Quantification and Bitter Taste Contribution of Lipids and Their Oxidation Products in Pea-Protein Isolates (Pisum sativum L.).

An ultra-high-performance liquid chromatography-differential ion mobility (DMS)-tandem mass spectrometry method was developed to quantify 14 bitter-tasting lipids in 17 commercial pea-protein isolates (Pisum sativum L.). The DMS technology enabled the simultaneous quantification of four hydroxyoctadecadienoic acid isomers, namely, (10E,12Z)-9-hydroxyoctadeca-10,12-dienoic acid (5), (10E,12E)-9-hydroxyoctadeca-10,12-dienoic acid (6), (9Z,11E)-13-hydroxyoctadeca-9,11-dienoic acid (7), and (9E,11E)-13-hydroxyoctadeca-9,11-dienoic acid (8). Based on quantitative data and human bitter taste recognition thresholds, dose-over-threshold factors were determined to evaluate the individual lipids' bitter impact and compound classes. The free fatty acids α-linolenic acid (10) and linoleic acid (13), as well as the trihydroxyoctadecenoic acids, especially 9,10,11-trihydroxyoctadec-12-enoic (3), and 11,12,13-trihydroxyoctadec-9-enoic acids (4), were shown to be key inducers to bitterness in the isolates. Additionally, the impact of 1-linoleoyl glycerol (9) on the bitter taste could be shown for 14 of the 17 tested pea-protein isolates.

Molecularization of Bitter Off-Taste Compounds in Pea-Protein Isolates (Pisum sativum L.).

Activity-guided fractionations, combined with taste dilution analyses (TDA), were performed to locate the key compounds contributing to the bitter off-taste of pea-protein isolates (Pisum sativum L.). Purification of the compounds perceived with the highest sensory impact, followed by 1D/2D-NMR, (LC-)MS/MS, LC-TOF-MS, and MSE experiments, led to the identification of 14 lipids and lipid oxidation products, namely, 9,10,13-trihydroxyoctadec-12-enoic acid, 9,12,13-trihydroxyoctadec-10-enoic acid, 9,10,11-trihydroxyoctadec-12-enoic, 11,12,13-trihydroxyoctadec-9-enoic acid, (10E,12E)-9-hydroxyoctadeca-10,12-dienoic acid, (9Z,11E)-13-hydroxyoctadeca-9,11-dienoic acid, (9E,11E)-13-hydroxyoctadeca-9,11-dienoic acid, 1-linoleoyl glycerol, α-linolenic acid, 2-hydroxypalmitic acid, 2-hydroxyoleic acid, linoleic acid, (9Z,11E)-13-oxooctadeca-9,11-dienoic acid, and octacosa-6,9,19,22-tetraen. Herein, we present the isolation, structure determination, and sensory activity of these molecules. Depending on their structure, the isolated compounds showed human bitter recognition thresholds between 0.06 and 0.99 mmol/L in water.

Characterization of Bitter-Tasting Oxylipins in Poppy Seeds (Papaver somniferum L.).

Activity-guided fractionation of poppy seed (Papaver somniferum L.) extracts and analysis of fatty acid oxidation model experiments, followed by liquid chromatography time-of-flight mass spectrometry, tandem mass spectrometry, and one-/two-dimensional nuclear magnetic resonance experiments, revealed the chemical structures of five bitter-tasting fatty acids (1-5), three monoglycerides (6-8), six C18-lipidoxidation products (9-14), and four lipid oxidation degradation products (15 and 17-19) as well as two previously unreported monoglyceride oxidation degradation products, namely, 9-(2',3'-dihydroxypropyloxy)-9-oxononaic acid (1-azeloyl-rac-glycerol, 16) and 1-(2',3'-dihydroxypropyl)-8-(5″-oxo-2″,5″-dihydrofruan-2″-yl)-octonoate (1-ODFO-rac-glycerol, 20). Sensory studies exhibited low bitter taste threshold concentrations between 0.08 and 0.29 mmol/L, particularly for the higher oxidated C18-fatty acids trihydroxyoctadecenoic acid (THOE, 12), 12,13-dihydroxy-9-oxo-10-octadecenoic acid (12,13-diOH-9-oxo, 13), and 9,10-dihydroxy-13-oxo-11-octadecenoic acid (9,10-diOH-13-oxo, 14) as well as for the lipidoxidation degradation products 4-hydroxy-2-noneic acid (4-HNA, 17), 4-hydroxy-2-docecendienoic acid (HDdiA, 18), and 8-(5'-oxo-2',5'-dihydrofuran-2'-yl)-octanoic acid (ODFO, 20).