Surface-enhanced Raman Spectrosocopy (SERS) is a highly sensitive form of Raman spectroscopy, with strong selectivity for Raman-active molecules adsorbed to plasmonic nanostructured surfaces. Extremely intense Raman signals derive from "hotspots", generally created by the aggregation of a silver nanospheres colloid. An alternative and cleaner approach is the use of anisotropic silver nanoparticles, with intrinsic "hotspots", allowing a more controlled enhancement effect as it is not dependent on disordered nanoparticle aggregation. Here, a simple SERS-based test is proposed for Portuguese white wines fingerprinting. The test is done by mixing microliter volumes of a silver nanostars colloid and the white wine sample. SERS spectra obtained directly from these mixtures, with no further treatments, are analyzed by principal component analysis (PCA), using a dedicated software. Depending on the duration of the incubation period, different discrimination can be obtained for the fingerprinting. A "mix-and-read" approach, with practically no incubation, allows for a simple discrimination between the three white wines tested. An overnight incubation allows for full discrimination between varieties of wine (Verde or Maduro), as well as between wines from different Maduro wine regions. This use of SERS in a straightforward, fast and inexpensive test for wine fingerprinting, avoiding the need for prior sample treatment, paves the way for the development of a simple and inexpensive authenticity assay for wines from specific appellations.
Keywords: authenticity test; fingerprinting; principal component analysis (PCA); silver nanostars; surface-enhanced Raman spectroscopy (SERS); white wine.