Application of calixarene to high active surface-enhanced Raman scattering (SERS) substrates suitable for in situ detection of polycyclic aromatic hydrocarbons (PAHs) in seawater

• Published in: Journal of Raman spectroscopy 2012-08, Vol.43 (8), p.1003-1009
• Main Authors: Kwon, Yong-Hyok, Sowoidnich, Kay, Schmidt, Heinar, Kronfeldt, Heinz-Detlef
• Format: Article
• Language: English
• Subjects: DMCX; Nanoparticles; Naphthalene; PAHs; Polycyclic aromatic hydrocarbons; Pyrenes; Raman scattering; Sea water; seawater; SERS; Silver; silver colloid; Sol gel process
• ISSN: 0377-0486; 1097-4555
• DOI: 10.1002/jrs.3157

The characteristics of the sol–gel matrix embedding Ag nanoparticles functionalized with 25,27‐dimercaptoacetic acid‐26,28‐dihydroxy‐4‐tert‐butylcalix[4]arene (DMCX) suitable for the in situ detection of polycyclic aromatic hydrocarbons (PAHs) in seawater is presented. The DMCX‐functionalized silver nanoparticles were produced by the thermal reduction method in xerogel film. The silver colloid blocks were formed in the sol–gel matrix, with a diameter ranging from 50 to 120 nm. DMCX forming the monolayer on the silver nanoparticle surface contributes to the surface‐enhanced Raman scattering (SERS) activity due to the aggregation of silver nanoparticles and the preconcentration of PAH molecules within the zone of electromagnetic enhancement. When selected, PAH molecules e.g. pyrene and naphthalene were adsorbed onto the SERS substrate; Raman band positions of PAH were slightly shifted. A calibration procedure reveals that this type of SERS substrate has a limit of detection of 3 × 10−10 mol/l for pyrene and 13 × 10−9 mol/l for naphthalene in artificial seawater. The Raman signal response on a pyrene concentration change in artificial seawater was evaluated using a 671‐nm Raman setup with a flow‐through cell. This type of SERS substrate will be suitable for the in situ trace detection of pollutant chemicals in seawater. Copyright © 2012 John Wiley & Sons, Ltd. Sol‐gel matrix embedding Ag nanoparticles with calix[4]arene was introduced for the detection of polycyclic aromatic hydrocarbons in seawater at very low concentrations using a 671‐nm diode laser excitation. A calibration procedure reveals that the surface‐enhanced Raman scattering substrates have a limit of detection that is less than 1 nmol/l for pyrene and 13 nmol/l for naphthalene in artificial seawater.