JaeHwan Lee

Sesamol is a natural antioxidant found in sesame oil from roasted sesame seeds. Activation energy and antioxidant capacity of sesamol were determined and compared with other free radical scavengers (FRSs) including tert‐butylated‐hydroxyquinone (TBHQ), butylated‐hydroxyanisol (BHA), or α‐tocopherol in a lard model system treated with different heating temperature. Each FRS was added in lard and heated at 90, 120, 150, and 180°C for 48, 24, 8, or 2 h, respectively and antioxidant capacity was evaluated by conjugated dienoic acid (CDA) value, conjugated diene hydroperoxides, p‐anisidine value (p‐AV), and a modified 2,2‐diphenyl‐1‐picrylhydrazyl (DPPH) method. Apparent activation energy of sesamol was determined as 12.98 kcal/mol in a lard model system. Antioxidant capacity of sesamol was as good as that of TBHQ and was higher than those of BHA and α‐tocopherol at 90, 120, and 150°C based on CDA, conjugated diene hydroperoxides, and p‐AV assays. The results of a modified DPPH method showed that each FRS showed different distribution of radical scavenging compounds from oxidized lipids (RSOLs) during oxidation. Sesamol may replace synthetic FRSs like TBHQ and BHA in processed foods treated with high temperature.Practical application: Processed foods are frequently treated with high temperature during oven‐drying, roasting, baking, and deep‐fat frying. This study showed that sesamol, one of natural antioxidants, had stronger antioxidant capacities than other synthetic FRSs at the temperature ranges from 90 to 180°C. The results of this study can be applied in food industries producing deep‐fat fried foods including snacks, chips, and French fries to extend the shelf‐life of final foods with high temperature treatment.

Analytical methods for food antioxidants including ascorbic acid, erythorbic acid, ascorbyl palmitate (AP), and ascorbyl stearate (AS), were validated using high performance liquid chromatography. Validation parameters such as linearity, limit of detection (LOD), limit of quantification (LOQ), and recovery were tested using lard and cider as food model systems. Linearity of ascorbic acid and erythorbic acid were both higher than (R2> 0.99), LOD of these compounds were 0.46 and 0.48 μg/mL, respectively and LOQ were 1.39 and 1.45 μg/mL, respectively. The recovery rates of these compounds were 86.35-94.78% and 84.76-95.02%, respectively. However, the concentration of AP and AS decreased in methanol stock solution. Four other solvents including ethanol, acetonitrile, mixture of methanol and acetonitrile, and mixture of ethanol and acetonitrile were tested to increase the stability of AP and AS under room temperature and refrigerated temperature. Ethanol provided better stability of AP and AS under both room and refrigerated temperature. This study can help to accurately analyze the content of ascorbic acid and its derivatives in processed foods.

Abstract:  Headspace volatiles of sesame oil (SO) from sesame seeds roasted at 9 different conditions were analyzed by a combination of solid phase microextraction (SPME)‐gas chromatography/mass spectrometry (GC/MS), electronic nose/metal oxide sensors (MOS), and electronic nose/MS. As roasting temperature increased from 213 to 247 °C, total headspace volatiles and pyrazines increased significantly ( P < 0.05). Pyrazines were major volatiles in SO and furans, thiazoles, aldehydes, and alcohols were also detected. Roasting temperature was more discrimination factor than roasting time for the volatiles in SO through the principal component analysis (PCA) of SPME‐GC/MS, electronic nose/MOS, and electronic nose/MS. Electronic nose/MS showed that ion fragment 52, 76, 53, and 51 amu played important roles in discriminating volatiles in SO from roasted sesame seeds, which are the major ion fragments from pyrazines, furans, and furfurals. SO roasted at 213, 230, and 247 °C were clearly differentiated from each other on the base of volatile distribution by SPME‐GC/MS, electronic nose/MOS, and electronic nose/MS analyses. Practical Application:  The results of this study are ready to apply for the discriminating samples using a combinational analysis of volatiles. Not only vegetable oils prepared from roasting process but also any food sample possessing volatiles could be targets for the SPME‐GC/MS and electronic nose assays. Contents and types of pyrazines in sesame seed oil could be used as markers to track down the degree of roasting and oxidation during oil preparation.

Profiles of triacylglycerols (TAG) and fatty acids were compared in soybean oil thermally oxidized at 180 °C for 60 min or methylene blue photosensitized for 10 h. Headspace oxygen in thermally oxidized and photosensitized soybean oil decreased significantly (p < 0.05) as oxidation time increased. Relative contents of linoleic and linolenic acids decreased and those of oleic acid increased during oxidation. In both thermal and photosensitized oxidation, TAG with lower than 44 equivalent carbon number including dilinoleoyllinolenoylglycerol (LLLn, 40), trilinolein (LLL, 42), oleoyllinoleoyllinolenoylglycerol (OLLn, 42), dilinoleoyloleoylglycerol (LLO, 44), and dilinoleoylpalmitoylglycerol (PLL, 44) significantly decreased, while those with dioleoyllinoleoylglycerol (OOL, 46) increased significantly in relative peak areas (p < 0.05). Photosensitized oxidation decreased TAG containing linoleic and linolenic acids significantly faster than thermal oxidation in soybean oil (p < 0.05), which may be due to the singlet oxygen reaction. Photosensitized soybean oils can be differentiated from thermally oxidized samples using the distributions of TAG by principal component analysis.

Abstract:  Photosensitized compounds from daidzein were studied in a riboflavin model system under visible light irradiation by high‐performance liquid chromatography (HPLC). As the period of light irradiation increased, concentration of daidzein decreased significantly ( P < 0.05) and new peaks of daidzein derivatives were observed and changed during photosensitization. Three new peaks from photosensitized daidzein were tentatively identified as 7‐, 3′, 4′‐trihydroxyisoflavone (or 3′‐hydroxydaidzein) and 2 dimmers of daidzein by a combination of HPLC‐mass spectrometry (MS) and retention times of standard compounds by HPLC. Addition of sodium azide and removal of headspace oxygen treatment affected the formation of newly formed peaks. The type I pathway of riboflavin photosensitization played more important roles than type II pathways on the formation of daidzein derivatives. Practical Application:  Isoflavones are important phytochemicals found in soy foods. Generally, many foods containing soy ingredients are displayed under visible light irradiation. Also, riboflavin can be found in many foods containing vegetables. The results of this study can be used to understand the stability and changes of isoflavone aglycones in soy and soy‐based foods under visible light irradiation.

ABSTRACT:  Antioxidant effectiveness of free radical scavengers (FRSs) of α‐tocopherol, sesamol, butylated hydroxytoluene (BHT), and tert ‐butylhydroquinone (TBHQ) were evaluated in thermally‐oxidized lard using methods of 2,2‐diphenyl‐1‐picrylhydrazyl (DPPH), conjugated dienoic acid (CDA), and p ‐anisidine value ( p ‐AV). Absorbance of DPPH with lard containing 2.5 μmol/g FRSs were low before oxidation while those with control lard was high due to the hydrogen atom donating ability of FRSs. During oxidation, DPPH absorbance with lard containing FRSs increased differently up to the certain point depending on the types of FRSs. DPPH absorbance of lard without FRSs started to decrease upon oxidation, which indicates that free radical scavenging compounds were generated from oxidized lipids. Results of CDA and p ‐AV showed that the highest antioxidant capacity was in the order of TBHQ = sesamol, BHT, and α‐tocopherol. Antioxidant effectiveness of FRS should consider the hydrogen atom donating rates of FRS, the reactivity and stability of FRS at treatment temperature, and characteristics of radicals from FRSs, which may be predicted by the results of DPPH method.

ABSTRACT:  The explosive puffing process may provide characteristic physicochemical properties in red ginseng. The effects of explosive puffing on the changes of volatiles in red ginseng were investigated using headspace‐solid phase microextraction (HS‐SPME)‐gas chromatograph (GC) with a mass selective detector (MS). Formation of porous structures and smaller pieces were clearly observed on the surface of puffed red ginseng by scanning electron microscopy. Total volatiles in puffed red ginseng increased by 87% compared to those in red ginseng. Hexanal, Δ‐selinene, and β‐panasinsene were major volatiles in red ginseng, whereas aristolene, β‐panasinsene, and calarene were main volatiles in puffed red ginseng. Puffing process decreased volatiles from lipid oxidation including aldehydes, ketones, and 2‐pentylfuran and increased terpenoids in red ginseng. Selective ion monitoring (SIM) mode for GC/MS results showed that 2‐furanmethanol and maltol were present at the concentrations of 0.20% and 0.24%, respectively, in red ginseng and 5.86% and 3.99%, respectively, in puffed red ginseng. The explosive puffing process increased 2‐furanmethanol and maltol in puffed red ginseng significantly ( P < 0.05) with the changes of microstructures.