Surface-enhanced Raman spectroscopy for the characterization of Vaccinium myrtillus L. bilberries of the Baltic–Nordic regions

In this study, an investigation of the wild bilberries (Vaccinium myrtillus L.) of the different Baltic–Nordic regions using surface-enhanced Raman spectroscopy (SERS) combined with principal component analysis (PCA) is presented. The bilberries were collected in Lithuania, Latvia, Finland and Norway. The set of the SERS spectra of the berry extracts (pH ~ 4) were recorded on the silver nanoparticles based SERS substrates. The SERS spectra of the extracts were acquired using 532 nm laser as an excitation source. The morphology of the SERS substrates was evaluated by scanning electron microscopy (SEM) and the presence of the silver nanoparticles was confirmed by the energy-dispersive X-ray spectroscopy (EDX). The enhancement factor (EF) of the silver SERS substrates was found to be 105. It has been shown that a strong fluorescence background, associated with the phenolic compounds found in bilberries, can be subtracted due to the fluorescence-quenching properties of the silver nanoparticles. Therefore, an application of the SERS technique allowed to observe the characteristic peaks of the bilberries and the PCA tool enabled to evaluate the spectral variation across the entire SERS data set. The results presented in this paper show that the SERS technique coupled with PCA chemometric analysis might serve as a complementary method that allows to identify the country of origin of the bilberries based on the spectral differences.