Surface-enhanced Raman study of organic sulfides adsorbed on silver: facile cleavage of sulfur-sulfur and carbon-sulfur bonds

Sandroff, C. J.; Herschbach, D. R.

doi:10.1021/j100214a002

Cited by 158 publications

(136 citation statements)

References 2 publications

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“…The peak at 542 cm Ϫ1 corresponding to the S-S stretching (21) in the OR spectrum is completely absent in the SER spectrum. This indicates the breaking of the S-S bond upon adsorption on Ag, which presumably involves homolytic cleavage of S-S bonds (7). Support for the silver-sulfur interaction on the surface is obtained from the weak broadband in the low frequency region (22) of the SER spectrum.…”

Section: Methodsmentioning

confidence: 91%

“…Evidence for the breaking of S-S bonds on adsorption also came from the absence of the C 6 H 5 -S-S bending mode, which is appearing at 340 cm Ϫ1 in the OR spectrum. The peaks at 998, 1018, and 1072 cm Ϫ1 are characteristic of the benzene thio group (7). Relative intensities of the peaks at 1571 and 998 cm Ϫ1 are decreased with respect to the peak at 1072 cm Ϫ1 upon adsorption.…”

Section: Methodsmentioning

confidence: 94%

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Self-assembled Monolayers of Two Aromatic Disulfides and a Diselenide on Polycrystalline Silver Films: An Investigation by SERS and XPS

Venkataramanan

Skanth

Bandyopadhyay

et al. 1999

Journal of Colloid and Interface Science

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Self-assembled monolayers of diphenyldisufide (DDS), naphthalenedisulfide (NDS), and diphenyldiselenide (DDSe) on polycrystalline silver films have been investigated by surface enhanced Raman spectroscopy (SERS) and X-ray photoelectron spectroscopy (XPS). DDS adsorbs on Ag through a homolytic cleavage of the S-S bond and resultant thiolate at the surface decomposes upon prolonged exposure to air. The geometry of the molecule is such that the benzene ring is almost horizontal to the surface. The Raman spectrum has been assigned in the light of ab-initio molecular orbital calculations. In DDSe, the Se-Se bond is retained upon adsorption and the molecule sticks up. In contrast, NDS is highly reactive on the microscopically rough surface so that a stable monolayer could not be prepared. A temperature dependent Raman study of the DDS monolayer shows the absence of any reorientation at the surface as one would expect from the adsorption geometry. XPS study complements the SERS data and shows the presence of Ag 2 S on an NDS exposed surface.

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Section: Methodsmentioning

confidence: 91%

Section: Methodsmentioning

confidence: 94%

Self-assembled Monolayers of Two Aromatic Disulfides and a Diselenide on Polycrystalline Silver Films: An Investigation by SERS and XPS

Venkataramanan

Skanth

Bandyopadhyay

et al. 1999

Journal of Colloid and Interface Science

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“…This peak is assigned to either an Ag-O bond from air oxygen or Ag 2 O, which may form upon air exposition of activated surface, 36 a Ag-N bond from the peptide, 37 or, less likely, from a sulfur containing contamination. This peak overlaps with the position of the n Ag-S vibration, 30 which would confirm the presence of a thiol bond. In summary, therefore, SERS confirms the XPS data, although SERS cannot confirm the generation of some thiol in the sample.…”

mentioning

confidence: 92%

“…This band indicates that some of the thioether is present as a chemisorbed thioether or in a cleaved stage, as thiol. 30 In the current case, however, SERS does not allow for a unambiguous distinction of thiol vs. chemisorbed thioether because of a broad emission peak at 200 to 320 cm…”

Section: -28mentioning

confidence: 99%

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Silver nanoparticle engineering via oligovaline organogels

et al. 2008

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L-Valine-based oligopeptides with the chemical structure Z-(L-Val) 3 -OMe and Z-(L-Val) 2 -L-Cys (S-Bzl)-OMe form stable organogels in butanol. Both peptides are efficient gelators, but Z-(L-Val) 2 -L-Cys(S-Bzl)-OMe crystallizes more readily than Z-(L-Val) 3 -OMe. The two peptides can form mixed fibers, which also gel butanol. The resulting organogels are very similar to oligovaline organogels reported earlier (Mantion and Taubert, Macromol. Biosci., 2007, 7, 208) as they also form highly ordered peptide fibers with a predominant b-sheet structure and diameters of ca. 100 nm. The fibers can be mineralized with silver nanoparticles using DMF as a reducing agent. The fraction of the sulfurcontaining peptide Z-(L-Val) 2 -L-Cys(S-Bzl)-OMe controls the shape and size of the resulting nanoparticles. At high Z-(L-Val) 2 -L-Cys(S-Bzl)-OMe content, small spherical particles are distributed all over the fiber. Lower contents of Z-(L-Val) 2 -L-Cys(S-Bzl)-OMe lead to a size increase of the particles and to more complex shapes like plate-like and raspberry-like silver particles. The interactions between peptide and silver ions or silver particles takes place via a complexation of the silver ions to the sulfur atom of the thioether moiety, and are shown to be the key interaction in controlling particle formation.

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Surface-enhanced Raman assays (SERA): measurement of bilirubin and salicylate

Sulk¹,

Chan²,

Guicheteau³

et al. 1999

J. Raman Spectrosc.

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Results of a study to detect bilirubin and salicylate using SERS and a reactive coating are presented. The motivation for this work was to develop an assay that would simplify an analysis by detecting the analyte in a whole blood sample. This would remove the risks and time associated with preparing a serum sample. Quantitative analysis was performed using partial least-squares. The results are that one can detect bilirubin and salicylate in whole blood at levels below the normal or therapeutic levels using a coating based on an argentiphilic diazonium molecule. The sharp Raman bands associated with the analyte-coating adduct are sufficiently resolved to allow the analyte to be detected in the presence of a complex matrix such as whole blood.

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Surface-enhanced Raman study of organic sulfides adsorbed on silver: facile cleavage of sulfur-sulfur and carbon-sulfur bonds

Cited by 158 publications

References 2 publications

Self-assembled Monolayers of Two Aromatic Disulfides and a Diselenide on Polycrystalline Silver Films: An Investigation by SERS and XPS

Self-assembled Monolayers of Two Aromatic Disulfides and a Diselenide on Polycrystalline Silver Films: An Investigation by SERS and XPS

Silver nanoparticle engineering via oligovaline organogels

Surface-enhanced Raman assays (SERA): measurement of bilirubin and salicylate

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