Suspect screening boosts bioaccessibility assays of phenolic compounds in food commodities: A proof of concept

The knowledge of the actual oral bioaccessibility of phenolic compounds through food intake in the human gut is a key factor for assessing their potential health benefits. To this end, there is a quest to develop advanced analytical methodologies that are able to expand the chemical space offered by targeted methods. In fact, suspect screening workflows using high-resolution mass spectrometry might shed light on the vast diversity of phenolic compounds in food commodities that might be released in the gut fluids. Herein, targeted and suspect screening assays of phenolic substances in gastric extracts were performed to investigate the relative bioaccessibility of these compounds in the crushed solid fruit as compared to the fruit juice intake. The analytical method was validated for 30 phenolic compounds using a targeted workflow in both positive and negative modes, with dynamic linear ranges spanning from 1.0 to 4000 ng/mL and repeatability values ranging from 0.3 to 13.6% under matrix-matched calibration. Validation was performed in a pH-adjusted gastric extract, with the negative mode offering the most sensitive detection for subsequent real sample analysis. Thereafter, suspect screening workflows of the phenolic compounds and their plant metabolites were conducted in juiced and crushed fruits after the gastric extraction process. The workflow resulted in the confirmation of 8 features with pure standards (level 1), and 24 additional tentative annotations in levels 2–4. The results demonstrated that 59.4% of phenolic compounds annotated in the gastric extracts have higher relative acid bioaccessibility from the solid fruit, 34.4% higher from the juiced samples, and 6.2% equally distributed. Additionally, the targeted and suspect results indicated that there was a significant correlation between the number of phenolic hydroxyls on the relative bioaccessibility of the compounds. However, the relevance of the type of phenolic compounds, e.g. , being flavonoid or non-flavonoid, was not statistically significant. This study aims to provide a holistic perspective on how the form of food intake (juice versus whole fruit) can be strategically selected according to specific phenolic compounds to achieve bespoke nutritional and food industry benefits. • First exhaustive comparison of relative oral bioaccessibility for crushed against juiced fruits. • Suspect screening and target approaches for the bioaccessible content of (poly)phenolic compounds. • A significant positive correlation is encountered between the number of phenolic hydroxides and bioaccessibility. • Annotation of (poly)phenolic compounds never before reported in oral bioaccessibility tests of fruits.