Elucidation of the bonding of a near infrared dye to hollow gold nanospheres: a chalcogen tripod

H. Kearns, S Sengupta, Ivan Ramos Sasselli, L Bromley, Karen Faulds, Christopher Tuttle, Matthew A. Bedics, Michael R. Detty, Luis Verlarde, Duncan Graham, W. E. Smith

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

Infrared surface enhanced Raman scattering (SERS) is an attractive technique for the in situ detection of nanoprobes in biological samples due to the greater depth of penetration and reduced interference compared to SERS in the visible region. A key challenge is to understand the surface layer formed in suspension when a specific label is added to the SERS substrate in aqueous suspension. SERS taken at different wavelengths, theoretical calculations, and surface-selective sum frequency generation vibrational spectroscopy (SFG-VS) were used to define the surface orientation and manner of attachment of a new class of infrared SERS label with a thiopyrylium core and four pendant 2-selenophenyl rings. Hollow gold nanospheres (HGNs) were used as the enhancing substrate and two distinct types of SERS spectra were obtained. With excitation close to resonance with both the near infrared electronic transition in the label (max 826 nm) and the plasmon resonance maximum (690 nm), surface enhanced resonance Raman scattering (SERRS) was obtained. SERRS indicates that the major axis of the core is near to perpendicular to the surface plane and SFG-VS obtained from a dried gold film gave a similar orientation with the major axis at an angle 64°-85° from the surface plane. Longer excitation wavelengths give SERS with little or no molecular resonance contribution and new vibrations appeared with significant displacements between the thiopyrylium core and the pendant selenophene rings. Analysis using calculated spectra with one or two rings rotated indicates that two rings on one end are rotated towards the metal surface to give an arrangement of two selenium and one sulphur atoms directly facing the gold structure. The spectra, together with a space filled model, indicate that the molecule is strongly adsorbed to the surface through the selenium and sulphur atoms in an arrangement which will facilitate layer formation.
LanguageEnglish
Pages5160-5170
Number of pages11
JournalChemical Science
Volume7
Issue number8
Early online date21 Apr 2016
DOIs
Publication statusPublished - 1 Aug 2016

Fingerprint

Chalcogens
Nanospheres
Gold
Coloring Agents
Infrared radiation
Raman scattering
Labels
Vibrational spectroscopy
Selenium
Sulfur
Suspensions
Nanoprobes
Frequency selective surfaces
Wavelength
Atoms

Keywords

  • Infrared surface enhanced Raman scattering
  • SERS
  • near infrared dye
  • hollow gold nanospheres
  • chalcogen tripod

Cite this

Kearns, H. ; Sengupta, S ; Ramos Sasselli, Ivan ; Bromley, L ; Faulds, Karen ; Tuttle, Christopher ; Bedics, Matthew A. ; Detty, Michael R. ; Verlarde, Luis ; Graham, Duncan ; Smith, W. E. / Elucidation of the bonding of a near infrared dye to hollow gold nanospheres : a chalcogen tripod. In: Chemical Science. 2016 ; Vol. 7, No. 8. pp. 5160-5170.
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abstract = "Infrared surface enhanced Raman scattering (SERS) is an attractive technique for the in situ detection of nanoprobes in biological samples due to the greater depth of penetration and reduced interference compared to SERS in the visible region. A key challenge is to understand the surface layer formed in suspension when a specific label is added to the SERS substrate in aqueous suspension. SERS taken at different wavelengths, theoretical calculations, and surface-selective sum frequency generation vibrational spectroscopy (SFG-VS) were used to define the surface orientation and manner of attachment of a new class of infrared SERS label with a thiopyrylium core and four pendant 2-selenophenyl rings. Hollow gold nanospheres (HGNs) were used as the enhancing substrate and two distinct types of SERS spectra were obtained. With excitation close to resonance with both the near infrared electronic transition in the label (max 826 nm) and the plasmon resonance maximum (690 nm), surface enhanced resonance Raman scattering (SERRS) was obtained. SERRS indicates that the major axis of the core is near to perpendicular to the surface plane and SFG-VS obtained from a dried gold film gave a similar orientation with the major axis at an angle 64°-85° from the surface plane. Longer excitation wavelengths give SERS with little or no molecular resonance contribution and new vibrations appeared with significant displacements between the thiopyrylium core and the pendant selenophene rings. Analysis using calculated spectra with one or two rings rotated indicates that two rings on one end are rotated towards the metal surface to give an arrangement of two selenium and one sulphur atoms directly facing the gold structure. The spectra, together with a space filled model, indicate that the molecule is strongly adsorbed to the surface through the selenium and sulphur atoms in an arrangement which will facilitate layer formation.",
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author = "H. Kearns and S Sengupta and {Ramos Sasselli}, Ivan and L Bromley and Karen Faulds and Christopher Tuttle and Bedics, {Matthew A.} and Detty, {Michael R.} and Luis Verlarde and Duncan Graham and Smith, {W. E.}",
year = "2016",
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Kearns, H, Sengupta, S, Ramos Sasselli, I, Bromley, L, Faulds, K, Tuttle, C, Bedics, MA, Detty, MR, Verlarde, L, Graham, D & Smith, WE 2016, 'Elucidation of the bonding of a near infrared dye to hollow gold nanospheres: a chalcogen tripod' Chemical Science, vol. 7, no. 8, pp. 5160-5170. https://doi.org/10.1039/C6SC00068A

Elucidation of the bonding of a near infrared dye to hollow gold nanospheres : a chalcogen tripod. / Kearns, H.; Sengupta, S; Ramos Sasselli, Ivan; Bromley, L; Faulds, Karen; Tuttle, Christopher; Bedics, Matthew A.; Detty, Michael R.; Verlarde, Luis; Graham, Duncan; Smith, W. E.

In: Chemical Science, Vol. 7, No. 8, 01.08.2016, p. 5160-5170.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Elucidation of the bonding of a near infrared dye to hollow gold nanospheres

T2 - Chemical Science

AU - Kearns, H.

AU - Sengupta, S

AU - Ramos Sasselli, Ivan

AU - Bromley, L

AU - Faulds, Karen

AU - Tuttle, Christopher

AU - Bedics, Matthew A.

AU - Detty, Michael R.

AU - Verlarde, Luis

AU - Graham, Duncan

AU - Smith, W. E.

PY - 2016/8/1

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N2 - Infrared surface enhanced Raman scattering (SERS) is an attractive technique for the in situ detection of nanoprobes in biological samples due to the greater depth of penetration and reduced interference compared to SERS in the visible region. A key challenge is to understand the surface layer formed in suspension when a specific label is added to the SERS substrate in aqueous suspension. SERS taken at different wavelengths, theoretical calculations, and surface-selective sum frequency generation vibrational spectroscopy (SFG-VS) were used to define the surface orientation and manner of attachment of a new class of infrared SERS label with a thiopyrylium core and four pendant 2-selenophenyl rings. Hollow gold nanospheres (HGNs) were used as the enhancing substrate and two distinct types of SERS spectra were obtained. With excitation close to resonance with both the near infrared electronic transition in the label (max 826 nm) and the plasmon resonance maximum (690 nm), surface enhanced resonance Raman scattering (SERRS) was obtained. SERRS indicates that the major axis of the core is near to perpendicular to the surface plane and SFG-VS obtained from a dried gold film gave a similar orientation with the major axis at an angle 64°-85° from the surface plane. Longer excitation wavelengths give SERS with little or no molecular resonance contribution and new vibrations appeared with significant displacements between the thiopyrylium core and the pendant selenophene rings. Analysis using calculated spectra with one or two rings rotated indicates that two rings on one end are rotated towards the metal surface to give an arrangement of two selenium and one sulphur atoms directly facing the gold structure. The spectra, together with a space filled model, indicate that the molecule is strongly adsorbed to the surface through the selenium and sulphur atoms in an arrangement which will facilitate layer formation.

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KW - Infrared surface enhanced Raman scattering

KW - SERS

KW - near infrared dye

KW - hollow gold nanospheres

KW - chalcogen tripod

U2 - 10.1039/C6SC00068A

DO - 10.1039/C6SC00068A

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SN - 2041-6520

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