, after passivation of the surface, molecular adsorption can proceed. The characteristics of the chalcogenized interface layer can be significantly different from the metal layer and can affect various properties such as electron conduction. For chalcogenophenes, the carbon–chalcogen atom-bond breaking can lead to opening of the ring and adsorption of an alkene chalcogenide. Such a disruption of the π-electron system affects charge transport along the chains. Awareness about these effects is of importance from the point of view of molecular electronics. We discuss some recent studies based on X-ray photoelectron spectroscopy that shed light on these aspects for a series of such organic molecules.

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Mercury Segregation and Diselenide Self-Assembly on Gold

Cited by 15 publications

References 62 publications

Electrochemical Study of Selenocystine Reactivity and Reduction at Metallic Surfaces

Electrochemical Study of Selenocystine Reactivity and Reduction at Metallic Surfaces

Voltammetric behavior of selenocystine at modified gold substrates

Case studies on the formation of chalcogenide self-assembled monolayers on surfaces and dissociative processes

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