High-performance liquid chromatography combined with diode array and electrospray ionization mass spectrometric detection was used to study soluble and insoluble forms of phenolic compounds in strawberries, raspberries (red and yellow cultivated and red wild), arctic bramble, and cloudberries. Hydroxycinnamic acids were present as free forms in cloudberries and mainly as sugar esters in the other berries. Quercetin 3-glucuronide was the typical flavonol glycoside in all of the berries studied. The composition of the predominant anthocyanins can be used to distinguish the studied red Rubus species from each other since cyanidin was glycosylated typically with 3-sophorose (56%) in cultivated red raspberry, with 3-sophorose (30%) and 3-glucose (27%) in wild red raspberry, and with 3-rutinose (80%) in arctic bramble. Ellagic acid was present as free and glycosylated forms and as ellagitannins of varying degrees of polymerization. Comparable levels of ellagitannins were obtained by the analysis of soluble ellagitannins as gallic acid equivalents and by the analysis of ellagic acid equivalents released by acid hydrolysis of the extracts.

Berries contain a wide range of phenolic compounds in different conjugated forms, a fact that makes their simultaneous analysis a difficult task. In this work, soluble and insoluble phenolic compounds were identified and quantified in 18 species of berries by reversed phase high-performance liquid chromatography combined with diode array detection. The analytical results and literature data were used for the identification of the predominant conjugated hydroxycinnamic acids, flavonol glycosides, and anthocyanins in berries from six families, viz. Grossulariaceae, Ericaceae, Rosaceae, Empetraceae, Elaeagnaceae, and Caprifoliaceae. The study showed distinctive similarities among berry species of the same family in the distribution of conjugated forms of phenolic compounds but differences in chromatographic profiles of conjugates and compositions of aglycones especially in the case of anthocyanins. The chromatographic profiles of chokeberry and the related sweet rowanberry (Rosaceae) were exceptionally similar. These data are informative to studies on the authenticity of berry raw materials as well as to those on the evaluation of berries as sources of phenolic compounds.

The berries of Vaccinium myrtillus L. are characterized by 15 anthocyanins. To study the variation in the anthocyanins on a south-north axis of about 1000 km in Finland, the berries from 179 individual bilberry plants in 20 populations were analyzed using an optimized RP-HPLC-DAD method. The mean content of the total anthocyanins was 2878 mg/100 g dry weight. There was extensive variation in the anthocyanin contents within and between the populations, suggesting differences in berry raw material. A significantly lower content of the total anthocyanins was observed in the berries of the southern region compared to those in the central and northern regions. Differences in the proportions of anthocyanins were also observed. The delphinidin glycosides dominated in the northern berries whereas the cyanidin glycosides were most common in the southern ones. Exceptional bilberry individuals were found mainly from eastern Finland with very low amounts of anthocyanidin glucosides. This is the first systematic study to reveal the extremely high variation in the content and distribution of anthocyanins in wild bilberries.