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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.
Oxidative stability assessment of industrial and laboratory-pressed fresh raspberry seed oil (Rubus idaeus L.) by differential scanning calorimetry
DSC melting profile of cold-pressed hemp seed oil as an authenticity fingerprint influenced by scanning rate
Among the variety of edible cold-pressed oils on the market, hemp seed oil is becoming increasingly popular among scientists and consumers due to its plethora of nutritional compounds. In this study, the goal was to examine the thermal characteristics of cold-pressed hemp seed oil pressed from seeds of the Henola cultivar procured by five different suppliers in two different seasons. This aim of this research was to establish how various scanning rates can affect the unique thermal profile of cold-pressed hemp seed oil in terms of an authenticity assessment. The melting transition was manifested by curves with four peaks for all hemp seed oils; however, they differed for each scanning rate in terms of the shape and peak intensity. Comparing the curves obtained at heating rates of 1 and 2 °C/min, noticeable differences were observed in the melting transition parameters between hemp seed oils, showing that small differences in fatty acid composition can cause changes in DSC profiles. In contrast, at a scanning rate 5 °C/min, the melting curves were similar for all hemp seed oils. It was also observed that for all the scanning rates, there was a strong negative correlation between the total content of polyunsaturated fatty acids (ƩPUFAs) and the peak temperature of the three peaks (Tm2, Tm3, and Tm4). The most abundant fatty acids were PUFAs, i.e., linoleic acid (C18:2), with contents ranging from 47 to 55%; and α-linolenic acid (C 18:3 n–3), with contents ranging from 17 to 25%. The application of linear discriminant analysis (LDA) enabled a discriminant model to be built based on the DSC data obtained for differentiation of oils pressed from fresh and stored seeds.
Physicochemical characteristics of cold-pressed blackcurrant-, strawberry-, and raspberry seed oils during storage and its influence on thermo-oxidative stability
Discrimination of Selected Cold-Pressed and Refined Oils by Untargeted Profiling of Phase Transition Curves of Differential Scanning Calorimetry
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 use the differential scanning calorimetry (DSC) technique to detect adulterations of cold-pressed flaxseed oil with refined rapeseed oil (RP). 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 a RP concentration of 5, 10, 20, 30, 50% (w/w). Significant linear correlations (p ≤ 0.05) between the RP concentration and all DSC parameters were observed, except for h1. 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, Artificial Neural Networks, ANNs); 2) regression models (Multiple Linear Regression, MLR, MARS, SVM, ANNs, 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. These results demonstrate the usefulness of the DSC technique combined with chemometrics for predicting the adulteration of cold-pressed flaxseed oil with refined rapeseed oil.
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).
DSC Phase Transition Profiles Analysed 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 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, 6 months of storing flaxseed oils, originated from five different cultivars. Four peaks at around -36, -30, -25, -12 °C were identified using the deconvolution analysis procedure, which enabled data to be collected on peak temperature (T), peak height (h) and the peak area (A), as well as the ratio calculated from these parameters. Control charts of DSC parameters, linked to the second peak (h2, A2) and calculated ratios of those parameters showed an increasing or decreasing trend within the storage time, thus were considered to be indicators of oil deterioration. Since DSC parameters related to the first peak (h1, A1) and third peak (h3, A3) remained unchanged within storage, they were established as the markers of flaxseed oil authenticity.
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.
Increasing the Oxidative Stability of the Wafer Lipid Fraction with Fruit Extract during Storage
Confectionary products are increasingly popular among consumers. However, since they usually have a long shelf life (about 12 months), their oxidative stability during long-term storage becomes a significant issue. Thus, the aim of this study was to investigate the effect of addition of commercially available fruit extract on the oxidative stability of lipid fraction, extracted from wafers sheets stored 13 months at 18 °C. For this purpose, the oxidation induction times (OIT) were determined by using isothermal differential scanning calorimetry (DSC). Conjugated diene content (CD) and 2,2-diphenyl-1-pikrylhydrazyl (DPPH) antioxidant activity were also monitored. All results obtained showed that the fruit extract addition slowed down effectively the peroxidation process of lipid fraction of wafer sheets. The rate of OIT and CD changes during the first six months of storage were about two times lower for the sample with the extract (LWE) than for the control (LWS). The DPPH antioxidant activity of LWE was higher than for the LWS sample until the 8th month of storage. It was stated that fruit extract effectively enhanced the oxidative stability of lipid fraction of wafers up until the 10th month of storage. After this period, CD values increased significantly for LWS and LWE samples, while at the same time there were no significant differences in OIT and DPPH values between both samples (p > 0.05).
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.