Elucidation of decomposition pathways of linoleic acid hydroperoxide isomers by GC-MS and LC-MS/MS.

Food lipid oxidation provides various volatile compounds involved in food flavor via the decomposition of lipid hydroperoxide (LOOH). This study predicted the pathways which can coherently explain LOOH decomposition focusing on hydroperoxy octadecadienoic acid (HpODE) isomers (9-EZ-HpODE, 9-EE-HpODE, 10-HpODE, 12-HpODE, 13-ZE-HpODE, and 13-EE-HpODE) which are the major LOOH contained in edible oils. Each standard was first prepared and thermally decomposed. Generated volatile and non-volatile compounds were analyzed by GC-MS and LC-MS/MS. The results showed that all HpODE decomposition was based on the factors such as favorable scission, radical delocalization, and cyclization. Interestingly, the formation of 8-HpODE and 14-HpODE were demonstrated during HpODE decomposition. The insights obtained in this study would explain the generation pathways of flavor involved in food quality.

Carboxylic acids derived from triacylglycerols that contribute to the increase in acid value during the thermal oxidation of oils.

Acid value (AV), is a widely used indicator of oil degradation that, by definition, measures the free fatty acids formed via the hydrolysis of triacyclglycerols. However, based on observations made in previous studies, we hypothesized that the oxidation of triacylglycerols leads to the formation of carboxylic acids with a glycerol backbone which are also calculated as AV. In this study, we aimed to identify such carboxylic acids and prove the above hypothesis. Heating a canola oil at 180 °C for 6 h without the addition of water resulted in an increase in AV from 0.054 to 0.241. However, the contribution of free fatty acids to this increase in AV was minimal; free fatty acid-derived AV before and after heating was 0.020 and 0.023, respectively. Then, via mass spectrometric analyses, we identified two 8-carboxy-octanoyl (azelaoyl) -triacylglycerols (i.e., dioleoyl-azelaoyl-glycerol and oleoyl-linoleoyl-azelaoyl-glycerol) in the heated oil. Azelaoyl-triacylglycerols-derived AV before and after heating the oil was 0.008 and 0.109, respectively, demonstrating that azelaoyl-triacylglycerols contribute to AV. Such an increase in AV by azelaoyl-triacylglycerols was also observed in an oil used to deep-fry potatoes (i.e., an oil with a relatively high water content). These results suggest that AV is also an indicator of the thermal oxidation of triacylglycerols.

Isolation and structural elucidation of unique γ-oryzanol species in rice bran oil.

Even though γ-oryzanol (OZ) such as 24-methylenecycloartanyl ferulate (24MCAFA) is abundant in purified rice bran oil, we realized that the oil contained the prospect of two additional novels of OZ species. To identify this, we isolated and analyzed their chemical structures by using HPLC-UV-MS, NMR, and IR. We revealed for the first time that the oil had also contained cyclobranyl ferulate (CBFA) and cyclosadyl ferulate (CSFA) which are likely to be exist due to the isomerism of 24MCAFA under acid condition. OZ profile including CBFA and CSFA was roughly similar between commercial rice bran oils and processed foods containing the oils, suggesting that people might have often consumed CBFA and CSFA from rice bran oils and/or processed foods. Since different OZ species are known to have different functionality, this study opens the chance to explore more the contribution of CBFA and CSFA for human health and wellness.

Revealing the thermal oxidation stability and its mechanism of rice bran oil.

Although the stability of rice bran oil (RBO) has been showed on several studies, the factors which make it capable on maintaining its stability under thermal oxidation has not been sure yet. We hypothesized that its fatty acid composition [high composition of oleic acid (OA), lower composition of linoleic acid (LA) and α-linolenic acid (LnA)] and/or its antioxidant agents [γ-oryzanol (OZ)] and vitamin E [tocopherol (Toc), tocotrienol (T3)] might be the biggest factor. To prove the hypothesis, we thermally oxidized RBO under 40 °C for 17 days to mimic the harsh daily storage condition, and compared it with soybean oil (SO) and rapeseed oil (RPO) then monitoring their primary oxidation products [triacylglycerol hydroperoxide (TGOOH)] from easily oxidized fatty acid contained in triacylglycerol (TG) and the amount loss of antioxidant agents. As a result, RBO showed the lowest TGOOH/TG ratio, followed by RPO and SO. The superior stability RPO compared SO might occur due to because of the influence of the fatty acid profile (higher OA and lower LA). For RBO's case, besides its fatty acid profile, the existence of OZ and the synergistic effect of OZ and vitamin E might have a greater contribution in maintaining its stability under thermal oxidation.

Author Correction: Definitive evidence of the presence of 24-methylenecycloartanyl ferulate and 24-methylenecycloartanyl caffeate in barley.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Absorption and Metabolism of γ-Oryzanol, a Characteristic Functional Ingredient in Rice Bran.

γ-Oryzanol (OZ), a functional substance found in rice bran, consists of multiple molecular species. In both in vitro and in vivo studies, the researches exploring the various function of rice bran OZ have been conducted for a long time, and it has become clear that OZ has a lot of pharmaceutical activities. It is assumed that each type of OZ molecular species may have different effects. In contrast, the profile behaviour of OZ inside the body has not been fully understood. This article reviews the previous studies about the digestion, absorption, metabolism, and effects of rice bran OZ and also introduces the new method to evaluate the OZ metabolic fate by using high-performance liquid chromatography (HPLC) combined with tandem mass-spectrometry (MS/MS) which has higher selectivity and sensitivity.

Definitive evidence of the presence of 24-methylenecycloartanyl ferulate and 24-methylenecycloartanyl caffeate in barley.

γ-Oryzanol (OZ), which has a lot of beneficial effects, is a mixture of ferulic acid esters of triterpene alcohols (i.e., triterpene alcohol type of OZ (TTA-OZ)) and ferulic acid esters of plant sterols (i.e., plant sterol type of OZ (PS-OZ)). Although it has been reported that OZ is found in several kinds of cereal typified by rice, TTA-OZ (e.g., 24-methylenecycloartanyl ferulate (24MCA-FA)) has been believed to be characteristic to rice and has not been found in other cereals. In this study, we isolated a compound considered as a TTA-OZ (i.e., 24MCA-FA) from barley and determined the chemical structure using by HPLC-UV-MS, high-resolution MS, and NMR. Based on these results, we proved for the first time that barley certainly contains 24MCA-FA (i.e., TTA-OZ). During the isolation and purification of 24MCA-FA from barley, we found the prospect that a compound with similar properties to OZ (compound-X) might exist. To confirm this finding, the compound-X was also isolated, determined the chemical structure, and identified as a caffeic acid ester of 24-methylenecycloartanol (24MCA-CA), which has rarely been reported before. We also quantified these compounds in various species of barley cultivars and found for the first time the existence of 24MCA-FA and 24MCA-CA in various barley. Through these findings, it opens the possibility to use barley as a new source of 24MCA-FA and 24MCA-CA.

The employment of FTIR spectroscopy in combination with chemometrics for analysis of rat meat in meatball formulation.

For Indonesian community, meatball is one of the favorite meat food products. In order to gain economical benefits, the substitution of beef meat with rat meat can happen due to the different prices between rat meat and beef. In this present research, the feasibility of FTIR spectroscopy in combination with multivariate calibration of partial least square (PLS) was used for the quantitative analysis of rat meat in the binary mixture of beef in meatball formulation. Meanwhile, the chemometrics of principal component analysis (PCA) was used for the classification between rat meat and beef meatballs. Some frequency regions in mid infrared region were optimized, and finally, the frequency region of 750-1000 cm(-1) was selected during PLS and PCA modeling.For quantitative analysis, the relationship between actual values (x-axis) and FTIR predicted values (y-axis) of rat meat is described by the equation of y= 0.9417x+ 2.8410 with coefficient of determination (R2) of 0.993, and root mean square error of calibration (RMSEC) of 1.79%. Furthermore, PCA was successfully used for the classification of rat meat meatball and beef meatball.