Adsorption behaviour of DNA bases at the Au(111) electrode

Camargo, A.; Baumgärtel, H.; Donner, C.

doi:10.1039/b208139c

Cited by 22 publications

(21 citation statements)

References 8 publications

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“…Obviously, this does not mean that C is not co-adsorbed. In fact, the peak potential obtained for the same [mC] is different when C is present, thus suggesting a co-adsorption as previously reported with other nucleobases [34,35]. This fact will difficult a direct electroanalytical determination of mC in presence of C because some pre-analysis, including a pre-determination of C as well as some previous calibration protocols will be required.…”

Section: Accepted Manuscriptmentioning

confidence: 77%

Electrochemical detection of cytosine and 5-methylcytosine on Au(111) surfaces

Brotons

Arán‐Ais

Feliu

et al. 2016

Electrochemistry Communications

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Please cite this article as: Ariadna Brotons, RosaM. Arán-Ais, Juan M. Feliu, Vicente Montiel, Jesús Iniesta, Francisco J. Vidal-Iglesias, José Solla-Gullón, Electrochemical detection of cytosine and 5-methylcytosine on Au(111) surfaces, Electrochemistry Communications (2016Communications ( ), doi: 10.1016Communications ( /j.elecom.2016 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. A C C E P T E D M A N U S C R I P T ACCEPTED MANUSCRIPT AbstractIn this communication we report a voltammetric study of the adsorption-desorption of cytosine (C) and methylcytosine (mC) on well-defined gold (Au) electrodes. The voltammetric measurements clearly indicate that these processes are extremely sensitive to the Au surface structure and in particular to the presence of (111) surface domains.Interestingly, on Au(111) surfaces, a linear correlation between the C and mC concentrations (logarithm scale) and the peak potential of the main voltammetric feature is found. In addition, in the simultaneous presence of both molecules, mC governs the electrochemical response, which has allowed its accurate quantification in C-mC mixtures. In situ FTIR spectroscopic measurements have been carried out to deepen on this mC electrochemical sensitivity. This research may contribute to the future development of an electrochemical sensor for the determination of the degree of methylation in DNA.

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Section: Accepted Manuscriptmentioning

confidence: 77%

Electrochemical detection of cytosine and 5-methylcytosine on Au(111) surfaces

Brotons

Arán‐Ais

Feliu

et al. 2016

Electrochemistry Communications

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“…Based on earlier studies on adenine adsorption on Au (111) in acid media [13] and reports in the literature for the adsorption of other nucleobases, [4,6,11,[14][15][16][17][18] region I was reconciled with the formation of a disordered and planar orientated layer of molecules, followed by (large peak between regions I and II) further adsorption of adenine and its deprotonation along with the lifting of the surface reconstruction, and the formation of an ordered, physisorbed film on the non-reconstructed surface (region II). The decrease …”

Section: Resultsmentioning

confidence: 99%

Surface‐Structure‐Sensitive Adsorption of Adenine on Gold Electrodes

2005

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Since the earlier work on Hg, and more recently on Ag, Au and Pt single-crystal electrodes, electrochemical studies have shown that DNA bases are strongly adsorbed at the metalsolution interfaces and generally undergo a two-dimensional first-order transition.[1] Although it is well-known that the surface atomic structure, as much as its chemical nature, can play a critical role in the formation of ordered adsorbed monolayers, only few detailed investigations have evaluated the effect of the presence of regular monoatomic steps on the adsorption of nucleobases and nucleosides. [2][3][4] The structure and properties of adsorbed nucleobase films deduced from electrochemical studies have been confirmed by several in situ spectroscopy techniques, such as subtractively normalized interfacial Fourier-transform infrared spectroscopy (SNIFTIRS), [5] surface-enhanced infrared reflection-absorption spectroscopy with the attenuated total reflection technique (ATR-SEIRAS), [4,6] surface-enhanced Raman spectroscopy (SERS), [7] surface X-ray scattering (SXS), [8] X-ray photoelectron spectroscopy (XPS), [9] and scanning tunnelling microscopy (STM). [9][10][11][12] These techniques, however, were mostly used to obtain information on monolayer films adsorbed on smooth basal planes or single-crystal surfaces with a low density of monotamic steps and hence reduced surface atomic corrugation. Although the macroscopic information that can be obtained by electrochemical techniques may not reflect the entire complexity of interfacial phenomena, it has long been used to assess the average systematic effect of surface atomic structure details such as regular monoatomic steps and kinks on, for example, the ionic and organic adsorption, electrocatalysis, under-potential deposition and two-dimensional film condensation.An electrochemical study was therefore initiated to reveal the effect of surface structure regularities, such as monoatomic steps and kinks, on the adsorption of the DNA bases at gold single crystal electrodes. We report here a preliminary overview of the influence of the surface crystallographic orientation on the adsorption of adenine in acid media. Results and DiscussionIn Figure 1 a, the cyclic voltamograms obtained for the Au (111) electrode in the presence and absence of adenine in 0.1 m HClO 4 are compared. The gold surface oxidation is inhibited in the presence of adenine and occurs at higher potential values suggesting that a strongly adsorbed layer is formed. The analysis of the charges involved in the oxidation and reduction processes shows that adenine oxidation is irreversible and concomitant with the gold surface oxidation (Q ox /Q red > 2). The same behavior was also observed for the other gold surfaces under study.The voltamogram obtained for Au (111) in the double layer region, Figure 1 b, as well as the capacitance curve, Figure 1 c, substantiate that a chemisorbed layer of adenine is formed at the more positive potential values (region III). Based on earlier studies on adenine adsorption on Au (111) in acid ...

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“…20,21 There have been a number of electrochemical studies of the adsorption of adenine on the Au͑111͒ and Au͑100͒ surfaces. 22,23 On a Au͑111͒ surface 22 there is evidence of a similar phase transition. In addition, the oxidation of the bare gold is suppressed by the adsorption of adenine and there is evidence in the capacitance data for the formation of an organic film.…”

Section: Introductionmentioning

confidence: 82%

Determination of the structure of adenine monolayers adsorbed at Au(110)/electrolyte interfaces using reflection anisotropy spectroscopy

Bowfield

Dolan

et al. 2009

The Journal of Chemical Physics

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Reflection anisotropy spectroscopy (RAS) has been used to show that at saturation coverage adenine adsorbs on the Au(110)/electrolyte interface in a base-stacking configuration with the plane of the bases orientated vertically on the surface and with the long axis of the molecules parallel to the [110] direction. Changes in the RAS observed from adsorbed adenine as a result of changes in the potential applied to the Au(110) electrode could arise from slight changes in the orientation of the molecules in the vertical plane.

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Adsorption behaviour of DNA bases at the Au(111) electrode

Cited by 22 publications

References 8 publications

Electrochemical detection of cytosine and 5-methylcytosine on Au(111) surfaces

Electrochemical detection of cytosine and 5-methylcytosine on Au(111) surfaces

Surface‐Structure‐Sensitive Adsorption of Adenine on Gold Electrodes

Determination of the structure of adenine monolayers adsorbed at Au(110)/electrolyte interfaces using reflection anisotropy spectroscopy

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