SERS detection of polyaromatic hydrocarbons on a β‐cyclodextrin containing polymer brush

Abstract

We have designed a new surface‐enhanced Raman scattering (SERS) sensor composed of β‐cyclodextrin (β‐CD) containing poly(glycidyl methacrylate) (PGMA) brush coated silicon substrate and per‐6‐deoxy‐(6‐thio)‐β‐cyclodextrin (β‐CD‐SH) modified gold nanoparticles for detection of polyaromatic hydrocarbons (PAHs; pyrene and anthracene). The β‐CD containing PGMA brushes were synthesized by the interface‐mediated Reversible addition‐fragmentation chain transfer (RAFT) polymerization of glycidyl methacrylate and followed an epoxide ring‐opening reaction to attach β‐CD molecules. Some PAHs, such as pyrene and anthracene, can be introduced into the hydrophobic space of β‐CD, which allows them to detect the SERS of PAHs. After separating pyrene or anthracene from the solution by the β‐CD containing PGMA brush coated silicon substrate, they were sandwiched with the SERS substrate consisting of per‐6‐deoxy‐(6‐thio)‐β‐cyclodextrin and rhodamine 6G (Raman reporter) on gold nanoparticles. The correlation between PAH concentrations and SERS signal was found to be linear in the range of 2.5 to 10 nM for anthracene and 10 and 25 nM for anthracene. The limit of detection values for pyrene and anthracene are 0.8 and 2.4 nM, respectively. Furthermore, the SERS sensor was also evaluated for the investigation of pyrene or anthracene specificity on different organic molecules and polyaromatic hydrocarbons.

Cyclodextrin-assisted surface-enhanced Raman spectroscopy: a critical review

“…Adapted with permission from ref. [24] signal and achieve the best LOD values. Therefore, the lack of reports dedicated to direct CD-SERS determination of aliphatic analytes can be explained by inappropriately low intensity of the analytical signal that starts to be comparable with the level of background signal formed by solvent, admixtures, and even capturing agent (i.e., CD-SH molecules).…”

“…As in SERS in general, spherical silver and gold nanoparticles (AgNPs and AuNPs, respectively) prepared using wet chemistry approaches are the mainly used substrates due to simplicity and reliability of production. Besides the use for label-free CD-SERS analysis, these substrates were also used for preparation of SERS nanotags [ 24 , 25 ]. Several reports were dedicated to the fabrication of conductive substrates suitable for electrospectral schemes of analysis, for example, electrochemically roughened metal electrodes [ 21 , 26 , 27 ], vacuum-deposited silver film [ 28 ], and silver-modified indium tin oxide electrodes [ 29 ].…”

“…Although the use of direct (label-free) SERS-based determination of the analytes is dominating, label-based CD-SERS systems have also been reported several times [ 24 , 25 , 37 , 56 ]. In this analysis format, CDs are used for the preparation of SERS nanotags that are a SERS substrate with fixed profile of the SERS signal [ 57 ].…”

Recent advances in linear and nonlinear Raman spectroscopy. Part XIII

“…Yan and co‐workers carried out a study of the thermal stability of ultrathin and high dielectric 1‐nm tetrahedral amorphous carbon films coated with Ag nanostructures for SERS detection . Zengin et al reported on the SERS detection of polyaromatic hydrocarbons on β‐cyclodextrin containing a polymer brush‐coated silicon substrate and β‐CD‐SH modified gold NPs for the detection of polyaromatic hydrocarbons pyrene and anthracene …”

“…[55] Zengin et al reported on the SERS detection of polyaromatic hydrocarbons on β-cyclodextrin containing a polymer brush-coated silicon substrate and β-CD-SH modified gold NPs for the detection of polyaromatic hydrocarbons pyrene and anthracene. [56] 9.4 | Tip-enhanced Raman spectroscopy…”