Comparing Different Chemometric Approaches to Detect Adulteration of Cold-Pressed Flaxseed Oil with Refined Rapeseed Oil Using Differential Scanning Calorimetry.

Flaxseed oil is one of the best sources of n-3 fatty acids, thus its adulteration with refined oils can lead to a reduction in its nutritional value and overall quality. The purpose of this study was to compare different chemometric models to detect adulteration of flaxseed oil with refined rapeseed oil (RP) using differential scanning calorimetry (DSC). Based on the melting phase transition curve, parameters such as peak temperature (T), peak height (h), and percentage of area (P) were determined for pure and adulterated flaxseed oils with an RP concentration of 5, 10, 20, 30, and 50% (w/w). Significant linear correlations (p ≤ 0.05) between the RP concentration and all DSC parameters were observed, except for parameter h1 for the first peak. In order to assess the usefulness of the DSC technique for detecting adulterations, three chemometric approaches were compared: (1) classification models (linear discriminant analysis-LDA, adaptive regression splines-MARS, support vector machine-SVM, and artificial neural networks-ANNs); (2) regression models (multiple linear regression-MLR, MARS, SVM, ANNs, and PLS); and (3) a combined model of orthogonal partial least squares discriminant analysis (OPLS-DA). With the LDA model, the highest accuracy of 99.5% in classifying the samples, followed by ANN > SVM > MARS, was achieved. Among the regression models, the ANN model showed the highest correlation between observed and predicted values (R = 0.996), while other models showed goodness of fit as following MARS > SVM > MLR. Comparing OPLS-DA and PLS methods, higher values of R2X(cum) = 0.986 and Q2 = 0.973 were observed with the PLS model than OPLS-DA. This study demonstrates the usefulness of the DSC technique and importance of an appropriate chemometric model for predicting the adulteration of cold-pressed flaxseed oil with refined rapeseed oil.

DSC Phase Transition Profiles Analyzed by Control Charts to Determine Markers for the Authenticity and Deterioration of Flaxseed Oil during Storage.

An approach of implementing X-bar and R control charts as a statistical control tool to monitor the changes in the melting profile of fresh and stored flaxseed oils by differential scanning calorimetry (DSC) was used. Phase transition melting profiles were collected after 0, 2, 4, and 6 months of storing flaxseed oils, originating from five different cultivars. Four peaks at around -36, -30, -25, and -12 °C were identified using the deconvolution analysis procedure, which enabled the data to be collected at peak temperature (T), peak height (h), the peak area (A), and the percentages of the area (P A), as well as the ratio calculated from these parameters. Control charts obtained for the second peak of the melting profile showed a significant decrease of peak height (h2) from 0.50 to 0.39 W/g and the percentage of the area (P A2) from 50 to 38%, within the storage time (p ≤ 0.05); thus, they were considered to be indicators of oil deterioration. Strong negative correlations of the unstable parameters of DSC with chemical indicators of the oils' oxidative stability (PV, p-AV, TOTOX) were found. For DSC parameters, related to the first peak (h1, A1) and the third peak (h3, A3), changes were statistically not significant within storage (p > 0.05); thus, they can be used as markers of flaxseed oil authenticity. The study demonstrated that X-bar and R control charts could effectively monitor changes in the specific peaks and calculated ratios from the DSC melting profile of fresh and stored flaxseed oils, serving as reliable indicators of oil deterioration.

Influence of Seeds' Age and Clarification of Cold-Pressed Raspberry (Rubus idaeus L.) Oil on the DSC Oxidative Stability and Phase Transition Profiles.

After cold-pressing, small particles of seed residue remain in raspberry seed oil (RSO), even after passing it through cold filtration. The removal of the remaining seed residue is rather an alternative option to improve the visual properties of RSO. This study investigated the influence that the seeds' age (0, 10, 20 months) and clarification process after pressing has on the oxidative stability and phase transition of RSO by means of differential scanning calorimetry (DSC). The results proved that the oil centrifugation process reduces the DPPH radical scavenging activity and oxidative stability measured by p-anisidine value (p-AnV) and DSC oxidation induction time (OIT) at 120 °C of all RSO samples, regardless of the age of the seeds (p ≤ 0.05). No significant differences were observed on the DSC melting and crystallization properties at 1 °C/min after the oil clarification by centrifugation (p > 0.05). The storage time of raspberry seeds, i.e., 10 and 20 months after expiry date, influenced the quality deterioration of RSO, as measured by higher p-AnV, lower DPPH, and OIT values (p ≤ 0.05). The results presented provide new information about oil production processing, suggesting that producers should reconsider giving up the clarification process of oil, since it lowers all quality parameters.

Authenticity Assessment from Sesame Seeds to Oil and Sesame Products of Various Origin by Differential Scanning Calorimetry.

The aim of this study was to conduct thermal characterization of sesame seeds and oils from various geographical origins (Ethiopia, India, Nigeria, Sudan, Turkey), different method of extraction (hexane and cold-pressing), and different types of derived products (halva and tahini). Thermal characterization was investigated using differential scanning calorimetry (DSC), which showed that origin of the seeds has no influence on the melting profile of sesame oil (peak temperature and enthalpy). Method of extraction (hexane and cold-pressing) influenced the peak temperatures of the resulting oils (p ≤ 0.05). The addition of 20% of palm olein to pure sesame oil influenced the significant changes in thermodynamic parameters such as peak temperature (Tm2), which was lowered from −5.89 °C to −4.99 °C, peak half width (T1/2), elevated from 3.01 °C to 4.52 °C, and the percentage of first peak area (% peak 1) lowered from 87.9 to 73.2% (p ≤ 0.05). The PCA method enabled to distinguish authentic and adulterated sesame oils of various origins. There were no significant differences in thermal properties among the products (halva, tahini) and the authentic sesame oil (p > 0.05). The obtained results showed DSC feasibility to characterize sesame oil and sesame products in terms of authenticity.

Assessment of Hemp Seed Oil Quality Pressed from Fresh and Stored Seeds of Henola Cultivar Using Differential Scanning Calorimetry.

Cold-pressed hemp (Cannabis Sativa L.) seed oil has become very popular amongst consumers and researchers, due to its manifold application in food and medicine industry. In this study, oils pressed from stored and fresh hemp seeds of the Henola cultivar were analyzed. Determination of the acid value (AV) and color of oil (a* parameter) revealed significant differences between the two groups of oils (fresh and stored seeds) in contrast to the peroxide value (PV), p-anisidine value (p-AV), and fatty acid composition. On the other hand, isothermal and non-isothermal assessments of the thermo-oxidative stability by differential scanning calorimetry (DSC) showed no significant differences in oxidation induction time (OIT) as well as in onset temperature (Ton) between two groups of oils (p > 0.05). The DSC isothermal test (OIT 160) showed significant correlations with mono- and polyunsaturated fatty acids as well as with values of AV and a* (p ≤ 0.05), in contrast to the non-isothermal test, for which correlations were not significant (p > 0.05). However, the best distinction of both groups of oils was obtained analyzing all results together (DSC, fatty acid and tocochromanols composition, color, and oxidative stability results) by principal component analysis (PCA).

Comprehensive Thermal Characteristics of Different Cultivars of Flaxseed Oil (Linum usittatissimum L.).

The aim of this study was to describe the thermal properties of selected cultivars of flaxseed oil by the use of the differential scanning calorimetry (DSC) technique. The crystallization and melting profiles were analyzed depending on different scanning rates (1, 2, 5 °C/min) as well as oxidative induction time (OIT) isothermally at 120 °C and 140 °C, and oxidation onset temperatures (Ton) at 2 and 5 °C/min were measured. The crystallization was manifested as a single peak, differing for a cooling rate of 1 and 2 °C/min. The melting curves were more complex with differences among the cultivars for a heating rate of 1 and 2 °C/min, while for 5 °C/min, the profiles did not differ, which could be utilized in analytics for profiling in order to assess the authenticity of the flaxseed oil. Moreover, it was observed that flaxseed oil was highly susceptible to thermal oxidation, and its stability decreased with increasing temperature and decreasing heating rate. Significant negative linear correlations were found between unsaturated fatty acid content (C18:2, C18:3 n-3) and DSC parameters (OIT, Ton). Principal component analysis (PCA) also established a strong correlation between total oxidation value (TOTOX), peroxide value (PV) and all DSC parameters of thermo-oxidative stability.