Mediterranean Propolis from the Adriatic Sea Islands as a Source of Natural Antioxidants: Comprehensive Chemical Biodiversity Determined by GC-MS, FTIR-ATR, UHPLC-DAD-QqTOF-MS, DPPH and FRAP Assay

There is no systematic report about propolis chemical biodiversity from the Adriatic Sea islands affecting its antioxidant capacity. Therefore, the samples from the islands Krk, Rab, Pag, Biševo and Korčula were collected. Comprehensive methods were used to unlock their chemical biodiversity: headspace solid-phase microextraction (HS-SPME) and hydrodistillation (HD) followed by gas chromatography and mass spectrometry (GC-MS); Fourier transform mid-infrared spectroscopy (FT-MIR); ultra high performance liquid chromatography with diode array detector and quadrupole time-of-flight mass spectrometry (UHPLC-DAD-QqTOF-MS) and DPPH and FRAP assay. The volatiles variability enabled differentiation of the samples in 2 groups of Mediterranean propolis: non-poplar type (dominated by α-pinene) and polar type (characterized by cadinane type sesquiterpenes). Spectral variations (FT-MIR) associated with phenolics and other balsam-related components were significant among the samples. The UHPLC profiles allowed to track compounds related to the different botanical sources such as poplar (pinobanksin esters, esters and glycerides of phenolic acids, including prenyl derivatives), coniferous trees (labdane, abietane diterpenes) and Cistus spp. (clerodane and labdane diterpenes, methylated myricetin derivatives). The antioxidant potential determined by DPPH ranged 2.6–81.6 mg GAE/g and in FRAP assay 0.1–0.8 mmol Fe(2+)/g. The highest activity was observed for the samples of Populus spp. origin. The antioxidant potential and phenolic/flavonoid content was positively, significantly correlated.