A classification and identification model of extra virgin olive oil adulterated with other edible oils based on pigment compositions and support vector machine.

Adulteration identification of extra virgin olive oil (EVOO) is a vital issue in the olive oil industry. In this study, chromatographic fingerprint data of pigments combined with machine learning methodologies were successfully identified and classified EVOO, refined-pomace olive oil (R-POO), rapeseed oil (RO), soybean oil (SO), peanut oil (PO), sunflower oil (SFO), flaxseed oil (FO), corn oil (CO), extra virgin olive oil adulterated with rapeseed oil (EVOO-RO) and extra virgin olive oil adulterated with corn oil (EVOO-CO). Support vector machine (SVM) classification of EVOO, other edible oils, and EVOO adulteration identification achieved 100% accuracy for the training set sample and 94.44% accuracy for the test set sample. As a result, this SVM model could identify effectively the adulteration EVOO with the limit of 1% RO and 1% CO. Therefore, the excellent classification and predictive power of this model indicated pigments could be used as potential markers for identifying EVOO adulteration.

Chemical conversions of free phytosterols during the bleaching of corn oil.

Phytosterols have health benefits; however, they are partially removed during the bleaching of corn oil. We evaluated the chemical conversion of free phytosterols (FPs) during bleaching. FP degradation accelerated with increased time and temperature, following a first-order kinetic model. In the n-heptane system, air and activated clay promoted the chemical conversion of the FPs. Sterenes formation was analysed under different conditions using a zero-order kinetic model. The apparent activation energies revealed sterene formation decreasing in the following order: campesta-3,5-diene ≈ stigmasta-3,5,22-triene > stigmasta-3,5-diene. Isomers of the above were not detected, indicating that these sterenes were the only primary products of FPs. The desorption test indicated that the FP loss from corn oil was not only due to FPs being adsorbed the activated clay, but also FPs adsorbed at acidic activated sites being degraded. This study presents a vital scientific foundation for retaining FPs to develop healthier and more nutritious oils.

Impairment of apoptosis pathway via Apaf1 downregulation during chlorpyrifos and/or cypermethrin induced lung damage.

Chlorpyrifos is an organophosphate and the cypermethrin is type 2 pyrethroid insecticide that are used for indoor and outdoor pest control. The present study aimed to investigate differential transcriptional profiling to identify the candidate gene associated with lung injury following exposure to chlorpyrifos and/or cypermethrin in a mouse model system. Swiss male albino mice (n = 24) were divided into three treatment groups (n = 6 each) that were given chlorpyrifos (2.76 mg kg-1 body weight), cypermethrin (2 mg kg-1 body weight) and the combination of both pesticides orally dissolved in corn oil and one control group (n = 6) that received corn oil for 90 days. The pulmonary expression of the Apaf1 was observed using RT2 Profiler PCR Array. The results showed that chronic exposure to chlorpyrifos, cypermethrin and their combination downregulated (67, 63 and 66 genes) and upregulated (4, 2 and 2 genes), respectively. The pulmonary expression of Apaf1 that plays important role in apoptosis was found to be downregulated. The immunohistochemistry depicted reduced expression of Apaf1 in both airway epithelium and alveolar septa following exposure to chlorpyrifos and/or cypermethrin. In conclusion, results demonstrated that exposure to chlorpyrifos, cypermethrin and their combination cause lung damage by the dysregulation of Apaf1 gene expression.

An ultrasensitive CH3NH3PbBr3 quantum dots@SiO2-based electrochemiluminescence sensing platform using an organic electrolyte for aflatoxin B1 detection in corn oil.

Mycotoxins contamination, especially aflatoxin B1 (AFB1) in edible oils, is a health hazard. Therefore, AFB1 trace analysis methods are urgently needed. Electrochemiluminescence (ECL) is a popular sensing method because of its low background interference and high sensitivity. However, existing ECL assays for AFB1 detection are based on aqueous rather than oil systems. Herein, we report a CH3NH3PbBr3 quantum dots (MAPB QDs)@SiO2-based ECL sensor for AFB1 quantification in corn oil using an organic electrolyte. The luminophore loading and stability of the MAPB QDs@SiO2 particles were significantly improved compared to those of bulky MAPB materials, resulting in an enhanced ECL response. Further, exploiting molecular imprinting technology, an ECL sensor for AFB1 detection with an ultra-low detection limit of 8.5 fg/mL was prepared. The reliability of the sensor was confirmed by comparable recoveries of corn oil samples with those obtained by high-performance liquid chromatography, indicating its potential for food safety evaluation.

Functional and emulsification characteristics of phospholipids and derived o/w emulsions from peony seed meal.

Peony seed phospholipids (PPLs), a kind of multifunctional plant-like phospholipids were extracted from peony seed meal. We investigated the functional properties of PPLs and compared their emulsification performance in corn oil-peony seed oil o/w emulsion systems with that of soy lecithin (DPLs). The PPLs were characterized with the higher content of phosphatidylcholine (PC) (416 ± 28 mg/g) and lyso-phosphatidylcholine (LPC) (43 ± 14 mg/g) fractions, and lower content of phosphatidylethanolamine (PE) (71 ± 13 mg/g). The polyunsaturated fatty acids showed higher content (83.25%), with the highest content of linoleic acid (46.05%) in PPLs. PPLs-emulsions showed smaller average particle size and higher loaded peony seed oil content at pH 5, temperature 50 °C, and about 60% corn oil content. PPLs-emulsions imparted better hydroxyl radical scavenging efficiency and reducing power than DPLs. Our results suggest that PPLs can be used as emulsifiers with improved antioxidant properties.

Unlocking the potential of minimally processed corn germ oil and high oleic soybean oil to prepare oleogels for bakery application.

In this study, the influence of sunflower wax (SFX) concentration (1, 3, 5, 7, and 9 wt%) on the properties of oleogels prepared using expeller-pressed corn germ oil (EPC) or high oleic soybean oil (EPS) was comprehensively investigated. Overall, oleogels can be prepared from both EP oils at an SFX level ≥3 wt%. The strength of oleogels depends on SFX concentration. EPS oleogels had better rheological properties and a higher amount of platelet-like crystals than EPC oleogels. The characteristics of cookies prepared with both oleogels were evaluated and compared to cookies prepared with commercial shortening. The lipid distribution in the cookies as visualized by CLSM suggested that EPS oleogels with a 5 or 7 wt% SFX had a greater possibility of replacing commercial shortening as they exhibited even lipid distribution which enabled good air-incorporation and air retention abilities. This research provides a foundation for developing healthy bakery products by using minimally processed oil based oleogels.

Development and establishment of a QuEChERS-based extraction method for determining tembotrione and its metabolite AE 1417268 in corn, corn oil and certain animal-origin foods by HPLC-MS/MS.

In this study, we established a rapid and sensitive HPLC-MS/MS method for quantitative determination of tembotrione and its metabolite AE 1417268 (M5) in corn, corn oil, beef, pork, chicken, and eggs. Both analytes eluted from a C18 column within 6 min. The electrospray ionisation-positive mode was used for tembotrione, whereas the negative mode was used for M5. Acetonitrile was the extractant for all samples, and the addition of 2 g NaCl to each homogenised sample facilitated the extraction of the analytes into acetonitrile. The extracted analytes were further purified by the addition of 50 mg of C18 sorbent (25 mg GCB was also added to corn samples) for subsequent HPLC-MS/MS analysis. Satisfactory calibration-curve linearities (R2 ≥ 0.997) were obtained for the two analytes at concentrations of 1-500 µg/L. Mean recoveries in different matrices ranged from 73.7% to 110.4%, whereas intra-day and inter-day relative standard deviations were <15% for all concentrations of spiked analytes. The limit of quantification was 2 µg/kg for each analyte in all matrices. In food samples obtained from markets, residual tembotrione and M5 were all below the limits of quantification. These results confirm that the method is suitable for the routine monitoring of residual tembotrione and M5 in a variety of food matrices.

Zearalenone Removal from Corn Oil by an Enzymatic Strategy.

The estrogen-like mycotoxin zearalenone (ZEN) is one of the most widely distributed contaminants especially in maize and its commodities, such as corn oil. ZEN degrading enzymes possess the potential for counteracting the negative effect of ZEN and its associated high safety risk in corn oil. Herein, we targeted enhancing the secretion of ZEN degrading enzyme by Pichia pastoris through constructing an expression plasmid containing three optimized expression cassettes of zlhy-6 codon and signal peptides. Further, we explored various parameters of enzymatic detoxification in neutralized oil and analyzed tocopherols and sterols losses in the corn oil. In addition, the distribution of degraded products was demonstrated as well by Agilent 6510 Quadrupole Time-of-Flight mass spectrometry. P. pastoris GSZ with the glucoamylase signal was observed with the highest ZLHY-6 secretion yield of 0.39 mg/mL. During the refining of corn oil, ZEN in the crude oil was reduced from 1257.3 to 13 µg/kg (3.69% residual) after neutralization and enzymatic detoxification. Compared with the neutralized oil, no significant difference in the total tocopherols and sterols contents was detected after enzymatic detoxification. Finally, the degraded products were found to be entirely eliminated by washing. This study presents an enzymatic strategy for efficient and safe ZEN removal with relatively low nutrient loss, which provides an important basis for further application of enzymatic ZEN elimination in the industrial process of corn oil production.

Random forest as one-class classifier and infrared spectroscopy for food adulteration detection.

This paper proposes the use of random forest for adulteration detection purposes, combining the random forest algorithm with the artificial generation of outliers from the authentic samples. This proposal was applied in two food adulteration studies: evening primrose oils using ATR-FTIR spectroscopy and ground nutmeg using NIR diffuse reflectance spectroscopy. The primrose oil was adulterated with soybean, corn and sunflower oils, and the model was validated using these adulterated oils and other different oils, such as rosehip and andiroba, in pure and adulterated forms. The ground nutmeg was adulterated with cumin, commercial monosodium glutamate, soil, roasted coffee husks and wood sawdust. For the primrose oil, the proposed method presented superior performance than PLS-DA and similar performance to SIMCA and for the ground nutmeg, the random forest was superior to PLS-DA and SIMCA. Also, in both applications using the random forest, no sample was excluded from the external validation set.

Quantification of polycyclic aromatic hydrocarbons and phthalic acid esters in deodorizer distillates obtained from soybean, rapeseed, corn and rice bran oils.

In this study, simple GC-MS methods for analysising sixteen PAHs and seven PAEs were individually established. The LOQs for PAHs and PAEs were ranging from 0.18 to 0.42 µg/kg and 0.19 to 1.50 µg/kg, respectively. The recoveries for DD samples were in the range of 84.8-115.5% and 84.2-109.3% for PAHs and PAEs, respectively. Furthermore, PAHs and PAEs concentrations in soybean, rapeseed, corn and rice bran oil distillates were evaluated. PAHs were found in all the DD samples and the concentrations of BaP, PAH4 and total PAHs were 0.89-55.58, 8.11-326.07 and 115.77-966.40 µg/kg, respectively. Correspondingly, total PAEs concentrations ranged from 2.45 to 24.52 mg/kg, and the mean value was 7.76 mg/kg. The results illustrated that the contents of PAHs and PAEs in the DDs were extremely higher than those in the edible oils, thus indicating that specific issues should be considered in the vegetable oil DDs and DD-based products.

Gas-Phase Ion/Ion Reactions Involving Tris-Phenanthroline Alkaline Earth Metal Complexes as Charge Inversion Reagents for the Identification of Fatty Acids.

Fatty acids (FA) play vital biological roles as energy sources, signaling molecules and key building blocks of complex lipids in cell membranes. Modifications to FA structure and composition are associated with the onset and progression of a number of chronic diseases. Consequently, the sensitive detection and unambiguous structure elucidation of FA is integral to the advancement of biomedical sciences. Recent advances in FA analysis have taken advantage of wet chemical derivatization to enhance detection and drive unique fragmentation in tandem mass spectrometry protocols. Here, we significantly further this approach through demonstrating gas-phase charge inversion of singly deprotonated FA ions, [M - H]-, using doubly charged tris-phenanthroline alkaline earth metal complexes, [Cat(Phen)3]2+ (Cat = Mg2+, Ca2+, Sr2+, or Ba2+). Metal cationized FA, [M - H + Cat]+ are obtained after the gas-phase ion/ion reaction. Low-energy collision-induced dissociation (CID) of the [M - H + Cat]+ cations facilitates double bond localization for a variety of monounsaturated and polyunsaturated FAs. Ultimately, detailed characterization presented unambiguous distinction among FA double bond positional isomers, such as n-3 and n-6 isomers. The method was successfully used to identify the FA profile of corn oil, including double bond localization for unsaturated FAs present.

A comparison of total inward leakage measured using sodium chloride (NaCl) and corn oil aerosol methods for air-purifying respirators.

The International Organization for Standardization (ISO) standard 16900-1:2014 specifies the use of sodium chloride (NaCl) and corn oil aerosols, and sulfur hexafluoride gas for measuring total inward leakage (TIL). However, a comparison of TIL between different agents is lacking. The objective of this study was to measure and compare TIL for respirators using corn oil and NaCl aerosols. TIL was measured with 10 subjects donning two models of filtering facepiece respirators (FFRs) including FFP1, N95, P100, and elastomeric half-mask respirators (ERs) in NaCl and corn oil aerosol test chambers, using continuous sampling methods. After fit testing with a PortaCount (TSI, Inc., St. Paul, MN) using the Occupational Safety and Health Administration (OSHA) protocol, five subjects were tested in the NaCl chamber first and then in the corn oil chamber, while other subjects tested in the reverse order. TIL was measured as a ratio of mass-based aerosol concentrations in-mask to the test chamber, while the subjects performed ISO 16900-1-defined exercises. The concentration of NaCl aerosol was measured using two flame photometers, and corn oil aerosol was measured with one light scattering photometer. The same instruments were used to measure filter penetration in both chambers using a Plexiglas setup. The size distribution of aerosols was determined using a scanning mobility particle sizer and charge was measured with an electrometer. Filter efficiency was measured using an 8130 Automated Filter Tester (TSI). Results showed the geometric mean TIL for corn oil aerosol for one model each of all respirator categories, except P100, were significantly (p < 0.05) greater than for NaCl aerosol. Filter penetration in the two test chambers showed a trend similar to TIL. The count median diameter was ∼82 nm for NaCl and ∼200 nm for corn oil aerosols. The net positive charge for NaCl aerosol was relatively larger. Both fit factor and filter efficiency influence TIL measurement. Overall, TIL determination with aerosols of different size distributions and charges using different methodologies may produce dissimilar results.

A Simple and Portable Screening Method for Adulterated Olive Oils Using the Hand-Held FTIR Spectrometer and Chemometrics Tools.

Extra virgin olive oil has been one of the most common targets for economically motivated food adulteration. This research employed the hand-held FTIR spectrometer to develop the simple and portable screening methods for extra virgin olive oils adulterated with other cheaper vegetable oils. With the help of the ATR probe and chemometrics tools, oil samples can be measured directly without any pretreatment, then the spectra can be interpreted automatically to determine the possibility of adulteration and estimate the content of adulterant oil. A feasibility study of the hand-held FTIR screening method was carried out using olive oils adulterated with canola oil, peanut oil, corn oil, soybean oil, and sunflower oil. The SIMCA model using the hand-held FTIR spectra can identify different kinds of vegetable oils correctly and recognize olive oils with not less than 10% of adulterant oils. Meanwhile, the content of adulterant oil in the range of 5% to 45% can be estimated by the PLS model using the hand-held FTIR spectra within an error of 3%. This research shows the potential of the hand-held FTIR technique in the rapid and field screening of olive oils adulterated with some cheaper vegetable oils. PRACTICAL APPLICATION: This research provide a rapid and automatic detection method for olive oils adulterated with other cheaper vegetable oils. An oil sample can be measured directly within one minute, and the hand-held instrument can be used anywhere needed.

High-throughput authentication of edible oils with benchtop Ultrafast 2D NMR.

We report the use of an Ultrafast 2D NMR approach applied on a benchtop NMR system (43 MHz) for the authentication of edible oils. Our results demonstrate that a profiling strategy based on fast 2D NMR spectra recorded in 2.4 min is more efficient than the standard 1D experiments to classify oils from different botanical origins, since 1D spectra on the same samples suffer from strong peak overlaps. Six edible oils with different botanical origins (olive, hazelnut, sesame, rapeseed, corn and sunflower) have been clearly discriminated by PCA analysis. Furthermore, we show how this approach combined with a PLS model can detect adulteration processes such as the addition of hazelnut oil into olive oil, a common fraud in food industry.

A validated fast difference spectrophotometric method for 5-hydroxymethyl-2-furfural (HMF) determination in corn syrups.

Corn syrups, important ingredients used in food and beverage industries, often contain high levels of 5-hydroxymethyl-2-furfural (HMF), a toxic contaminant. In this work, an in house validation of a difference spectrophotometric method for HMF analysis in corn syrups was developed using sophisticated statistical tools by the first time. The methodology showed excellent analytical performance with good selectivity, linearity (R2=99.9%, r>0.99), accuracy and low limits (LOD=0.10mgL-1 and LOQ=0.34mgL-1). An excellent precision was confirmed by repeatability (RSD (%)=0.30) and intermediate precision (RSD (%)=0.36) estimates and by Horrat value (0.07). A detailed study of method precision using a nested design demonstrated that variation sources such as instruments, operators and time did not interfere in the variability of results within laboratory and consequently in its intermediate precision. The developed method is environmentally friendly, fast, cheap and easy to implement resulting in an attractive alternative for corn syrups quality control in industries and official laboratories.

Triacylglycerol compositions of sunflower, corn and soybean oils examined with supercritical CO2 ultra-performance convergence chromatography combined with quadrupole time-of-flight mass spectrometry.

A supercritical CO2 ultra-performance convergence chromatography (UPC2) system was utilized with a quadrupole time-of-flight mass spectrometry (Q-TOF MS) to examine the triacylglycerol compositions of sunflower, corn and soybean oils. UPC2 provided an excellent resolution and separation for the triacylglycerols, while the high performance Q-TOF MS system was able to provide the molecular weight and fragment ions information for triacylglycerol compound characterization. A total of 33 triacylglycerols were identified based on their elementary compositions and MS2 fragment ion profiles, and their levels in the three oils were estimated. The combination of UPC2 and Q-TOF MS may determine triacylglycerol compositions for oils and fats, and provide sn-position information for fatty acids, which may be important for food nutritional value and stability.

Physicochemical properties of nixtamalized corn flours with and without germ.

This research studied the influence of the germ components on the physicochemical properties of cooked corn and nixtamalized corn flours as a function of the calcium hydroxide content (from 0 to 2.1 w/w) and steeping time (between 0 and 9h). A linear relationship was found between calcium content in germ and steeping time used during nixtamalization process. X-ray diffraction analysis showed that calcium carbonate is formed into the germ structure to 2.1 w/w of calcium hydroxide and 9h steeping time. The presence of the germ improves the development of peak viscosity in flours, and it is related to the increases in calcium concentration in germ and the formation of amylose-lipid complexes. No significant changes were observed in palmitic, stearic, oleic and linoleic acids of corn oil. The levels of further corn oil deterioration were 2.1 w/w of calcium hydroxide concentration and 9h of steeping time.

Hyphenation of supercritical fluid chromatography with tandem mass spectrometry for fast determination of four aflatoxins in edible oil.

RATIONALE: Aflatoxins (AFTs) are of great concern all over the world. Supercritical fluid chromatography (SFC) has the advantage of fast, high resolution and excellent compatibility with a broad range of organic solvents and samples, thus hyphenating SFC with tandem mass spectrometry (MS/MS) can be used for the easy and fast determination of AFTs in edible oils. METHODS: Edible oil was spiked with isotope-labeled aflatoxin standards, diluted with hexane and extracted with acetonitrile. The extraction was directly loaded to an SFC apparatus and separated on a UPC(2) 2-EP column with CO2 -methanol gradient elution. A post-column make-up flow was introduced to facilitate mass spectrometry performance, and the mixture was analyzed by MS/MS with an electrospray ionization (ESI) source. RESULTS: The SFC conditions including separation column, modifier and sample solvent were optimized, and the four target aflatoxins were baseline separated. The ESI interface parameters were also investigated, implicating the make-up flow as a critical factor for sensitive determination by SFC-MS/MS. The LOQs for the AFTs were 0.05-0.12 µg L(-1) , while the RSDs were lower than 8.5%. CONCLUSIONS: Supercritical fluid chromatography was successfully coupled to tandem mass spectrometry to establish a simple, fast and sensitive method for the analysis of four aflatoxins in edible oil. This shows the combination of SFC-MS/MS has great potential in determination of trace contaminants in food. Copyright © 2016 John Wiley & Sons, Ltd.

Corn oil versus lard: Metabolic effects of omega-3 fatty acids in mice fed obesogenic diets with different fatty acid composition.

Mixed results have been obtained regarding the level of insulin resistance induced by high-fat diets rich in saturated fatty acids (SFA) when compared to those enriched by polyunsaturated fatty acids (PUFA), and how metabolic effects of marine PUFA of n-3 series, i.e. docosahexaenoic acid (DHA) and eicosapentaenoic acid (EPA), depend on dietary lipid background. Here we compared two high-fat diets, in which the major lipid constituent was based either on SFA in the form of pork lard (LHF diet) or PUFA of n-6 series (Omega-6) as corn oil (cHF diet). Both cHF and LHF parental diets were also supplemented with EPA+DHA (∼30 g/kg diet) to produce cHF+F and LHF+F diet, respectively. Male C57BL/6N mice were fed the experimental diets for 8 weeks. Insulin sensitivity was assessed by hyperinsulinemic-euglycemic clamps in mice fed LHF and cHF diets, and then metabolic effects of cHF+F and LHF+F diets were assessed focusing on the liver and epididymal white adipose tissue (eWAT). Both LHF and cHF induced comparable weight gain and the level of insulin resistance, however LHF-fed mice showed increased hepatic steatosis associated with elevated activity of stearoyl-CoA desaturase-1 (SCD1), and lower plasma triacylglycerol levels when compared to cHF. Despite lowering hepatic SCD1 activity, which was concomitant with reduced hepatic steatosis reaching the level observed in cHF+F mice, LHF+F did not decrease adiposity and the weight of eWAT, and rather further impaired insulin sensitivity relative to cHF+F, that tended to improve it. In conclusion, high-fat diets containing as much as ∼35 weight% as lipids induce similar weight gain and impairment of insulin sensitivity irrespective whether they are based on SFA or Omega-6. Although the SFA-rich diet containing EPA+DHA efficiently reduced hepatic steatosis, it did so without a corresponding improvement in insulin sensitivity and in the absence of effect on adiposity.

Novel qPCR systems for olive (Olea europaea L.) authentication in oils and food.

The traceability of olive oil is an unresolved issue that remains a challenge. In this field, DNA-based techniques are very powerful tools for discrimination that are less negatively influenced by environmental conditions than other techniques. More specifically, quantitative real time PCR (qPCR) achieves a high degree of sensitivity, although the DNA that it can directly isolate from these oils presents drawbacks. Our study reports the analysis of eight systems, in order to determine their suitability for olive detection in oil and oil-derived foodstuffs. The eight systems were analyzed on the basis of their sensitivity and specificity in the qPCR assay, their relative sensitivity to olive DNA detection and DNA mixtures, their sensitivity and specificity to olive in vegetable oils and the detection of olive in commercial products. The results show that the PetN-PsbM system, designed in this study, is a suitable and reliable technique in relation to olive oil and olive ingredients in both food authentication and food safety processes.