This paper investigates the influence of cultivar (Annurca, Golden Delicious, Red Chief, and Stayman Neepling), rural practice (integrated and organic), and growing region (different Italian regions) on polyphenol composition and antiradical activity of the pulp and skin of apples, as presented to the consumer at the market. Antiradical activity of fruit was strongly related with the total polyphenolic content, determined both by the spectrophotometric Folin-Ciocalteu method ( R (2) = 0.90; P < 0.01) and by HPLC ( R (2) = 0.85; P < 0.01). Considering the edible portion of the fruit, polyphenolics contribute toward explaining approximately 90% of the overall antiradical activity, thus highlighting their important role in human health protection. Therefore, the data indirectly indicated that ascorbic acid and other antiradical molecules differing from polyphenols play a much less important role in explaining the health-protecting properties of apples. Cultivar effect was by far the most important, and Annurca and Golden Delicious were respectively the best and the worst apples from the point of view of the health-protecting attributes.

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High-performance liquid chromatography coupled with ion spray mass spectrometry in the tandem mode with both negative and positive ionization was used for investigating a variety of polyphenolic compounds in four genotypes of Fragaria vesca berries. About 60 phenolic compounds belonging to the compound classes of phenolic acids, ellagitannins, ellagic acid derivatives, flavonols, monomeric and oligomeric flavanols, dihydrochalcones and anthocyanins were reported, providing for the first time a quite complete picture of polyphenolic composition of F. vesca berries. Some of the polyphenols herein investigated, such as a tris-galloyl-hexahydroxydiphenoyl-hexose, two castalagin/vescalagin-like isomers and peonidin-malonylglucoside, were described for the first time. Principal component analysis applied on original HPLC-MS/MS data, acquired in multiple reaction monitoring mode, successfully discriminated the four investigated cultivars on the basis of their polyphenolic composition, highlighting the fundamental role of mass spectrometry for food characterization.

Ultra-high-performance liquid chromatography coupled with high-resolution quadrupole-time of flight mass spectrometry with both negative and positive ionization was used for comprehensively investigating the phenolic and polyphenolic compounds in berries from three spontaneous or cultivated Vaccinium species (i.e., Vaccinium myrtillus, Vaccinium uliginosum subsp. gaultherioides, and Vaccinium corymbosum). More than 200 analytes, among phenolic and polyphenolic compounds belonging to the classes of anthocyanins, monomeric and oligomeric flavonols, flavanols, dihydrochalcones, phenolic acids, together with other polyphenolic compounds of mixed structural characteristics, were identified. Some of the polyphenols herein investigated, such as anthocyanidin glucuronides and malvidin-feruloyl-hexosides in V. myrtillus, or anthocyanindin aldopentosides and coumaroyl-hexosides in V. uliginosum subsp. gaultherioides and a large number of proanthocyanidins with high molecular weight in all species, were described for the first time in these berries. Principal component analysis applied on original LC-TOF data, acquired in survey scan mode, successfully discriminated the three Vaccinium berry species investigated, on the basis of their polyphenolic composition, underlying one more time the fundamental role of mass spectrometry for food characterization.

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