Chromatographic framework for coffee ring effect-driven separation of small molecules in surface enhanced Raman spectroscopy analysis.

The applications of coffee ring effect (CRE) in analytical chemistry have been increasingly expanded from particles and macromolecules to small molecules, in particular coupled to surface-enhanced Raman spectroscopy (SERS). Despite the theory behind the formation of CRE itself from a single drop evaporation onto the dry surface is well established, the theoretical aspects of CRE-driven separation, especially the analyte-surface interactions involving small molecules, have not been conceived. Herein, we have developed a theoretical framework to describe the CRE-driven separation process of small molecules, using SERS analysis of dimethylarsinic acid (DMA), dimethylmonothioarsinic acid (DMMTA), and dimethyldithioarsinic acid (DMDTA) on gold nanofilm (AuNF) as an example.

Arsenic Speciation on Silver Nanofilms by Surface-Enhanced Raman Spectroscopy.

Surface-enhanced Raman spectroscopy (SERS), as a nondestructive and fast detection technique, is a promising alternative approach for arsenic detection, particularly for in situ applications. SERS-based speciation analysis according to the fingerprint SERS signals of different arsenicals has the potential to provide a superior technique in species preservation over the conventional chromatographic separation methods, albeit with some difficulties due to the similarity in SERS patterns. In this study, we explored a novel SERS method for arsenic speciation by using the separation potential of the coffee ring effect on negatively charged silver nanofilms (AgNFs).