Exploring the Bioactive Content of Liquid Waste and Byproducts Produced by Two-Phase Olive Mills in Laconia (Greece): Is There a Prospect for Added-Value Applications?

The use of a two-phase decanter (TwPD) for olive-oil extraction produces wastes and byproducts (a small volume of water from oil washing, olive leaves from the defoliator, and a high moisture pomace which can be destoned) that contain valuable bioactive compounds, such as phenolics and/or triterpenic acids. So far, there is no (water) or limited information (leaves and the destoned pomace fraction) on their content of bioactives, especially triterpenic acids. To contribute to the characterization of such streams from cultivars of international interest, in the present study, samples obtained from five mills from the region of Laconia (from one or two harvests) in Greece, where Koroneiki cv dominates, were screened for phenols and/or triterpenic acids. The leaves and pomace were dried at two temperatures (70 °C and/or 140 °C), and the pomace was also destoned before analysis. The liquid wastes contained low amounts of total (TPC) phenols (<140 mg gallic acid/L), hydroxytyrosol (<44 mg/L), and tyrosol (<33 mg/L). The olive leaves varied widely in TPC (12.8-57.4 mg gallic acid/g dry leaf) and oleuropein (0.4-56.8 mg/g dry leaf) but contained an appreciable amount of triterpenic acids, mainly oleanolic acid (~12.5-31 mg/g dry leaf, respectively). A higher drying temperature (140 vs. 70 °C) affected rather positively the TPC/oleuropein content, whereas triterpenic acids were unaffected. The destoned pomace TPC was 15.5-22.0 mg gallic acid/g dw, hydroxytyrosol 3.9-5.6 mg/g dw, and maslinic 5.5-19.3 mg/g dw. Drying at 140 °C preserved better its bioactive phenols, whereas triterpenic acids were not influenced. The present findings indicate that TwPD streams may have a prospect as a source of bioactives for added-value applications. Material handling, including drying conditions, may be critical but only for phenols.

Effects of Enriched-in-Oleuropein Olive Leaf Extract Dietary Supplementation on Egg Quality and Antioxidant Parameters in Laying Hens.

The objective of the present study was to evaluate the effects of an olive leaf extract obtained with an up-to-date laboratory method, when supplemented at different levels in laying hens' diets, on egg quality, egg yolk antioxidant parameters, fatty acid content, and liver pathology characteristics. Thus, 96 laying hens of the ISA-Brown breed were allocated to 48 experimental cages with two hens in each cage, resulting in 12 replicates per treatment. Treatments were: T1 (Control: basal diet); T2 (1% olive leaf extract); T3 (2.5% olive leaf extract); T4 (Positive control: 0.1% encapsulated oregano oil). Eggshell weight and thickness were improved in all treatments compared to the control, with T2 being significantly higher till the end of the experiment (p < 0.001). Egg yolk MDA content was lower for the T2 and T4 groups, while total phenol content and Haugh units were greater in the T2. The most improved fatty acid profile was the one of T3 yolks. The α-tocopherol yolk content was higher in all groups compared to T1. No effect was observed on cholesterol content at any treatment. Based on the findings, it can be inferred that the inclusion of olive leaf extract at a concentration of 1% in the diet leads to enhancements in specific egg quality attributes, accompanied by an augmentation of the antioxidant capacity.

Improving the functionality of virgin and cold-pressed edible vegetable oils: Oxidative stability, sensory acceptability and safety challenges.

In recent years, there has been a growing demand for minimally processed foods that offer health benefits and premium sensory characteristics. This trend has led to increased consumption of virgin (VOs) and cold-pressed (CPOs) oils, which are rich sources of bioactive substances. To meet consumer needs for new oil products conferring multi-functional properties over a longer storage period, the scientific community has been revisiting traditional enrichment practices while exploring novel fortification technologies. In the last four years, the interest has been growing faster; an ascending number of annually published studies are about the addition of different plant materials, agri-food by-products, or wastes (intact or extracts) to VOs and CPOs using traditional or innovative fortification processes. Considering this trend, the present review aims to provide an overview and summarize the key findings from relevant papers that were retrieved from extensively searched databases. Our meta-analysis focuses on exposing the most recent trends regarding the exploitation of VOs and CPOs as substrates, the fortification agents and their form of use, as well as the fortification technologies employed. The review critically discusses possible health claim and labeling issues and highlights some chemical and microbial safety concerns along with authenticity issues and gaps in quality specifications that manufacturers have yet to address. All these aspects are examined from the perspective of developing new oil products with well-balanced techno-, senso- and bio-functional characteristics.

Effects of Dietary Supplementation of a Resin-Purified Aqueous-Isopropanol Olive Leaf Extract on Meat and Liver Antioxidant Parameters in Broilers.

Olive leaves are byproducts οf the agro-industrial sector and are rich in bioactive compounds with antioxidant properties. They could be supplemented in poultry diets powdered or less frequently as extracts to improve performance, health and product quality. The objective of this study was to investigate the possible beneficial effects of an aqueous isopropanol olive leaf extract-purified through filtration (250-25 µm) and a resin (XAD-4)-when supplemented in broiler chickens' diets, on meat quality parameters, focusing mainly on antioxidant parameters as there is limited published information. For this purpose, four-hundred-and-eighty-day-old broilers were randomly assigned to four dietary treatments: T1 (control: basal diet); T2 (1% olive leaf extract); T3 (2.5% olive leaf extract); T4 (positive control: 0.1% encapsulated oregano oil commercially used as feed additive). At the end of the experimental period (day 42), the birds were slaughtered, and samples from breast, thigh meat and liver were collected for antioxidant parameters evaluation. On day 1, after slaughter, in thigh meat, Malondialdehyde (MDA) was lower in T2 compared to T3, and total phenolic content (TPC) was higher in T2 compared to T3 and T4. Total antioxidant capacity (TAC) was increased in T2 and T4 breast meat compared to the control. In liver, T4 treatment resulted in higher TPC. The lack of dose-dependent effect for olive leaf extract may be attributed to the pro-oxidant effects of some bioactive compounds found in olive leaves, such as oleuropein, when supplemented at higher levels. In summary, it can be inferred that the inclusion of 1% olive leaf extract in the feed of broilers has the potential to mitigate oxidation in broiler meat and maybe enhance its quality.

Minor bioactive lipids.

Bioactive lipids-major and minor-comprise an array of compounds belonging to different chemical categories. Among the minor bioactive lipids carotenoids, sterols and tocochromanols attract continuously the interest of food scientists, nutritionists and medical doctors for their importance in food processing, preservation and for their health properties. Provitamin A and non-provitamin A carotenoids are found in various food sources of plant and animal origin and are added to foods as colorants. Their interactions with other food ingredients are critical because of their role against reactive oxygen species. The role of cholesterol through the diet after decades of disputes is better justified whereas at the same time emphasis is given to the technological and health aspects of phytosterols, which became very efficiently part of the daily diet for many population groups. Last but not least the importance of vitamin E is in a continuous debate for over 100years whereas studies on tocotrienols are intensified as a result of a transient to palm oil product consumption globally. Chemistry, natural occurrence, absorption and metabolism, dietary intake and dietary recommendations, major health impacts and key technological issues are updated and discussed with the support of recent findings.

White rice enrichment with phenols upon cooking in olive leaf infusion: a preliminary study.

BACKGROUND: White rice is poor in health-promoting phytochemicals; therefore, the production of a phenol-enriched commodity is highly desirable. Recent findings on its enrichment via cooking in plant extracts are promising, yet studies employing aqueous extracts of olive leaves (OLs), containing well-recognized bioactive phenols (e.g. oleuropein) are absent. In addition, little is known about the levels of phenols that are maintained after rice drying and rehydration, an important aspect for the future design of 'ready-to-eat' functional rice. RESULTS: The examination, for the first time, of white rice adsorption capacity of phenols from OLs upon cooking in infusions containing different levels of phenols, after freeze-drying and rehydration, showed the following: (i) the total phenol content, the antioxidant activity (assessed via 2,2-diphenyl-1-picrylhydrazyl radical and ferric reducing antioxidant power assays), the oleuropein and luteolin-7-O-glucoside levels increased dose dependently; (ii) upon rehydration, the average decrease of total phenol content and antioxidant activity values was significantly lower when an exact volume of water was used compared with an excess (~10% versus 63%). A similar trend was observed for oleuropein (36% versus 83%) and the luteolin-7-O-glucoside (24 versus 82%) levels; (iii) the dried enriched kernels were less bright with a hay-yellow hue (CIELab coordinates). CONCLUSION: White rice enrichment with biophenols from OLs, a by-product of olive tree cultivation, was successful using a simple approach. Despite leaching upon freeze-drying/rehydration, sufficient amounts were maintained to obtain a functional rice that could serve as an alternative dietary source of OLs phenols to non-traditional olive tree product consumers or those refraining from sodium and fats. © 2023 Society of Chemical Industry.

The Contribution of Theoretical Prediction Studies to the Antioxidant Activity Assessment of the Bioactive Secoiridoids Encountered in Olive Tree Products and By-Products.

Assessment of the antioxidant activity of different types of natural compounds is a complex research area that encompasses various in vitro tests and in vivo studies. Sophisticated modern analytical tools permit the unambiguous characterization of the compounds present in a matrix. The contemporary researcher, knowing the chemical structure of the compounds present, can carry out quantum chemical calculations that provide important physicochemical information assisting the prediction of antioxidant potential and the mechanism behind the activity of target compounds before further experimentation. The efficiency of calculations is steadily improved due to the rapid evolution of both hardware and software. It is possible, consequently, to study compounds of medium or even larger size, incorporating also models that simulate the liquid phase (solution). This review contributes to the establishment of theoretical calculations as an inherent part of the antioxidant activity assessment process, having as a case study the complex mixtures of olive bioactive secoiridoids (oleuropein, ligstroside, and related compounds). The literature indicates great variability in theoretical approaches and models used so far for only a limited number of this group of phenolic compounds. Proposals are made for standardization of methodology (reference compounds, DFT functional, basis set size, and solvation model) to facilitate comparisons and communication of findings.

Bay Laurel (Laurus nobilis L.) Essential Oil as a Food Preservative Source: Chemistry, Quality Control, Activity Assessment, and Applications to Olive Industry Products.

Essential oils (EOs) find application as flavoring agents in the food industry and are also desirable ingredients as they possess preservative properties. The Mediterranean diet involves the use of a lot of herbs and spices and their products (infusions, EOs) as condiments and for the preservation of foods. Application of EOs has the advantage of homogeneous dispersion in comparison with dry leaf use in small pieces or powder. Among them, Laurus nobilis (bay laurel) L. EO is an interesting source of volatiles, such as 1,8-cineole and eugenol, which are known for their preservative properties. Its flavor suits cooked red meat, poultry, and fish, as well as vegetarian dishes, according to Mediterranean recipes. The review is focused on its chemistry, quality control aspects, and recent trends in methods of analysis and activity assessment with a focus on potential antioxidant activity and applications to olive industry products. Findings indicate that this EO is not extensively studied in comparison with those from other Mediterranean plants, such as oregano EO. More work is needed to establish authenticity and activity methods, whereas the interest for using it for the preparation of flavored olive oil or for the aromatization and preservation of table oils must be further encouraged.

Strategic Priorities of the Scientific Plan of the European Research Infrastructure METROFOOD-RI for Promoting Metrology in Food and Nutrition.

The pan-European distributed Research Infrastructure for Promoting Metrology in Food and Nutrition (METROFOOD-RI) has evolved in the frame of the European Strategy Forum on Research Infrastructures (ESFRI) to promote high-quality metrology services across the food chain. The METROFOOD-RI comprises physical facilities and electronic facilities. The former includes Reference Material plants and analytical laboratories (the 'Metro' side) and also experimental fields/farms, processing/storage plants and kitchen-labs (the 'Food' side). The RI is currently prepared to apply for receiving the European Research Infrastructure Consortium (ERIC) legal status and is organised to fulfil the requirements for operation at the national, European Union (EU) and international level. In this view, the METROFOOD-RI partners have recently reviewed the scientific plan and elaborated strategic priorities on key thematic areas of research in the food and nutrition domain to which they have expertise to contribute to meet global societal challenges and face unexpected emergencies. The present review summarises the methodology and main outcomes of the research study that helped to identify the key thematic areas from a metrological standpoint, to articulate critical and emerging issues and demands and to structure how the integrated facilities of the RI can operate in the first five years of operation as ERIC.

On the Role of the Carboxyl Group to the Protective Effect of o-dihydroxybenzoic Acids to Saccharomyces cerevisiae Cells upon Induced Oxidative Stress.

In the present work, the role of the carboxyl group of o-dihydroxybenzoic acids (pyrocatechuic, 2,3-diOH-BA and protocatechuic, 3,4-diOH-BA) on the protection against induced oxidative stress in Saccharomyces cerevisiae was examined. Catechol (3,4-diOH-B) was included for comparison. Cell survival, antioxidant enzyme activities, and TBARS level were used to evaluate the efficiency upon the stress induced by H2O2 or cumene hydroperoxide. Theoretical calculation of atomic charge values, dipole moment, and a set of indices relevant to the redox properties of the compounds was also carried out in the liquid phase (water). Irrespective of the oxidant used, 2,3-diOH-BA required by far the lowest concentration (3-5 µM) to facilitate cell survival. The two acids did not activate catalase but reduced superoxide dismutase activity (3,4-diOH-BA>2,3-diOH-BA). TBARS assay showed an antioxidant effect only when H2O2 was used; equal activity for the two acids and inferior to that of 3,4-diOH B. Overall, theoretical and experimental findings suggest that the 2,3-diOH-BA high activity should be governed by metal chelation. In the case of 3,4-diOH BA, radical scavenging increases, and chelation capacity decreases. The lack of carboxyl moiety (3,4-diOH B) improves to radical scavenging, interaction with lipophilic free radicals, and antioxidant enzymes. The present study adds to our knowledge of the antioxidant mechanism of dietary phenols in biological systems.

Suggestions on the Contribution of Methyl Eugenol and Eugenol to Bay Laurel (Laurus nobilis L.) Essential Oil Preservative Activity through Radical Scavenging.

The present study examined the radical scavenging potential of the two benzene derivatives found in the bay laurel essential oil (EO), namely methyl eugenol (MEug) and eugenol (Eug), theoretically and experimentally to make suggestions on their contribution to the EO preservative activity through such a mechanism. Calculation of appropriate molecular indices widely used to characterize chain-breaking antioxidants was carried out in the gas and liquid phases (n-hexane, n-octanol, methanol, water). Experimental evidence was based on the DPPH• scavenging assay applied to pure compounds and a set of bay laurel EOs chemically characterized with GC-MS/FID. Theoretical calculations suggested that the preservative properties of both compounds could be exerted through a radical scavenging mechanism via hydrogen atom donation. Eug was predicted to be of superior efficiency in line with experimental findings. Pearson correlation and partial least square regression analyses of the EO antioxidant activity values vs. % composition of individual volatiles indicated the positive contribution of both compounds to the radical scavenging activity of bay laurel EOs. Eug, despite its low content in bay laurel EOs, was found to influence the most the radical scavenging activity of the latter.

FoodOmicsGR_RI. A Consortium for Comprehensive Molecular Characterisation of Food Products.

The national infrastructure FoodOmicsGR_RI coordinates research efforts from eight Greek Universities and Research Centers in a network aiming to support research and development (R&D) in the agri-food sector. The goals of FoodOmicsGR_RI are the comprehensive in-depth characterization of foods using cutting-edge omics technologies and the support of dietary/nutrition studies. The network combines strong omics expertise with expert field/application scientists (food/nutrition sciences, plant protection/plant growth, animal husbandry, apiculture and 10 other fields). Human resources involve more than 60 staff scientists and more than 30 recruits. State-of-the-art technologies and instrumentation is available for the comprehensive mapping of the food composition and available genetic resources, the assessment of the distinct value of foods, and the effect of nutritional intervention on the metabolic profile of biological samples of consumers and animal models. The consortium has the know-how and expertise that covers the breadth of the Greek agri-food sector. Metabolomics teams have developed and implemented a variety of methods for profiling and quantitative analysis. The implementation plan includes the following research axes: development of a detailed database of Greek food constituents; exploitation of "omics" technologies to assess domestic agricultural biodiversity aiding authenticity-traceability control/certification of geographical/genetic origin; highlighting unique characteristics of Greek products with an emphasis on quality, sustainability and food safety; assessment of diet's effect on health and well-being; creating added value from agri-food waste. FoodOmicsGR_RI develops new tools to evaluate the nutritional value of Greek foods, study the role of traditional foods and Greek functional foods in the prevention of chronic diseases and support health claims of Greek traditional products. FoodOmicsGR_RI provides access to state-of-the-art facilities, unique, well-characterised sample sets, obtained from precision/experimental farming/breeding (milk, honey, meat, olive oil and so forth) along with more than 20 complementary scientific disciplines. FoodOmicsGR_RI is open for collaboration with national and international stakeholders.

Virgin olive oil metabolomics: A review.

Metabolomics involvement in the study of foods is steadily growing. Such a rise is a consequence of the increasing demand in the food sector to address challenges regarding the issues of food safety, quality, and authenticity in a more comprehensive way. Virgin olive oil (VOO) is a key product of the Mediterranean diet, with a globalized consumer interest as it may be associated with various nutritional and health benefits. Despite the strict legislation to protect this high added-value agricultural commodity and offer guarantees to consumers and honest producers, there are still analytical issues needing to be further addressed. Thus, this review aims to present the efforts made using targeted and untargeted metabolomics approaches, namely nuclear magnetic resonance (NMR) spectroscopy and mass spectrometry-based techniques (mainly LC/GC-MS) combined with multivariate statistical analysis. Case-studies focusing on geographical/varietal classification and detection of adulteration are discussed with regards to the identification of possible markers. The advantages and limitations of each of the aforementioned techniques applied to VOO analysis are also highlighted.

Getting inside on virgin olive oil (VOO) photooxidation kinetics through combined generalized 2D correlation analysis and moving window 2D correlation analysis of ATR-FTIR spectra.

The generalized two-dimensional correlation spectroscopy (g2D-COR spectroscopy) analysis combined with its extended version moving-window 2D-COR (MW-2D-COR) was performed on a set of kinetic ATR-FTIR spectral data. The former is a mathematical method that is applied to a set of spectra collected for a sample exposed to an external perturbation (e.g. storage time). Virgin olive oils (VOOs) of similar fatty acid composition, chlorophyll, and a-tocopherol content were photooxidized (10,912 Lx, no headspace, 24 h). The proposed approach revealed hidden information under specific ATR-FTIR bands and the order of events was established using appropriate rules. MW-2D-COR analysis displayed the evolution of changes during storage. In this way, the detection of the time interval upon which spectral changes are observed was evidenced. As an overview, MW plots of the analyzed samples revealed three time-zones in which changes tend to maximize, with the first one to reach a peak at ~2.5 h. The area around 2850-2930 cm-1 including bands assigned to the symmetric and asymmetric stretching vibration of the aliphatic -CH2- bonds, was the one found to be affected in all VOOs. The time interval upon which spectral changes are first detected in the corresponding area could serve as an index for the commencement of the loss of freshness. Present findings highlight the need to combine the two types of correlation analyses to obtain meaningful information on VOO photooxidation kinetics. Lipid scientists may gain an extra tool in their efforts to understand oxidation phenomena.

Toward a Harmonized and Standardized Protocol for the Determination of Total Hydroxytyrosol and Tyrosol Content in Virgin Olive Oil (VOO). The Pros of a Fit for the Purpose Ultra High Performance Liquid Chromatography (UHPLC) Procedure.

Τoward a harmonized and standardized procedure for the determination of total hydroxytyrosol and tyrosol content in virgin olive oil (VOO), the pros of a recently published in house validated ultra high performance liquid chromatography (UHPLC) protocol are discussed comparatively with those of other procedures that determine directly or indirectly the compounds hosted under the health claim on "olive oil polyphenols" (EC regulation 432/2012). Authentic VOOs were analyzed with five different liquid chromatographic separation protocols and 1H-NMR one in five different laboratories with expertise in VOO phenol analysis within three months. Data comparison indicated differences in absolute values. Method comparison using appropriate tools (Passing-Bablok regression and Bland Altman analyses) for all protocols vs. the UHPLC one indicated slight or statistically significant differences. The results were also discussed in terms of cost effectiveness, detection means, standard requirements and ways to calculate the total hydroxytyrosol and tyrosol content. Findings point out that the in-house validated fit for the purpose UHPLC protocol presents certain pros that should be exploited by the interested parties. These are the simplicity of sample preparation, fast elution time that increase the number of samples analyzed per day and integration of well-resolved peaks with the aid of only two commercially available external standards. Importance of correction factors in the calculations is stressed.

Real time monitoring of the combined effect of chlorophyll content and light filtering packaging on virgin olive oil photo-stability using mesh cell-FTIR spectroscopy.

The present work aimed at examining the combined effect of chlorophyll content and light filtering packaging material on the photo-stability of virgin olive oil (VOO) via mesh cell-FTIR spectroscopy monitoring. Four different VOOs of Koroneiki cultivar differing in total chlorophyll content (∼12-46 mg/kg) were exposed in parallel to direct visible light (6000 lx, 24 °C, 344 h) and FTIR spectra were recorded periodically with or without applying light protection by an industrial filter used for packaging. Findings suggested that the protective role of light filtering material was more evident in the VOO with the lowest total chlorophyll content. Real time monitoring of VOO by mesh cell-FTIR was found to be a useful tool to follow the combined effect of pro-oxidant chlorophylls and the protective light filtering materials on the photo-oxidation process of VOO employing a minute sample amount.

In House Validated UHPLC Protocol for the Determination of the Total Hydroxytyrosol and Tyrosol Content in Virgin Olive Oil Fit for the Purpose of the Health Claim Introduced by the EC Regulation 432/2012 for "Olive Oil Polyphenols".

An ongoing challenge in olive oil analytics is the development of a reliable procedure that can draw the consensus of all interested parties regarding the quantification of concentrations above the required minimum value of 5 mg of bioactive "olive oil polyphenols" per 20 g of the oil, to fulfill the health claim introduced by the European Commission (EC) Regulation 432/2012. An in-house validated ultra-high performance liquid chromatography (UHPLC) protocol fit for this purpose is proposed. It relies on quantification of the total hydroxytyrsol (Htyr) and tyrosol (Tyr) content in the virgin olive oil (VOO) polar fraction (PF) before and after acidic hydrolysis of their bound forms. PF extraction and hydrolysis conditions were as previously reported. The chromatographic run lasts ~1/3 of the time needed under high performance liquid chromatography (HPLC) conditions, this was also examined. Eluent consumption for the same piece of information was 6-fold less. Apart from being cost effective, a larger number of samples can be analyzed daily with less environmental impact. Two external curves, detection at 280 nm and correction factors for molecular weight difference are proposed. The method, which is fit for purpose, is selective, robust with satisfactory precision (percentage relative standard deviation (%RSD) values < 11%) and recoveries higher than 87.6% for the target analytes (Htyr, Tyr). Standard operational procedures are easy to apply in the olive oil sector.

Functional Teas from the Leaves of Arbutus unedo: Phenolic Content, Antioxidant Activity, and Detection of Efficient Radical Scavengers.

The phenolic content/composition and antioxidant activity of hot/cold infusion and decoction from the leaves of Arbutus unedo were studied for the first time. 1,1-diphenyl-2-picrylhydrazyl (DPPH●), 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) radical cation (ABTS●+), crocin-bleaching, copper-reducing, and liposome accelerated oxidation assays were used for the evaluation of the activity in vitro. In vivo, the extracts were examined for their ability to protect S. cerevisiae cells from H2O2 induced oxidative stress. An on-line high-performance liquid chromatography-DPPH● assay was applied to identify potent radical scavengers and comment on their contribution to the total activity. The addition of leaves to boiling water (decoction) was the most appropriate practice to apply since the highest phenol intake (220.2 mg gallic acid/cup served) was obtained. Additionally, its antioxidant activity was equal or superior to that of the other extracts. Flavonols (~51-61 mg/g dry extract) were the main phenols in all the extracts, with quercitrin accounting for ~20% of the total phenol amount. The on-line DPPH● method verified the high potency of the decoction and indicated as the most active radical scavengers, two galloylquinic acid derivatives and myricitrin, accounting for ~28-45% and ~11-13% of the total scavenging, respectively. Present data may contribute to the future exploitation of A. unedo leaves by the food industry for health-promoting herbal tea preparations and dietary supplements.

Effect of Cα-Cß Bond Type on the Radical Scavenging Activity of Hydroxy Stilbenes: Theoretical Insights in the Gas and Liquid Phase.

Density functional theory/Becke's three-parameter hybrid functional combined with the Lee-Yang-Parr correlation functional (DFT/B3LYP) was used to examine the radical scavenging potential of resveratrol, piceatannol, and their dehydro/dihydro counterparts. For this reason, the values of molecular descriptors predicting the hydrogen atom transfer (HAT) and the single electron transfer preceding (SET-PT) or following a proton transfer (SPLET) were computed in the gas and liquid (benzene, water) phases. The double bond, resulting in molecular planarity, was predicted to favor the single hydrogen or electron transfer. The triple bond, resulting in a linear backbone, was predicted to decrease the ease of these transfers, whereas the saturation, resulting in loss of planarity, was expected to decrease the activity even more. The impact of saturation was predicted to be detrimental for resveratrol. However, for piceatannol, an enhancement of activity was proposed only under stepwise HAT because allylic hydrogen atoms could be prone for abstraction after the formation of quinone. The predictions (gas, liquid phase) were in agreement with experimental evidence for resveratrol and its derivatives. The lipophilicity, which may affect antioxidant activity in real systems, increased according to partition coefficient (log P) values as follows: dihydrostilbene > stilbene > dehydrostilbene. On the basis of dipole moment values, no clear trend was observed.

Applicability of PTR-MS in the quality control of saffron.

The applicability of the emerging non-destructive technique, proton transfer reaction mass spectrometry (PTR-MS), was explored for the first time in the quality control of saffron. Monitoring of volatile organic compounds (VOCs) was achieved using a minute sample (35 mg). Fresh saffron was stored under selected conditions (25 and 40 °C, aw=0.64) over a five weeks period to produce lower quality material, which was used to prepare mixtures with fresh saffron. Analysis showed that the VOCs fingerprint changed upon storage, and the concentration of initially dominant VOC safranal decreased progressively. Examination of calculated and recorded fingerprints for various admixtures showed that PTR-MS VOCs analysis, in combination with chemometrics, could be used to screen for the presence of lower quality saffron in a commercial product in a few minutes. The technique can be used in a complementary fashion, adding to the battery of advanced analytical techniques available to address the quality and authenticity issues of saffron.