Surface-enhanced resonance Raman scattering from water-soluble porphyrins adsorbed on a silver electrode

Cotton, Therese M.; Schultz, Steven G.; Duyne, Richard P. Van

doi:10.1021/ja00388a008

Cited by 106 publications

(73 citation statements)

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“…However, one noticeable difference between SERR and RR spectra in this excitation region is that b 1g modes are much weaker than b 2g modes in the SERR spectra, but the opposite behavior was observed in RR spectra, 26 despite the fact that both b 1g and b 2g modes gain their (resonance) intensity via the JT effect. For example, 10 (1650), 11 (1505) and 13 (1185) all display higher intensities than 29 (1356) and 34 (1195) in Soret-excited RR spectra, 26,27,29 but the opposite pattern is observed here in SERRS. The redistribution of JT activity from the b 1g to b 2g mode in SERR spectra with Soret excitation is very likely associated with the orientation of NiP on the colloid surface, reflecting an interplay between SERS effect and resonance (vibronic) effect (see below).…”

Section: Enhancement Patterns In Serrsmentioning

confidence: 50%

Surface‐enhanced resonance Raman spectroscopy of water‐insoluble Ni(II) porphine adsorbed on aqueous silver sol: suppression of antisymmetric scattering, antiresonance effect and higher order scattering

Петров

Chen

et al. 2001

J Raman Spectroscopy

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With the intention of examining how adsorption on a SERS-active surface affects the electronic resonance enhancement in surface-enhanced resonance Raman scattering (SERRS) from Ni(II) porphine (NiP), we acquired high-quality SERR spectra from very low concentrations of NiP (∼10 −8 M) in aqueous Ag sol from 50 to 3500 cm −1 with excitations across both the Soret and Q absorption bands. Water-insoluble NiP was transferred to aqueous silver sol surface by using pyridine as carrying solvent, taking advantage of the fact that it both dissolves NiP and is partially miscible with water at the same time. It was found that SERS boosts the overall sensitivity of resonance Raman scattering by providing extra enhancement (the surface enhancement) to a 1g , b 1g and b 2g modes, but not to a 2g modes. As a consequence, a relative 'suppression' effect of antisymmetric scattering by a 2g modes was observed when excitation was tuned into the Q absorption band region in SERR spectra. With excitations in the valley between the Soret and Q absorption bands, an antiresonance effect was observed in the SERR spectra for the totally symmetric n 6 mode at 995 cm −1 which was attributed to the destructive interference between Franck-Condon and Herzberg-Teller mechanisms. Strong second-order and weak third-order Raman scattering were observed in the SERR spectra of NiP when excitation was tuned close to and across the Q 1 absorption band. A vibronic theory based on the extension of Albrecht's formalism was developed to account for the activation of high-order Raman scattering and for the antiresonance effect of the n 6 band. More than 100 Raman wavenumbers, including both fundamentals and overtones/combinations, both in-plane and out-of-plane modes, were observed for NiP in its SERRS spectra. The wavenumbers from the SERR spectra agree very well with those obtained from RR spectra from a homogeneous NiP solution and FTIR data from KBr (CsI) pellets, suggesting that adsorption of NiP on a SERS-active surface is physisorption in nature, and that such adsorption has a negligibly small effect to the vibrational wavenumbers. The observed Raman wavenumbers from SERR spectra are also in excellent agreement with those predicted from ab initio/DFT calculations for both in-plane and out-of-plane modes. Many out-of-plane modes and IR-active in-plane modes were observed in the SERR spectra of NiP, suggesting that the effective symmetry of the adsorbed NiP is lower than the ideal planar D 4h .

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Section: Enhancement Patterns In Serrsmentioning

confidence: 50%

Surface‐enhanced resonance Raman spectroscopy of water‐insoluble Ni(II) porphine adsorbed on aqueous silver sol: suppression of antisymmetric scattering, antiresonance effect and higher order scattering

Петров

Chen

et al. 2001

J Raman Spectroscopy

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“…6 shows the relationship between log I p and log ν for the different peaks seen in the Raman spectra are characteristic for those of a CoTSPor molecule. In addition, the Raman band positions and bandwidth are similar to those of pure crystalline substances (1528, 1451, 748 and 681 cm −1 ) [15][16]. Spectra of the CoTSPor particles are shown in Fig.…”

Section: Scan Rate Studymentioning

confidence: 53%

Study of the deposition and characterisation of a 5,10,15,20-tetrakis-(4-sulphonatophenyl)porphyrin Co(II) layer at gold surfaces in alkaline solution

Wael

Westbroek

Vandenabeele

et al. 2005

Electrochimica Acta

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“…The similarity of the spectra of a H 2 TSPor modified gold electrode and that of a CoTSPor modified electrode indicates the incorporation of gold atoms into the porphyrin ligand structure. This phenomenon is already described for Ag incorporation into a porphyrin structure during an anodization step [23] but was never observed for gold. Therefore it is assumed that a AuTSPor layer is formed onto the gold electrode.…”

Section: Electrochemical Deposition Of H 2 Tspor At a Gold Array Strumentioning

confidence: 55%

Electrochemical deposition of 5,10,15,20-tetrakis-(4-sulphonatophenyl) porphyrin and its Co(II) derivative at a gold microelectrode array

Wael

Adriaens

Temmerman

2005

Analytica Chimica Acta

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This paper describes the fabrication and surface modification of gold microelectrode array structures. The modification is done by continuous cycling of the electrode array in a pH 12 buffer solution containing 8.01 mmol L −1 5,10,15,20-tetrakis-(4-sulphonatophenyl)porphyrin tetrasodium salt (H 2 TSPor). Incorporation of gold ions in the ligand during the potential cycling of the gold electrode is assumed. Only ring processes appear in the current potential curves, which do not change with scan number, indicating a fast adsorption. A second modification was performed through the electrodeposition of 5,10,15,20-tetrakis-(4-sulphonatophenyl)porphyrin Co(II) (CoTSPor) at a gold micro-electrode array.

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Surface-enhanced resonance Raman scattering from water-soluble porphyrins adsorbed on a silver electrode

Cited by 106 publications

References 0 publications

Surface‐enhanced resonance Raman spectroscopy of water‐insoluble Ni(II) porphine adsorbed on aqueous silver sol: suppression of antisymmetric scattering, antiresonance effect and higher order scattering

Surface‐enhanced resonance Raman spectroscopy of water‐insoluble Ni(II) porphine adsorbed on aqueous silver sol: suppression of antisymmetric scattering, antiresonance effect and higher order scattering

Study of the deposition and characterisation of a 5,10,15,20-tetrakis-(4-sulphonatophenyl)porphyrin Co(II) layer at gold surfaces in alkaline solution

Electrochemical deposition of 5,10,15,20-tetrakis-(4-sulphonatophenyl) porphyrin and its Co(II) derivative at a gold microelectrode array

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