Metabolomic Characterization and Evaluation of the Antioxidant Potential of Stingless Bee Honeys (Borá, Jataí, Mandaçaia, and Manduri)

Abstract

Stingless bee honeys have attracted increasing scientific interest due to their distinctive chemical composition and biological potential, particularly because of the presence of bioactive metabolites associated with antioxidant and functional properties. However, despite the growing number of chromatographic studies involving these products, several stingless bee species from southern Brazil still lack detailed information regarding their metabolomic composition and antioxidant potential. Therefore, this study aimed to identify and quantify sugars and secondary metabolites through chromatographic analyses, as well as to evaluate the antioxidant potential of honeys produced by Borá (Tetragona clavipes), Jataí (Tetragonisca angustula), Mandaçaia (Melipona quadrifasciata), and Manduri (Melipona marginata). Sugar composition was determined by HPLC, metabolomic profiling by UHPLC-MS/MS, and antioxidant activity by the ABTS assay. Fructose, glucose, and sucrose were identified in all honey samples, with the highest fructose (38.745 ± 0.028 mg mL–1) and glucose (26.238 ± 0.171 mg mL–1) concentrations observed in Mandaçaia honey, whereas Borá honey presented the highest sucrose concentration (9.237 ± 0.021 mg mL–1). Metabolomic analysis enabled the detection of 24 compounds, including phenolic acids, flavonoids, aldehydes, and methylxanthines, such as caffeic acid, gallic acid, kaempferol, quercetin, rutin, caffeine, and theobromine. Among the 24 annotated metabolites, the highest concentrations were observed for p-coumaric acid (0.2343 ± 0.0047 μg g–1) and sinapic acid (0.2315 ± 0.0011 μg g–1) in Jataí honey, vanillic acid (0.2254 ± 0.0057 μg g–1) and salicylic acid (0.2174 ± 0.0110 μg g–1) in Mandaçaia honey, rutin (0.2077 ± 0.0106 μg g–1) in Borá honey, and theobromine (0.2012 ± 0.0057 μg g–1), also in Mandaçaia honey. The ABTS assay demonstrated promising antioxidant activity, with lower IC50 values observed for Manduri (166.68 ± 0.6 mg 100 g–1) and Mandaçaia (168.79 ± 1.2 mg 100 g–1) honeys. Overall, these findings highlight the chemical complexity, antioxidant potential, and functional relevance of stingless bee honeys, contributing to the valorization and characterization of products derived from Brazilian sociobiodiversity.