Reduced Self-Aggregation and Improved Stability of Silica-Coated Fe3O4/Ag SERS-Active Nanotags Functionalized With 2-Mercaptoethanesulfonate

Maria Żygieło; Piotr Piotrowski; Marcin Witkowski; Grzegorz Cichowicz; Jacek Szczytko; Agata Królikowska

doi:10.3389/fchem.2021.697595

Reduced Self-Aggregation and Improved Stability of Silica-Coated Fe₃O₄/Ag SERS-Active Nanotags Functionalized With 2-Mercaptoethanesulfonate

Front Chem. 2021 Jun 16:9:697595. doi: 10.3389/fchem.2021.697595. eCollection 2021.

Authors

Maria Żygieło¹, Piotr Piotrowski¹, Marcin Witkowski¹, Grzegorz Cichowicz¹, Jacek Szczytko², Agata Królikowska¹

Affiliations

¹ Faculty of Chemistry, University of Warsaw, Warsaw, Poland.
² Institute of Experimental Physics, Faculty of Physics, University of Warsaw, Warsaw, Poland.

Abstract

Nanocomposites combining magnetic and plasmonic properties are very attractive within the field of surface-enhanced Raman scattering (SERS) spectroscopy. Applications presented so far take advantage of not only the cooperation of both components but also synergy (enhanced properties), leading to multi-approach analysis. While many methods were proposed to synthesize such plasmonic-magnetic nanoparticles, the issue of their collective magnetic behavior, inducing irreversible self-aggregation, has not been addressed yet. Thus, here we present a simple and fast method to overcome this problem, employing 2-mercaptoethanesulfonate (MES) ions as both a SERS tag and primer molecules in the silica-coating process of the previously fabricated Fe₃O₄/Ag nanocomposite. The use of MES favored the formation of silica-coated nanomaterial comprised of well-dispersed small clusters of Fe₃O₄/Ag nanoparticles. Furthermore, adsorbed MES molecules provided a reliable SERS response, which was successfully detected after magnetic assembly of the Fe₃O₄/Ag@MES@SiO₂ on the surface of the banknote. Improved chemical stability after coating with a silica layer was also found when the nanocomposite was exposed to suspension of yeast cells. This work reports on the application of 2-mercaptoethanesulfonate not only providing a photostable SERS signal due to a non-aromatic Raman reporter but also acting as a silica-coating primer and a factor responsible for a substantial reduction of the self-aggregation of the plasmonic-magnetic nanocomposite. Additionally, here obtained Fe₃O₄/Ag@MES@SiO₂ SERS nanotags showed the potential as security labels for the authentication purposes, retaining its original SERS performance after deposition on the banknote.

Keywords: SERS nanotags; controlled clustering; iron oxide nanoparticles; magnetic self-aggregation; plasmonic-magnetic nanocomposite; silica coating; silver nanoparticles; surface-enhanced Raman scattering.