Thermal and oxidative stability of the Ocimum basilicum L. essential oil/β-cyclodextrin supramolecular system

Ocimum basilicum L. essential oil and its β-cyclodextrin (β-CD) complex have been investigated with respect to their stability against the degradative action of air/oxygen and temperature. This supramolecular system was obtained by a crystallization method in order to achieve the equilibrium of complexed–uncomplexed volatile compounds in an ethanol/water solution at 50 °C. Both the raw essential oil and its β-CD complex have been subjected to thermal and oxidative degradation conditions in order to evaluate the protective capacity of β-CD. The relative concentration of the O. basilicum L. essential oil compounds, as determined by GC–MS, varies accordingly with their sensitivity to the thermal and/or oxidative degradation conditions imposed. Furthermore, the relative concentration of the volatile O. basilicum L. compounds found in the β-CD complex is quite different in comparison with the raw material. An increase of the relative concentration of linalool oxide from 0.3% to 1.1%, in addition to many sesquiterpene oxides, has been observed. β-CD complexation of the O. basilicum essential oil modifies the relative concentration of the encapsulated volatile compounds. Thus, linalool was better encapsulated in β-CD, while methylchavicol (estragole) was encapsulated in β-CD at a concentration close to that of the raw essential oil. Higher relative concentrations from the degradation of the oxygenated compounds such as linalool oxide and aromadendren oxide were determined in the raw O. basilicum L. essential oil in comparison with the corresponding β-CD complex. For the first time, the protective capability of natural β-CD for labile basil essential oil compounds has been demonstrated

Antioxidant Activity and Discrimination of Organic Apples (Malus domestica Borkh.) Cultivated in the Western Region of Romania: A DPPH· Kinetics–PCA Approach

Apple (Malus domestica Borkh.) is one of the most used fruit for beverages in Romania. The goal of the study was to evaluate the antioxidant activity and discrimination of various parts of organic and non-organic apple varieties cultivated in the western region of Romania using the DPPH kinetics–PCA (principal component analysis) approach. Organic and non-organic apples were subjected to solid–liquid ethanol extraction. Core and shell extracts were mixed with DPPH· and spectrophotometrically monitored at 517 nm. Antioxidant activity and mean DPPH· reaction rate at various time ranges reveal significant differences between organic and non-organic samples, as well as apple parts. Organic core and shell extracts had higher antioxidant activities than the corresponding non-organic samples (74.5–96.9% and 61.9–97.2%, respectively, 23.5–94.3% and 59.5–95.5%). Significant differences were observed for the DPPH· reaction rate for the first ½ min, especially in the presence of organic core extracts (3.7–4.8 μM/s). The organic samples were well discriminated by DPPH· kinetics–PCA, the most important variables being the DPPH· reaction rate for the first time range. This is the first DPPH· kinetics–PCA approach applied for discriminating between organic and non-organic fruits and can be useful for evaluating the quality of such type of fruits

Discrimination of β-cyclodextrin/hazelnut (Corylus avellana L.) oil/flavonoid glycoside and flavonolignan ternary complexes by Fourier-transform infrared spectroscopy coupled with principal component analysis

The goal of the study was the discrimination of β-cyclodextrin (β-CD)/hazelnut (Corylus avellana L.) oil/antioxidant ternary complexes through Fourier-transform infrared spectroscopy coupled with principal component analysis (FTIR–PCA). These innovative complexes combine the characteristics of the three components and improve the properties of the resulting material such as the onsite protection against oxidative degradation of hazelnut oil unsaturated fatty acid glycerides. Also, the apparent water solubility and bioaccessibility of the hazelnut oil components and antioxidants can be increased, as well as the controlled release of bioactive compounds (fatty acid glycerides and antioxidant flavonoids, namely hesperidin, naringin, rutin, and silymarin). The appropriate method for obtaining the ternary complexes was kneading the components at various molar ratios (1:1:1 and 3:1:1 for β-CD hydrate:hazelnut oil (average molar mass of 900 g/mol):flavonoid). The recovering yields of the ternary complexes were in the range of 51.5–85.3% and were generally higher for the 3:1:1 samples. The thermal stability was evaluated by thermogravimetry and differential scanning calorimetry. Discrimination of the ternary complexes was easily performed through the FTIR–PCA coupled method, especially based on the stretching vibrations of CO groups in flavonoids and/or CO/CC groups in the ternary complexes at 1014.6 (± 3.8) and 1023.2 (± 1.1) cm−1 along the second PCA component (PC2), respectively. The wavenumbers were more appropriate for discrimination than the corresponding intensities of the specific FTIR bands. On the other hand, ternary complexes were clearly distinguishable from the starting β-CD hydrate along the first component (PC1) by all FTIR band intensities and along PC2 by the wavenumber of the asymmetric stretching vibrations of the CH groups at 2922.9 (± 0.4) cm−1 for ternary complexes and 2924.8 (± 1.4) cm−1 for β-CD hydrate. The first two PCA components explain 70.38% from the variance of the FTIR data (from a total number of 26 variables). Other valuable classifications were obtained for the antioxidant flavonoids, with a high similarity for hesperidin and naringin, according to FTIR–PCA, as well as for ternary complexes depending on molar ratios. The FTIR–PCA coupled technique is a fast, nondestructive and cheap method for the evaluation of quality and similarity/characteristics of these new types of cyclodextrin-based ternary complexes having enhanced properties and stability

A DPPH· Kinetic Approach on the Antioxidant Activity of Various Parts and Ripening Levels of Papaya (Carica papaya L.) Ethanolic Extracts

Papaya fruits (Carica papaya L.) are valuable both as food, including concentrates and mixed beverages and in traditional medicine. The goal of the study was to evaluate the antioxidant activity of various parts of unripe and ripe papaya fruit from the DPPH· kinetics point of view. Peel, pulp, seed, and seed-pulp of unripe and ripe papaya fruits (¼ and >¾ level of ripening) were extracted with ethanol and monitored at 517 nm in the presence of DPPH·. The radical scavenging capacity (RSC) at various time ranges and DPPH· reaction rates for specific time intervals were determined. The highest RSC values were obtained for papaya pulp extracts, consistently higher for the ripe samples in comparison with the unripe ones (86.4% and 41.3%). The DPPH· rates significantly differ for the unripe and ripe papaya extracts, especially for the first time range. They are more than double for the ripe papaya. These values were 2.70, 4.00, 3.25, 2.75 μM/s for the peel, pulp, seed, seed-pulp extracts from the ripe papaya and only 1.00, 1.65, 1.40, 1.80 μM/s for the unripe samples. DPPH· kinetic approach can be useful for a fast and simple evaluation of the overall antioxidant properties of fruit extracts

FTIR–PCA Approach on Raw and Thermally Processed Chicken Lipids Stabilized by Nano-Encapsulation in β-Cyclodextrin

This study evaluated similarities/dissimilarities of raw and processed chicken breast and thigh lipids that were complexed by β-cyclodextrin, using a combined FTIR–PCA technique. Lipid fractions were analyzed as non-complexed and β-cyclodextrin-complexed samples via thermogravimetry, differential scanning calorimetry and ATR-FTIR. The lipid complexation reduced the water content to 7.67–8.33%, in comparison with the β-cyclodextrin hydrate (~14%). The stabilities of the complexes and β-cyclodextrin were almost the same. ATR-FTIR analysis revealed the presence of important bands that corresponded to the C=O groups (1743–1744 cm−1) in both the non-complexed and nano-encapsulated lipids. Furthermore, the bands that corresponded to the vibrations of double bonds corresponding to the natural/degraded (cis/trans) fatty acids in lipids appeared at 3008–3011 and 938–946 cm−1, respectively. The main FTIR bands that were involved in the discrimination of raw and processed chicken lipids, and of non-complexed and complexed lipids, were evaluated with PCA. The shifting of specific FTIR band wavenumbers had the highest influence, especially vibrations of the α(1→4) glucosidic bond in β-cyclodextrin for PC1, and CH2/3 groups from lipids for PC2. This first approach on β-cyclodextrin nano-encapsulation of chicken lipids revealed the possibility to stabilize poultry fatty components for further applications in various ingredients for the food industry

Fatty Acid Profile of Lipid Fractions of Mangalitza (<i>Sus scrofa domesticus</i>) from Northern Romania: A GC-MS-PCA Approach

Mangalitza pig (Sus scrofa domesticus) becomes more popular in European countries. The goal of this study was to evaluate the fatty acid profile of the raw and thermally processed Mangalitza hard fat from Northern Romania. For the first time, the gas chromatography-mass spectrometry-Principal component analysis technique (GC-MS-PCA)—was applied to evaluate the dissimilarity of Mangalitza lipid fractions. Three specific layers of the hard fat of Mangalitza from Northern Romania were subjected to thermal treatment at 130 °C for 30 min. Derivatized samples were analyzed by GC-MS. The highest relative content was obtained for oleic acid (methyl ester) in all hard fat layers (36.1–42.4%), while palmitic acid was found at a half (21.3–24.1%). Vaccenic or elaidic acids (trans) were found at important concentrations of 0.3–4.1% and confirmed by Fourier-transform infrared spectroscopy. These concentrations are consistently higher in thermally processed top and middle lipid layers, even at double values. The GC-MS-PCA coupled technique allows us to classify the unprocessed and processed Mangalitza hard fat specific layers, especially through the relative concentrations of vaccenic/elaidic, palmitic, and stearic acids. Further studies are needed in order to evaluate the level of degradation of various animal fats by the GC-MS-PCA technique

Fatty Acid Profile of Lipid Fractions of Mangalitza (Sus scrofa domesticus) from Northern Romania: A GC-MS-PCA Approach

Mangalitza pig (Sus scrofa domesticus) becomes more popular in European countries. The goal of this study was to evaluate the fatty acid profile of the raw and thermally processed Mangalitza hard fat from Northern Romania. For the first time, the gas chromatography-mass spectrometry-Principal component analysis technique (GC-MS-PCA)&mdash;was applied to evaluate the dissimilarity of Mangalitza lipid fractions. Three specific layers of the hard fat of Mangalitza from Northern Romania were subjected to thermal treatment at 130 &deg;C for 30 min. Derivatized samples were analyzed by GC-MS. The highest relative content was obtained for oleic acid (methyl ester) in all hard fat layers (36.1&ndash;42.4%), while palmitic acid was found at a half (21.3&ndash;24.1%). Vaccenic or elaidic acids (trans) were found at important concentrations of 0.3&ndash;4.1% and confirmed by Fourier-transform infrared spectroscopy. These concentrations are consistently higher in thermally processed top and middle lipid layers, even at double values. The GC-MS-PCA coupled technique allows us to classify the unprocessed and processed Mangalitza hard fat specific layers, especially through the relative concentrations of vaccenic/elaidic, palmitic, and stearic acids. Further studies are needed in order to evaluate the level of degradation of various animal fats by the GC-MS-PCA technique

Estimation of the Controlled Release of Antioxidants from β-Cyclodextrin/Chamomile (<i>Matricaria chamomilla</i> L.) or Milk Thistle (<i>Silybum marianum</i> L.), Asteraceae, Hydrophilic Extract Complexes through the Fast and Cheap Spectrophotometric Technique

This is the first study on the modeling of the controlled release of the estimated antioxidants (flavonoids or flavonolignans) from β-cyclodextrin (β-CD)/hydrophilic vegetable extract complexes and the modeling of transdermal pharmaceutical formulations based on these complexes using an overall estimation by the spectrophotometric method. The Korsmeyer–Peppas model was chosen for evaluating the release mechanisms. β-CD/chamomile (Matricaria chamomilla L., Asteraceae) ethanolic extract and β-CD/milk thistle (Silybum marianum L., Asteraceae) ethanolic extract complexes were obtained by the co-crystallization method with good recovering yields of 55–76%, slightly lower than for β-CD/silibinin or silymarin complexes (~87%). According to differential scanning calorimetry (DSC) and Karl Fischer water titration (KFT), the thermal stability of complexes is similar to β-CD hydrate while the hydration water content is lower, revealing the formation of molecular inclusion complexes. In the Korsmeyer–Peppas model, β-CD/M. chamomilla flower extract complexes reveal Case II transport mechanisms, while the corresponding complexes with leaf extracts indicate non-Fickian diffusion for the controlled release of antioxidants in ethanol 60 and 96%. The same non-Fickian diffusion was revealed by β-CD/S. marianum extract and β-CD/silibinin complexes. On the contrary, almost all model transdermal pharmaceutical formulations based on β-CD/M. chamomilla extract complexes and all those based on β-CD/S. marianum extract complexes revealed non-Fickian diffusion for the antioxidant release. These results indicate that H-bonding is mainly involved in the diffusion of antioxidants into a β-CD based matrix, while the controlled release of antioxidants in model formulations is mainly due to hydrophobic interactions. Results obtained in this study can be further used for studying the particular antioxidants (namely rutin or silibinin, quantified, for example, by liquid chromatographic techniques) for their transdermal transport and biological effects in innovatively designed pharmaceutical formulations that can be obtained using “green” methods and materials

Karl Fischer Water Titration—Principal Component Analysis Approach on Bread Products

(1) Background: The water content and the way of bonding in the food matrices, including bread, can be easily and simply evaluated by Karl Fischer titration (KFT). The goal was to identify the main KFT parameters that influence the similarity/dissimilarity of commercial bread products, using multivariate statistical analysis. (2) Methods: Various commercial bread samples were analyzed by volumetric KFT and the water content, parameters from titration process and KFT kinetics were used as input for principal component analysis (PCA). (3) Results: The KFT water content was in the range of 35.1&ndash;44.2% for core samples and 19.4&ndash;22.9% for shell samples. The storage and transportation conditions consistently influence the water content of bread. The type of water molecules can be evaluated by means of KFT water reaction rates. The mean water reaction rates up to 2 min are consistently higher for bread core samples, which indicates a high fraction of &ldquo;surface&rdquo; water. PCA reveals the similarity of core samples and various bread types, as well as dissimilarity between bread parts, mainly based on KFT kinetic parameters. (4) Conclusions: KFT kinetics can be a useful tool for a rapid and simple differentiations between various types of bread products

Fatty acid profile of Romanian's common bean (Phaseolus vulgaris L.) lipid fractions and their complexation ability by β-cyclodextrin.

The goal of the present study was the evaluation of the fatty acid (FA) profile of lipid fraction from dry common beans (Phaseolus vulgaris L.) (CBO) harvested from North-East (NE) and South-West (SW) of Romania and to protect against thermal and oxidative degradation of the contained omega-3 and omega-6 polyunsaturated fatty acid (PUFA) glycerides by β-cyclodextrin (β-CD) nanoencapsulation, using kneading method. The most abundant FAs in the CBO samples were PUFAs, according to gas chromatography-mass spectrometry (GC-MS) analysis. Linoleic acid (methyl ester) was the main constituent, having relative concentrations of 43.4 (±1.95) % and 35.23 (±0.68) % for the lipid fractions separated from the common beans harvested from the NE and SW of Romania, respectively. Higher relative concentrations were obtained for the omega-3 α-linolenic acid methyl ester at values of 13.13 (±0.59) % and 15.72 (±0.30) % for NE and SW Romanian samples, respectively. The omega-3/omega-6 ratio consistently exceeds the lower limit value of 0.2, from where the PUFA glyceride mixture is valuable for the human health. This value was 0.32 (±0.02) for the NE samples and significantly higher for the CBO-SW samples, 0.51 (±0.01). These highly hydrophobic mixtures especially consisting of PUFA triglycerides provide β-CD complexes having higher thermal and oxidative stability. Kneading method allowed obtaining β-CD/CBO powder-like complexes with higher recovery yields of >70%. Thermal analyses of complexes revealed a lower content of hydration water (3.3-5.8% up to 110°C in thermogravimetry (TG) analysis and 154-347 J/g endothermal effect in differential scanning calorimetry (DSC) analysis) in comparison with the β-CD hydrate (12.1% and 479.5-480 J/g, respectively). These findings support the molecular inclusion process of FA moieties into the β-CD cavity. Attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) analysis reveals the formation of the β-CD/CBO inclusion complexes by restricting the vibration and bending of some bonds from the host and guest molecules. Moreover, powder X-ray diffractometry (PXRD) analysis confirm the formation of the host-guest complexes by modifying the diffractograms for β-CD/CBO complexes in comparison with the β-CD and β-CD + CBO physical mixtures. A significant reduction of the level of crystallinity from 93.3 (±5.3) % for β-CD to 60-60.9% for the corresponding β-CD/CBO complexes have been determined. The encapsulation efficiency (EE), the profile of FAs, as well as the controlled release of the encapsulated oil have also been evaluated. The EE was >40% in all cases, the highest value being obtained for β-CD/CBO-SW complex. The SFA content increased, while the unsaturated FA glycerides had lower relative concentrations in the encapsulated CBO samples. It can be emphasized that the main omega-3 FA (namely α-linolenic acid glycerides) had close concentrations in the encapsulated and raw CBOs (13.13 (±0.59) % and 14.04 (±1.54) % for non-encapsulated and encapsulated CBO-NE samples, 15.72 (±0.30) % and 12.41 (±1.95) % for the corresponding CBO-SW samples, respectively). The overall unsaturated FA content significantly decreased after complexation (from 19.03-19.16% for the raw CBOs to 17.3-17.7% for encapsulated oils in the case of MUFAs, and from 55.7-58.8% to 35.13-43.36% for PUFAs). On the other hand, the omega-3/omega-6 ratio increased by β-CD nanoencapsulation to 0.51 (±0.07) and 0.76 (0.26) for β-CD/CBO-NE and β-CD/CBO-SW complexes, respectively. As a conclusion, the lipid fractions of the Romanian common beans are good candidates for β-CD complexation and they can be protected against thermal and oxidative degradation in common beans based food products such as functional foods or food supplements using natural CDs