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Cold Pressed Oil from Japanese Quince Seeds (Chaenomeles japonica): Characterization Using DSC, Spectroscopic, and Monolayer Data

2025, Kamińska, Wiktoria, Neunert, Grażyna, Siejak, Przemysław, Polewski, Krzysztof, Tomaszewska-Gras, Jolanta

The cold-pressed oil from Japanese quince seeds (JQSO) is notable for its favorable fatty acid profile, low oxidation rate, and bioactive compounds like antioxidants, sterols, and carotenoids. This study offers a detailed molecular-level physical characterization of JQSO and its minor components using differential scanning calorimetry (DSC), Langmuir monolayer studies, and various spectroscopic methods, including UV–vis absorption, fluorescence, and FTIR. DSC analysis identified five peaks related to triglyceride (TG) fractions and provided insights into the melting and crystallization behavior of JQSO. The Langmuir monolayer studies revealed high compressibility, indicative of superior emulsification properties. Viscoelastic modulus measurements suggested strong intermolecular interactions, contributing to the oil’s resilience under stress—an attribute typical of oils high in saturated or monounsaturated fatty acids. Spectroscopic methods confirmed the presence of phenolic acids, tocopherols, carotenoids, and their derivatives. The total fluorescence spectra highlighted prominent peaks at 290 nm/330 nm and 360 nm/440 nm, while the total synchronous fluorescence spectra revealed key excitation–emission regions (10–50 nm/300 nm and 40–140 nm/360 nm), corroborating the presence of tocopherols, phenols, polyphenols, flavones, and carotenoids. No evidence of chlorophyll was detected. The ATR-FTIR spectra validated the presence of fatty acids and triacylglycerols, emphasizing a high degree of esterification and the dominance of unsaturated fatty acids in oil structures. The methods used provided the opportunity to perform a label-free, fast, and reliable determination of the properties of JQSO. The findings confirmed that crude, cold-pressed JQSO retains its valuable bioactive components, aligning with previous research on its chemical and physical properties.

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Chemical composition and structure of foods

2023, Tomaszewska-Gras, Jolanta, Staroszczyk, Hanna, Sikorski, Zdzisław E.

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Assessment of DPPC Liposome Disruption by Embedded Tocopheryl Malonate

2023, Neunert, Grażyna, Tomaszewska-Gras, Jolanta, Gauza-Włodarczyk, Marlena, Witkowski, Stanislaw, Polewski, Krzysztof

In this study, the effect of α-tocopheryl malonate (TM) on physical and structural properties of DPPC liposomes was investigated using ANS fluorescence, DPH, and TMA–DPH anisotropy fluorescence and differential scanning calorimetry (DSC) methods. The presence of embedded TM in DPPC liposomes caused alteration in its phase transition temperatures, structural order, dynamics, and hydration of head groups increasingly with growing TM concentration. The ANS fluorescence results demonstrated that increasing TM presence in the DPPC gel phase due to interrupted membrane structure caused the formation of new binding sites. Temperature investigations in the range of 20 °C to 60 °C showed that increasing temperature rises ANS fluorescence which reaches local and global maxima at 36 °C and 42 °C, respectively. The rising TM concentration at the phase transition temperature of DPPC led to the lowering of ANS fluorescence, indicating a decreased binding of ANS. Simultaneously, during heating, a roughly 10-nm shift of ANS emission maximum was observed. The results indicated that in the fluid phase, the observed quenching appears as a result of increasing accessibility of water molecules into ANS in this region. The DPH results indicated that in the gel phase presence of TM introduced disorder in the hydrophobic acyl chain region led to its fluidization. The TMA–DPH results indicated an increasing disorder in the interface region and an increasing hydration of head group atoms at the surface of the membrane. The increasing concentration of TM results in the formation of multicomponent DSC traces, suggesting the formation of another structural phase. The applied methods proved that the incorporation of TM into DPPC membrane results in the interaction of malonate moiety with DPPC head group atoms in the interphase layer and induces the interruption in the membrane packing order, leading to its structural changes. The presented results show that TM presence could regulate the membrane properties, thus it may indicate one of the possible mechanisms responsible for the effective disruption of cell membranes by TM. The knowledge of molecular mechanism how TM interacts with the membrane will help to elucidate its possible pharmacological activity.

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

2023, Islam, Mahbuba, Kaczmarek, Anna Maria, Grygier, Anna, Tomaszewska-Gras, Jolanta

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.

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Differential scanning calorimetry as a tool to assess the oxidation state of cold-pressed oils during shelf-life

2023, Islam, Mahbuba, Kaczmarek, Anna Maria, Tomaszewska-Gras, Jolanta

AbstractCold-pressed oils are highly prone to the peroxidation process, which causes a rapid decline in quality. Thus, there is a need to develop instrumental methods instead of conventional chemical analysis consuming large quantities of harmful chemicals. Differential scanning calorimetry (DSC) is a valuable analytical tool for assessing the oxidative stability of oils. Cold-pressed flaxseed, camelina and hemp seed oils from different cultivars, which had been stored for six months in room conditions under natural light exposure, were tested. Chemical methods for measuring changes in oxidative stability during storage of oils included determination of peroxide value (PV), p-Anisidine value (p-AV), total oxidation value (TOTOX) value and acid value (AV). Parameters like oxidation induction time (OIT) in isothermal mode (120, 140 °C) and onset temperature (Ton) in non-isothermal mode (heating rate 2, 5 °C/min) were established from DSC curves. Data for OIT and Ton plotted against time showed a strong, significant (p ≤ 0.05) descending trend for all oils. However, flaxseed and hempseed oils revealed a more rapid deterioration during storage compared to camelina seed oils. All DSC results showed promising repeatability of the oxidative characteristics for three types of cold-pressed oils, regardless of their origins in different cultivars. However, the most suitable for monitoring the deteriorative changes in oils during storage was the isothermal test carried out at a temperature of 120 °C, for which the correlations with chemical indicators (PV, p-AV, TOTOX) were highly significant (p ≤ 0.0001). Linear discriminant analysis (LDA) based on the DSC results revealed, that the first discriminating function significantly separated the fresh oils from stored oils. The study showed that, based on a starting point defined for fresh oils, the DSC technique can be used to effectively and ecologically monitor the deterioration of oils by oxidation, instead of harmful chemical analyses.

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LC-MS-based glyceride profiling of cold-pressed fruit seed oils for effective authenticity testing

2025, Kozub-Pędrak, Anna, Nikolaichuk, Hanna, Przykaza, Kacper, Sumara, Agata, Pitucha, Monika, Tomaszewska-Gras, Jolanta, Fornal, Emilia

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The Effects of Cellular Membrane Damage on the Long-Term Storage and Adhesion of Probiotic Bacteria in Caco-2 Cell Line

2023, Kiepś, Jakub, Juzwa, Wojciech, Olejnik, Anna, Sip, Anna, Tomaszewska-Gras, Jolanta, Dembczyński, Radosław

Adhesion is one of the main factors responsible for the probiotic properties of bacteria in the human gut. Membrane proteins affected by cellular damage are one of the key aspects determining adhesion. Fluid-bed-dried preparations containing probiotic bacteria were analyzed in terms of their stability (temperature of glass transition) and shelf life in different conditions (modified atmosphere, refrigeration). Imaging flow cytometry was utilized to determine four subpopulations of cells based on their physiological and morphological properties. Lastly, adhesion was measured in bacteria cultured in optimal conditions and treated with heat shock. The results show that the subpopulations with no or low levels of cell membrane damage exhibit the ability to adhere to Caco-2 cells. The temperature of protein denaturation in bacteria was recorded as being between 65 °C and 70 °C. The highest glass transition temperature (Tg) value for hydroxypropyl methylcellulose (used as a coating substance) was measured at 152.6 °C. Drying and coating can be utilized as a sufficient treatment, allowing a long shelf-life (up to 12 months). It is, however, worth noting that technological processing, especially with high temperatures, may decrease the probiotic value of the preparation by damaging the bacterial cells.

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Fusion of DSC and FTIR data with physicochemical profiling to distinguish berry seed oils by extraction methods

2025, Rajagukguk, Yolanda Victoria, Grygier, Anna, Siger, Aleksander, Waśkiewicz, Agnieszka, Ryszczyńska, Sylwia, Tomaszewska-Gras, Jolanta

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Advanced authenticity screening of commercial berry seed oils using full FTIR spectra and DSC curves coupled with chemometrics

2025, Rajagukguk, Yolanda Victoria, Tomaszewska-Gras, Jolanta

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Different Chemometric Approaches to Detect Adulteration of Cold‐Pressed Flaxseed oil with Refined Rapeseed Oil Using Differential Scanning Calorimetry

2023, Islam, Mahbuba, Kaczmarek, Anna Maria, Montowska, Magdalena, Tomaszewska-Gras, Jolanta

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.

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Changes in Resveratrol Containing Phytosterol Liposomes During Model Heating

2025, Igielska-Kalwat, Joanna, Rudzińska, Magdalena, Grygier, Anna, Kmiecik, Dominik, Cieślik-Boczula, Katarzyna, Tomaszewska-Gras, Jolanta

Background: Phytosterols are bioactive lipids susceptible to oxidation, particularly under thermal stress. Incorporation into liposomes may enhance their stability, while resveratrol—a natural antioxidant—could further limit thermal degradation. Stigmasterol esters, which contain fatty acid residues prone to oxidation, require additional characterization to understand their behavior under heating. Methods: Liposomes composed of dipalmitoylphosphatidylcholine (DPPC) were enriched with free stigmasterol (ST), stigmasteryl myristate (ME), or stigmasteryl oleate (OE), with or without resveratrol (RES). Liposomal systems were characterized using transmission electron microscopy, zeta potential, and hydrodynamic diameter analyses. Samples were heated at 60 °C and 180 °C for 8 h to evaluate stigmasterol degradation, oxyphytosterol (SOP) formation, and decomposition of fatty acid residues in the esters. Results: Liposomes remained structurally stable at 60 °C but underwent marked alterations at 180 °C. ST formed the smallest particles, while ME and OE systems exhibited larger hydrodynamic diameters. Incorporation of resveratrol enhanced thermal and oxidative stability, reducing stigmasterol degradation (7.73–18.86% at 60 °C; 29.66–35.28% at 180 °C) and limiting SOP formation. Differences in the breakdown of myristic versus oleic acid residues highlighted the role of fatty acid type in determining thermal resistance. Conclusions: Resveratrol effectively improves the stability of liposomes containing stigmasterol or its esters and mitigates oxidative damage under thermal stress. Protective effects were particularly evident at moderate temperatures, indicating the potential of resveratrol–phytosterol liposomes as thermally stable delivery systems.

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Determining the Behavior of Water in Buttermilk Cheese with Polymerized Whey Protein Using Differential Scanning Calorimetry and Nuclear Magnetic Resonance Analysis

2022, Cais-Sokolińska, Dorota, Bielska, Paulina, Baranowska, Hanna M., Tomaszewska-Gras, Jolanta

In this research, the behavior of water in buttermilk cheese with the addition of polymerized whey proteins was determined. Various parameters of the produced cheese, such as texture, color, water activity, and unbound protein fraction, were examined. Four different samples of buttermilk cheese were prepared, including no addition of whey protein concentrate (BMC); addition of whey protein concentrate (BMC/WPC; 5.62%, w/v), single-heated polymerized whey protein (BMC/SPWP; 28%, w/v), and double-heated polymerized whey protein (BMC/DPWP; 28%, w/v). Differential Scanning Calorimetry (DSC) analysis showed that the highest percentage of freezable water in the water fraction and the lowest of unfreezable water was found in buttermilk cheese with WPC and buttermilk cheese with DPWP. Nuclear magnetic resonance (NMR) analysis showed that the relaxation times were longer in buttermilk cheese with WPC, compared to buttermilk cheese with SPWP and DPWP. Single heat treatment of whey proteins increased stickiness almost 3-fold, and double heat treatment had almost a 2-fold increase in work of shear of cheese samples. The calculated total color difference (ΔE) of the cheese samples suggested that those with polymerized whey protein may increase consumer acceptability.

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Oxidative stability assessment of industrial and laboratory-pressed fresh raspberry seed oil (Rubus idaeus L.) by differential scanning calorimetry

2023, Rajagukguk, Yolanda Victoria, Islam, Mahbuba, Siger, Aleksander, Fornal, Emilia, Tomaszewska-Gras, Jolanta

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Physicochemical characteristics of cold-pressed blackcurrant-, strawberry-, and raspberry seed oils during storage and its influence on thermo-oxidative stability

2024, Rajagukguk, Yolanda Victoria, Islam, Mahbuba, Grygier, Anna, Siger, Aleksander, Rudzińska, Magdalena, Tomaszewska-Gras, Jolanta

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Increasing the Oxidative Stability of the Wafer Lipid Fraction with Fruit Extract during Storage

2023, Bełkowska, Liliana, Muzolf-Panek, Małgorzata, Islam, Mahbuba, Tomaszewska-Gras, Jolanta

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).

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Discrimination of Selected Cold-Pressed and Refined Oils by Untargeted Profiling of Phase Transition Curves of Differential Scanning Calorimetry

2023, Islam, Mahbuba, Montowska, Magdalena, Emilia, Fornal, Tomaszewska-Gras, Jolanta

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Oxidative stability and colour changes of fat- and sugar-reduced wafer creams during the storage

2025, Bełkowska, Liliana, Muzolf-Panek, Małgorzata, Waśkiewicz, Agnieszka, Rudzińska, Magdalena, Tomaszewska-Gras, Jolanta

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Research Project

Identyfikacja lipidomicznych biomarkerów rozpoznawania autentyczności olejów jadalnych wsparta profilowaniem DSC i chemometrią

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Thermal and spectroscopic profiles variation of cold-pressed raspberry seed oil studied by DSC, UV/VIS, and FTIR techniques

2023, Rajagukguk, Yolanda Victoria, Islam, Mahbuba, Grygier, Anna, Tomaszewska-Gras, Jolanta

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Lipidomic characteristics of three edible cold-pressed oils by LC/Q-TOF for simple quality and authenticity assurance

2023, Kozub, Anna, Nikolaichuk, Hanna, Przykaza, Kacper, Tomaszewska-Gras, Jolanta, Fornal, Emilia