Degradation of β-Carbolines Harman and Norharman in Edible Oils during Heating

The β-carbolines, mainly including harman and norharman, are a group of naturally occurring, plant-derived alkaloids, and are also considered as nonpolar heterocyclic aromatic amines. Sesame seed oils contain a high level of β-carbolines (harman and norharman). In China, sesame seed oil blends are one of the most popular types of vegetable oils blends, which can be used as cooking oils or frying oils. Thus, it is meaningful to investigate the degradation of β-carbolines (harman and norharman) in sesame seed oil blends as frying oils during heating. In this work, the loss of harman and norharman in different types of sesame seed oil blends have been investigated. The results showed that the degradation of harman and norharman were dependent both on the type of oil blends, heating temperature and time. Harman and norharman were more degraded during heating (150 °C, 180 °C) in oleic acid-rich oil blends compared to polyunsaturated acid-rich oil blends. Mechanistic investigation suggested that the reduction in harman and norharman in oil blends during heating was mainly due to the oxidative degradation reaction between β-carbolines and lipid oxidation products. Therefore, the contents of β-carbolines (harman and norharman) in sesame seed oil blends when used as frying oils and heated can be decreased with prolonged cooking time.

Hierarchical Zeolites as Catalysts for Biodiesel Production from Waste Frying Oils to Overcome Mass Transfer Limitations

Hierarchical crystals with short diffusion path, conventional microcrystals and nanocrystals of ZSM-5 zeolites were used for biodiesel production from waste frying oils and were assessed for their catalytic activity in regard to their pore structure and acidic properties. Produced zeolites were characterized using XRD, nitrogen adsorption–desorption, SEM, TEM, X-ray fluorescence, and FTIR. Pore size effect on molecular diffusion limitation was assessed by Thiele modulus calculations and turnover frequencies (TOF) were used to discuss the correlation between acidic character and catalytic performance of the zeolites. Owing to the enhanced accessibility and mass transfer of triglycerides and free fatty acids to the elemental active zeolitic structure, the catalytic performance of nanosponge and nanosheet hierarchical zeolites was the highest. A maximum yield of 48.29% was reached for the transesterification of waste frying oils (WFOs) using HZSM-5 nanosheets at 12:1 methanol to WFOs molar ratio, 180 °C, 10 wt % catalyst loading, and 4 h reaction time. Although HZSM-5 nanosponges achieved high conversions, these more hydrophilic zeolites did not function according to their entire acidic strength in comparison to HZSM-5 nanosheets. NSh-HZSM5 catalytic performance was still high after 4 consecutive cycles as a result of the zeolite regeneration.

Enhanced sophorolipid production and effective conversion of waste frying oil using dual lipophilic substrates

A highly efficient sophorolipid (SL) fermentation process using dual lipophilic substrates (DLS) was developed. Using DLS consisting of palm oil and oleic acid in the flask fermentation with SL-producing yeast Starmerella bombicola, the productivity and yield of SL improved 2.4- and 1.7-times, in comparison to when using palm olein alone. In the jar fermentation process with DLS, the SL productivity and yield of 127 g/L and 62.4% was achieved in 7 days, with the complete consumption of residual lipophilic substrates in the culture medium. This process was successfully applied to the effective conversion of waste frying oil to SL, maintaining a high SL productivity and yield of 142.8 g/L and 72% in 9 days. It is concluded that the newly developed fermentation process with DLS can be useful for industrial production of SL from renewable biological sources, especially waste frying oils.

Commentary: Iconoclastic Reflections on the ‘Safety’ of Polyunsaturated Fatty Acid-Rich Culinary Frying Oils: Some Cautions regarding the Laboratory Analysis and Dietary Ingestion of Lipid Oxidation Product Toxins

Continuous or frequent ingestion of fried foods containing cytotoxic/mutagenic/genotoxic lipid oxidation products (LOPs) may present significant human health risks; such toxins are generated in thermally stressed polyunsaturated fatty acid (PUFA)-rich culinary frying oils (CFOs) during standard frying practices. Since monounsaturated and saturated fatty acids (MUFAs and SFAs, respectively) are much less susceptible to peroxidation than PUFAs, in this study CFOs of differential unsaturated fatty acid contents were exposed to laboratory-simulated shallow-frying episodes (LSSFEs). Firstly, we present a case study exploring the time-dependent generation of aldehydic LOPs in CFO products undergoing LSSFEs, which was then used to evaluate the relative potential health risks posed by them, and also to provide suitable recommendations concerning their safety when used for frying purposes. Sunflower, rapeseed, extra-virgin olive and coconut oils underwent LSSFEs at 180 °C: Samples were collected at 0–90 min time-points (n = 6 replicates per oil). Aldehydes therein were determined by high-resolution 1H NMR analysis at 400 and 600 MHz operating frequencies. For one of the first times, CFO LOP analysis was also performed on a non-stationary 60 MHz benchtop NMR spectrometer. 1H NMR analysis confirmed the thermally promoted, time-dependent production of a wide range of aldehydic LOPs in CFOs. As expected, the highest levels of these toxins were produced in PUFA-rich sunflower oil, with lower concentrations formed in MUFA-rich canola and extra-virgin olive oils; in view of its very high SFA content, only very low levels of selected aldehyde classes were generated in coconut oil during LSSFEs. Secondly, 1H NMR results acquired are discussed with regard to the suitability and validity of alternative, albeit routinely employed, spectrophotometric methods for evaluating the peroxidation status of CFOs and lipid-containing foods. Thirdly, an updated mini-review of the toxicological properties of and intake limits for LOPs, and deleterious health effects posed by their ingestion, is provided. In conclusion, exposure of PUFA-rich CFOs to high-temperature frying practices generates very high concentrations of aldehydic LOP toxins from thermally promoted, O2-powered, recycling peroxidation processes; these toxins penetrate into and hence are ‘carried’ by fried foods available for human consumption. Such toxins have the capacity to contribute towards the development and progression of non-communicable chronic diseases (NCDs) if cumulatively ingested by humans.