A core–shell column approach to a comprehensive high-performance liquid chromatography phenolic analysis of Vitis vinifera L. and interspecific hybrid grape juices, wines, and other matrices following either solid phase extraction or direct injection

Four high-throughput reverse-phase chromatographic protocols utilizing two different core–shell column chemistries have been developed to analyze the phenolic profiles of complex matrices, specifically targeting juices and wines produced from interspecific hybrid grape cultivars. Following pre-fractionation via solid-phase extraction or direct injection, individual protocols were designed to resolve, identify and quantify specific chemical classes of compounds including non-anthocyanin monomeric phenolics, condensed tannins following acid hydrolysis, and anthocyanins. Detection levels ranging from 1.2 ppb to 27.5 ppb, analyte %RSDs ranging from 0.04 to 0.38, and linear ranges of quantitation approaching five orders of magnitude were achieved using conventional HPLC instrumentation. Using C18 column chemistry, the non-anthocyanin monomeric protocol effectively separated a set of 16 relevant phenolic compounds comprised flavan-3-ols, hydroxycinnamic acids, and flavonols in under 14 min. The same column was used to develop a 15-min protocol for hydrolyzed condensed tannin analysis. Two anthocyanin protocols are presented, one utilizing the same C18 column, best suited for anthocyanidin and monoglucoside analysis, the other utilizing a pentafluorophenyl chemistry optimized to effectively separate complex mixtures of coexisting mono- and diglucoside anthocyanins. These protocols and column chemistries have been used initially to explore a wide variety of complex phenolic matrices, including red and white juices and wines produced from Vitis vinifera and interspecific hybrid grape cultivars, juices, teas, and plant extracts. Each protocol displayed robust matrix responses as written, yet are flexible enough to be easily modified to suit specifically tailored analytical requirements.

► Four rapid HPLC methods for phenolic analysis using core–shell columns are proposed.
► Three C18 methods separated multiple monomeric and hydrolyzed tannin fractions.
► A PFP-based method resolved all mono and diglucosides of the five grape anthocyanins.
► Superior resolution, precision, ppb IDL/IQLs and short analysis times were achieved.
► Applicable to Vitis vinifera and hybrid wines, juices, teas, plant extracts and others.