SERS observation of soft C–H vibrational mode of bifunctional alkanethiol molecules adsorbed at Au and Ag electrodes

Razmutė-Razmė, Inga; Kuodis, Zenonas; Eicher‐Lorka, Olegas; Niaura, Gediminas

doi:10.1039/b921291d

Cited by 20 publications

(23 citation statements)

References 24 publications

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“…a). Such band in the SERS spectra was assigned to soft C−H vibrational modes of the methylene groups interacting with the electrode surface . Thus, on the Ag electrode at −1.000 V, the peptide is in close proximity to the surface.…”

Section: Resultsmentioning

confidence: 99%

Influence of applied potential on bradykinin adsorption onto Ag, Au, and Cu electrodes

Proniewicz

Skołuba

Ignatjev

et al. 2013

J Raman Spectroscopy

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Surface‐enhanced Raman scattering, electrochemistry, and generalized two‐dimensional correlation analysis (G2DCA) methods were used to characterize bradykinin (BK), a hormone which is known to be involved in small‐cell and non‐small‐cell lung carcinoma and prostate cancer. BK was deposited onto Ag, Au, and Cu electrode surfaces under different applied electrode potentials (−1.000 V to 0.200 V) in aqueous solutions. Based on the analysis of the enhancement, the broadening, and the shifts in the wavenumbers of individual bands, specific conclusions were drawn regarding the peptide geometry and changes in this geometry that occurred when the electrode type and applied electrode potential were varied. Briefly, BK deposited onto the Ag, Au, and Cu electrode surfaces showed bands that were due to the vibrations of moieties in contact with or in close proximity to the electrode surfaces and were thus located on the same side of the polypeptide backbone. These moieties included the Phe, Arg, and Pro residues. The findings for adsorbed BK were fully supported by G2DCA, which also allowed us to determine the order in which changes occurred when the electrode potential was changed. In addition, it was found that at negative electrode potentials, the Phe rings and methylene groups interact with Ag electrode surface. No such interaction was observed for Au and Cu electrodes. Copyright © 2013 John Wiley & Sons, Ltd.

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Section: Resultsmentioning

confidence: 99%

Influence of applied potential on bradykinin adsorption onto Ag, Au, and Cu electrodes

Proniewicz

Skołuba

Ignatjev

et al. 2013

J Raman Spectroscopy

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“…Previously we have identified an unusually low frequency (2820-2830 cm À1 ) methylene stretching band in SERS spectra of adsorbed bifunctional alkanethiols associated with direct contact of methylene groups with the metal surface. 40 Similar soft methylene stretching bands were detected in the infrared reflection absorption spectroscopy (IRRAS) studies of various alkyl chains containing molecules adsorbed at metal surfaces. [54][55][56][57][58] In fact, the two bands associated with the surface-interactive CH 2 group were observed; softened band originating from the proximal to surface C-H group below 2850 cm À1 and stretching band of the distal C-H group, which projects away from the surface near 2890-2907 cm À1 .…”

Section: Temperature Dependence Of Sers Bands' Frequencymentioning

confidence: 54%

“…The shoulder near 2830 cm À1 (À1.000 V) was previously assigned to the stretching vibration of C-H groups which contact the electrode surface. 40 Bands due to the QC-H stretching vibrations of the aromatic rings are visible at 3064 and 3060 cm À1 for spectra recorded at À0.600 and À1.000 V, respectively.…”

Section: Paper Pccpmentioning

confidence: 96%

“…Its position may depend on several factors, including interaction between the methylene groups, gauche defects in the alkyl chain, and contact with the metal surface. 40,52,53 To get insight into the possible interaction of the methylene groups with the electrode surface, the 2700-3200 cm À1 region was analyzed in detail (Fig. 9).…”

Section: Temperature Dependence Of Sers Bands' Frequencymentioning

confidence: 99%

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Effect of potential on temperature-dependent SERS spectra of neuromedin B on Cu electrode

Ignatjev

Proniewicz

et al. 2013

Phys. Chem. Chem. Phys.

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Adsorption of decapeptide neuromedin B (NMB) on copper electrode has been investigated by in situ surface-enhanced Raman scattering (SERS) spectroelectrochemistry in the temperature interval from 12 to 72 °C at -0.600 and -1.000 V potentials. It was found that intensities of peptide bands decrease at temperatures above 30 °C with higher decrease slope at -1.000 V. Frequency of F12 mode (1004 cm(-1)) of non-surface-interactive phenylalanine residue was found to be insensitive to temperature variation at both studied electrode potentials, while frequency-temperature curves for surface-interactive groups (Amide-III, methylene) were found to be controlled by the potential. In particular, opposite frequency-temperature trends were detected for Amide-III (Am-III) mode indicating decrease in H-bonding interaction strength of amide C[double bond, length as m-dash]O and N-H groups above 38 °C for -0.600 V, and increase in H-bonding interaction strength between 12 and 72 °C for -1.000 V. Anomalous Am-III temperature-dependence of the frequency at -1.000 V was explained by temperature-induced transformation of a disordered secondary structure to a helix-like conformation. The potential-difference spectrum revealed interaction of methylene groups with Cu surface at sufficiently negative potential values because of the appearance of a soft C-H stretching band near 2825 cm(-1) and a broad band near 2904 cm(-1) assigned to vibration of a distal C-H bond of the surface-confined methylene group. Consequently, a rapid decrease in frequency of CH(2)-stretching band with temperature was observed at -1.000 V, while no essential frequency changes were detected for this mode at -0.600 V. The results show that electrode potential controls the temperature-dependence of the frequency for vibrations associated with surface-interactive molecular groups.

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“…As a nondestructive sensitive tool for studying the metal adsorbate inter actions and the reactivity of adsorbed species surface enhanced Raman scattering (SERS) is used since it can provide unique information about the structure and the orientation of the molecules adsorbed on the metal surface [24][25][26][27][28]. Specific applications of SERS have been described for studies of the orientation and configuration of adsorbed complex molecules on metal surfaces [29,30], self assembled monolayers [31][32][33][34][35][36][37][38][39][40], chemical analysis [41,42], biochemistry and biophysics [43][44][45][46] and single molecule detection [47][48][49].…”

Section: Introductionmentioning

confidence: 99%

Surface enhanced Raman spectroscopy of self-assembled monolayers of 2-mercaptopyridine on a gold electrode

Hassan

Holze

2012

Russ J Electrochem

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SERS observation of soft C–H vibrational mode of bifunctional alkanethiol molecules adsorbed at Au and Ag electrodes

Cited by 20 publications

References 24 publications

Influence of applied potential on bradykinin adsorption onto Ag, Au, and Cu electrodes

Influence of applied potential on bradykinin adsorption onto Ag, Au, and Cu electrodes

Effect of potential on temperature-dependent SERS spectra of neuromedin B on Cu electrode

Surface enhanced Raman spectroscopy of self-assembled monolayers of 2-mercaptopyridine on a gold electrode

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