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Edible mushrooms are valuable food resources due to their high dietary fiber and protein contents, low lipid levels, and diverse chemical composition. Brazil harbors considerable edible mushroom diversity, yet many native species remain insufficiently characterized. This study aimed to determine the nutritional, fatty acid, and volatile composition of five edible Atlantic Forest mushrooms undergoing domestication: Irpex rosettiformis, Oudemansiella platensis, Pleurotus albidus, Pleurotus djamor, and Lentinula raphanica. Samples cultivated by IFungiLab at the Federal Institute of São Paulo were harvested, frozen, lyophilized, and ground. Proximate composition was determined according to AOAC methods, soluble and insoluble dietary fiber according to Asp et al., and lipids were extracted using the Bligh and Dyer method. Fatty acids were analyzed by gas chromatography with flame ionization detection (GC-FID), while volatile compounds were characterized by headspace gas chromatography–mass spectrometry (HS-GC-MS). Atherogenicity, thrombogenicity, hypocholesterolemic/hypercholesterolemic, and lipid peroxidation indices were calculated. Principal component analysis (PCA) and hierarchical clustering were applied to investigate differences in volatile profiles. All species exhibited high moisture contents (84.64–91.91%), indicating the importance of appropriate preservation strategies. On a dry-weight basis, protein contents ranged from 16.56% in L. raphanica to 26.77% in P. djamor, while dietary fiber represented 42.52–52.21% and ash contents ranged from 5.27% to 7.81%. These findings highlight their potential as sources of protein, fiber, and minerals. Lipid contents ranged from 4.06% to 12.24%. Unsaturated fatty acids predominated in four species, with linoleic acid as the major polyunsaturated fatty acid, reaching 34.78 mg/100 mg in L. raphanica. In contrast, O. platensis presented a distinctive lipid profile, with saturated fatty acids accounting for 70.0% of total fatty acids, predominantly lauric acid (55.4%). This composition was reflected in its higher atherogenicity (2.6) and thrombogenicity (0.78) indices compared with the other species (≤0.2 and 0.37–0.44, respectively), indicating a less favorable lipid profile. The hypocholesterolemic/hypercholesterolemic ratio suggested a potentially beneficial lipid profile for the other four species, whereas lipid peroxidation indices indicated greater oxidative susceptibility in P. albidus and L. raphanica. Volatile analysis revealed species-specific chemical fingerprints, with the first two principal components explaining 73.2% of total variance. O. platensis exhibited the greatest volatile diversity, with 39 putatively identified compounds, including prominent lauric acid esters and derivatives of medium-chain fatty acids. These findings are consistent with the coconut-like aroma perceived sensorially in this species and suggest a relationship between its distinctive lipid composition and volatile profile. The Pleurotus species showed greater similarity, sharing major volatile compounds such as 3-octanone, 1-octen-3-ol, and hexanal. Overall, these findings demonstrate the nutritional potential and chemical diversity of native Atlantic Forest mushrooms. Their species-specific lipid and volatile profiles provide valuable information to support domestication, processing, and storage strategies that preserve nutritional quality and desirable sensory characteristics.
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