Flavonol glycosides and antioxidant capacity of various blackberry and blueberry genotypes determined by high-performance liquid chromatography/mass spectrometry

Flavonol glycoside composition and content in blueberry and blackberry extracts were determined using a high-performance liquid chromatographic (HPLC) separation method coupled with photodiode array (PDA) and mass spectrometric (MS) detection. The hydrophilic antioxidant capacities of crude and fractionated flavonol extracts were also determined by the oxygen radical-absorbing capacity (ORAC(FL)) and photochemiluminescence (PCL) assays. Eight flavonols of quercetin and quercetin-sugar conjugates were identified in Kiowa blackberry, namely rutinoside, galactoside, methoxyhexoside, glucoside, pentoside, [6"-(3-hydroxy-3-methylglutaroyl)]-beta-galactoside, glucosylpentoside and oxalylpentoside. Thirteen flavonols were detected in Ozarkblue blueberry. Of these, myricetin 3-hexoside and 12 quercetin-sugar conjugates, namely rutinoside, galactoside, methoxyhexoside, glucoside, pentoside, glucosylpentoside, caffeoylglucoside, oxalylpentoside, rhamnoside, dimethoxyrhamnoside, acetylgalactoside and acetylglucoside, were identified. In Bluecrop blueberry, two additional quercetin-sugar conjugates were identified, namely glucuronide and caffeoylgalactoside. Quercetin glycosides accounted for 75% of total flavonols in the blueberry genotypes. Total flavonol contents ranged from 99 to 150 mg kg(-1) for blackberries and from 192 to 320 mg kg(-1) for blueberries. Quenching of peroxyl and superoxide anion radicals by the flavonol fractions ranged from 1.5 to 2.3 mmol Trolox equivalents (TE) kg(-1) and from 0.5 to 0.7 mmol TE kg(-1) respectively for blackberries and from 2.9 to 5.2 mmol TE kg(-1) and from 0.8 to 1.4 mmol TE kg(-1) respectively for blueberries. The HPLC method allowed for complete separation and identification of flavonols commonly found in blackberries, and blueberries. Our results showed that blueberry and blackberry genotypes varied significantly in flavonol content and antioxidant capacity. Even though total flavonol content did not correlate well with antioxidant capacity, their ability to scavenge peroxyl and superoxide anion radicals was apparent.