Development of an antioxidant formula based on peanut by-products and effects on sensory properties and aroma stability of fortified peanut snacks during storage.

BACKGROUND: An antioxidant formula based on peanut skins and hulls was developed and characterized for total and single polyphenols, as well as antioxidant power, considering the contribution provided by each peanut by-product. Subsequently, it was evaluated for its effect on the sensory properties and aroma stability of peanut bars over a 100-day period. To this purpose, snacks fortified, or not, with the natural additive were experimentally produced. RESULTS: Peanut hulls contributed to a greater extent than skins with respect to boosting the content of bioactives and the antioxidnt activity of the antioxidant formula, which was marked by a phenol content of (approximately 807 mg gallic acid equivalents g-1 ) and a 2,2-diphenyl-1-picrylhydrazyl activity similar to that of butylated hydroxytoluene (85.96% and 89.30%, respectively). From a sensory perspective, the incorporation of the formulation in snacks caused only a slightly stronger perception of astringent and bitter notes. Pyrazines, phenol, furan and pyrrole derivatives defined the aroma of snacks, being more abundant in fortified than in conventional samples. Such volatiles faded over storage, with different trends in the examined products. For example, the sum of 2,5-dimethylpyrazine, 2-ethylpyrazine and 2,3-dimethylpyrazine was 9.49 and 8.87 ppm at day 15; 5.57 and 7.16 ppm at day 45; and 5.03 and 4.65 ppm at day 100, respectively, in fortified and conventional snacks. Hydroxymethylfurfural decreased constantly over storage in conventional samples and only after day 45 in fortified bars. CONCLUSION: Overall, the antioxidant formulation did not compromise the sensory desirability of peanut snacks and induced a preservative effect on their aroma, especially during the first 15 days of storage. © 2020 Society of Chemical Industry.

Flavonoid Composition of Tarocco (Citrus sinensis L. Osbeck) Clone "Lempso" and Fast Antioxidant Activity Screening by DPPH-UHPLC-PDA-IT-TOF.

INTRODUCTION: Clonal selection and hybridisation are valid strategies to obtain fruits with enhanced sensorial and nutraceutical properties. Within Citrus sinensis varieties, Tarocco clone "Lempso" is a typical product of the Calabria region (Italy) characterised by its red pulp. This is the first report concerning its accurate profiling. OBJECTIVE: To characterise in detail the flavonoid composition of Lempso clone and to compare its antioxidant potential with other Citrus varieties by a fast screening method. METHODOLOGY: Extracts were subjected to solid phase extraction and the qualitative/quantitative profile was elucidated through ultra-high performance liquid chromatography (UHPLC) coupled to photodiode array (PDA) and ion trap time-of-flight (IT-TOF) mass spectrometry detection, and compared to both Cleopatra mandarin (Citrus reticulata) and blood orange (Citrus sinensis (L.) Osbeck) Sanguinello varieties. The antioxidant activity was assessed by pre-column 2,2'-diphenyl-1-picrylhydrazyl (DPPH) reaction coupled to UHPLC-PDA. RESULTS: Lempso is characterised by flavonoids (17) and anthocyanins (8). Flavanones content (Hesperidin: 57.19 ± 0.49, Vicenin-2: 4.59 ± 0.03, Narirutin: 5.78 ± 0.13 mg/100 mL) was considerably higher than Cleopatra and Sanguinello varieties. The developed DPPH-UHPLC-PDA method provides information regarding the single contributions to antioxidant activity, highlighting how Ferulic acid, Quercetin and Cyanidin derivatives possess considerable radical scavenging activity (> 50%). The total antioxidant activity was also evaluated and compared with positive controls, showing higher scavenging activity than Cleopatra and Sanguinello (IC50 : 333.76 ± 10.81 µg/mL vs. 452.62 ± 10.81 and 568.39 ± 26.98 µg/mL, respectively). CONCLUSION: These data evidence the nutraceutical potential of Lempso variety, which could be an ingredient for functional beverages. Copyright © 2017 John Wiley & Sons, Ltd.

Exploring Influence of Production Area and Harvest Time on Specialized Metabolite Content of Glycyrrhiza glabra Leaves and Evaluation of Antioxidant and Anti-Aging Properties.

Calabrian Glycyrrhiza glabra is one of the most appreciated licorice varieties worldwide, and its leaves are emerging as a valuable source of bioactive compounds. Nevertheless, this biomass is usually discarded, and its valorization could contribute to boost the economic value of the licorice production chain. In this study, the effects of production area and harvest time on the specialized metabolite content of G. glabra leaves (GGL) and also the antioxidant and anti-aging properties are evaluated to explore the potential of this untapped resource and to select the most optimal harvesting practices. GGL exhibited high levels of specialized metabolites (4-30 g/100 g of dry leaf) and the most abundant ones are pinocembrin, prenylated flavanones (licoflavanone and glabranin), and prenylated dihydrostilbenes. Their levels and antioxidant capacity in extracts are influenced by both production area and harvest time, showing a decisive role on specialized metabolites accumulation. Interestingly, GGL extracts strongly attenuate the toxicity of α-synuclein, the intracellular reactive oxygen species (ROS) content, and cellular senescence on Saccharomyces cerevisiae expressing human α-synuclein model, showing great potential to prevent aging and age-related disorders. These results provide insights into the phytochemical dynamics of GGL, identifying the best harvesting site and period to obtain bioactive-rich sources with potential uses in the food, nutraceutical, and pharmaceutical sectors.

UHPLC-PAD Protocol for the Simultaneous Identification of Polyphenols and Bitter Acids: Organoleptic and Nutraceutical Fingerprinting of Bergamot-Flavored Craft Beer.

In this study, a UHPLC-PDA method for the simultaneous identification of polyphenols and bitter acids (alpha, beta, and isoalpha) in beer was developed. The resulting chemical profiles were leveraged to distinguish the characteristics of four (IPA, Lager, Blanche, ALE) bergamot-flavored beers, produced on a pilot-scale plant. In a streamlined 29 min analysis, thirty polyphenols and fourteen bitter acids were successfully identified under optimized separation conditions. Validation, encompassing parameters such as LOD (from 0.028 ppm for isorhamnetin to 0.106 for narirutin), LOQ (from 0.077 ppm for naringenin to 0.355 for narirutin), R2 (always more than 0.9992), repeatability (from 0.67% for tangeretin to 6.38% for myricetin), and reproducibility (from 0.99% for sinensetin to 6% for naringin), was conducted for polyphenol quantification using constructed calibration curves with seven levels. Exploring polyphenolic components as potential discriminators among different beer styles, a total of thirty-two polyphenolic compounds were identified and quantified, including characteristic bergamot peel polyphenols like neoeriocitrin (from 7.85 ppm for CBS2 to 11.95 ppm in CBS1); naringin (from 4.56 ppm for CBS4 to 10.96 in CBS1), and neohesperidin (from 5.93 in CBS3 to 15.95 for CBS2). The multivariate analysis provided additional insights into variations among specific beer styles, revealing discrepancies in the presence or relative concentrations of specific compounds linked to brewing ingredients and processes. This research enhances the fingerprinting of the chemistry governing beer quality through a straightforward and cost-effective analytical approach.

The LimoFish Circular Economy Process for the Marine Bioeconomy.

The outcomes of applying the zero-waste extraction "LimoFish" process based on defatting fish processing waste with limonene to leftovers of European sardine (Sardina pilchardus) and European anchovy (Engraulis encrasicolus), compared to conventional extraction with oil-derived solvents such as n-hexane and with petroleum ether, show that the process has general applicability. Meeting the principles of green extraction and those of the marine biorefinery requiring high process efficiency, the process establishes an "innovation through integration" circular economy production route enabling the marine bioeconomy.

A Predictive Model to Correlate Amino Acids and Aromatic Compounds in Calabrian Honeys.

To better understand the biochemistry of the organoleptic properties of honey influencing its commercial value, a predictive model for correlating amino acid profiles to aromatic compounds was built. Because the amino acid composition of different varieties of honey plays a key role as a precursor of specific aroma bouquets, it is necessary to relate the amino acid typesetting to aromatic molecules. A selection of unifloral honeys produced in Calabria, South Italy, were used, and a new methodology based on the use of HILIC-UHPLC-ESI-MS/MS and HS-SPME-GC-MS combined with multivariate processing has been developed. This study, carried out for the first time on honey, shows its excellent potential as a modern analytical tool for a rapid multicomponent analysis of food-quality indicators. Data obtained showed strong positive linear correlations between aldehydes and isoleucine, valine, leucine, and phenylalanine. Furans are correlated with isoleucine, leucine, and phenylalanine; hydrocarbons with serine, glutamic acid, and aspartic acid; and ketones with serine, alanine, glutamine, histidine, asparagine, and lysine. Alcohols were more associated with tyrosine than esters with arginine. Proline, tryptophan, and threonine showed poor correlations with all the classes of aroma compounds.

Effect of microbial fermentation on functional traits and volatiloma profile of pâté olive cake.

In this study, the pâté olive cake (POC), a by-product of the olive oil industry, was subjected to fermentation in a bioreactor using three microbial strains, Lactiplantibacillus plantarum, Wickerhamomyces anomalus and Candida boidinii, previously isolated from fermented table olive brines. Chemical, microbiological and molecular analyses were carried out at the beginning and at the end of fermentation. The lowest pH value (4.09) was reached after 10 days in sample inoculated with C. boidinii. Microbiological analyses exhibited the dominance of yeasts throughout the whole process (from 5.5 to 7.80 Log10 CFU/g), as confirmed by PCR-DGGE analysis. The microbial cultures affected both phenolic and volatile organic compound profiles. Moreover, the POC samples treated with different microbial strains were investigated for biological assays. The sample fermented with W. anomalus showed the greatest diffusion speed of transepithelial transport through Caco-2 cell, the highest inhibitory activity towards the tested cyclooxygenases and the highest antioxidant activity.

Onion Peel: Turning a Food Waste into a Resource.

Food waste is a serious problem for food processing industries, especially when it represents a loss of a valuable source of nutrients and phytochemicals. Increasing consumer demand for processed food poses the problem of minimizing waste by conversion into useful products. In this regard, onion (Allium cepa) waste consisting mainly of onion skin is rich in bioactive phenolic compounds. Here, we characterized the flavonoid profiles and biological activities of onion skin wastes of two traditional varieties with protected geographical indication (PGI), the red "Rossa di Tropea" and the coppery "Ramata di Montoro", typically cultivated in a niche area in southern Italy. The phytochemical profiles of exhaustive extracts, characterized by ultra-high-performance liquid chromatography coupled with ultraviolet (UV) detection and high-resolution mass spectrometry, revealed that flavonols and anthocyanins were the characteristic metabolite classes of onion skins. Quercetin, quercetin glucosides and their dimer and trimer derivatives, and, among anthocyanins, cyanidin 3-glucoside, were the most abundant bioactive compounds. The potential of onion skins was evaluated by testing several biological activities: ABTS/oxygen radical absorbance capacity (ORAC) and in vitro alpha-glucosidase assays were performed to evaluate the antioxidant and anti-diabetic properties of the extracts and of their main compounds, respectively, and proliferative activity was evaluated by MTT assay on human fibroblasts. In the present study, by observing various biological properties of "Rossa di Tropea" and "Ramata di Montoro" onion-dried skins, we clearly indicated that this agricultural waste can provide bioactive molecules for multiple applications, from industrial to nutraceutical and cosmetical sectors.

Effect of Organic Fertilizers on Selected Health Beneficial Bioactive Compounds and Aroma Profile of Red Topepo Sweet Pepper.

Phytochemicals and antioxidant properties of red sweet pepper cv Topepo grown in soil amended with different organic fertilizers were compared with that grown in unamended soil. Organic fertilizers are an environmentally friendly alternative to recovery infertile soils that resulted from the intensified agricultural practices in red Topepo production. The aim was to discriminate the effects of organic fertilizers one from each other on the quality of red Topepo to find out the better sustainable fertilization practice for its cultivation. Results showed that compost from vegetable residues (CV) enhanced the synthesis of total phenols, flavonoids, ascorbic acid, vitamin E, carotenoids, anthocyanins, as well as carbohydrates, antioxidant activities, and aroma profiling, compared to horse manure (HD), compost from olive pomace (CO), and control (CTR). The results indicated a specificity between the quality of red Topepo and compost composition, highlighting that vegetable residues increased the synthesis of secondary metabolites, enhancing sustainably, the nutraceutical, sensorial, and economic value of red Topepo. The fertilizer composition resulted largely responsible for the synthesis of bioactive compounds, flavor, and aroma of this fruit.

High-Performance Anion Exchange Chromatography with Pulsed Amperometric Detection (HPAEC-PAD) and Chemometrics for Geographical and Floral Authentication of Honeys from Southern Italy (Calabria region).

High-performance anion exchange chromatography with pulsed amperometric detection (HPAEC-PAD) combined with chemometric analysis was developed to describe, for the first time, the sugar profile of sixty-one honeys of different botanical origin produced in southern Italy (Calabria Region). The principal component and linear discriminant analysis used to describe the variability of sugar data were able to discriminate the honeys according to their botanical origin with a correlation index higher than 90%. For the purpose of the robustness of the conclusions of this study, the analytical advantages of the HPAEC-PAD method have been statistically demonstrated compared to the official Italian HPLC-RI method (Refractive Index detection). Finally, as the characterization of the floral and geographical origin of honey became an important issue due to high consumer demand, 13 acacia honeys originating from Europe and China were studied by using the same method. By chemometric method it was possible to discriminate the different geographical origin with an index of 100%. All results proved the possibility to identify the sugar profile obtained by HPAEC-PAD combined with a robust statistical analysis, as a tool of authentication.

Characterisation of nutraceutical compounds from different parts of particular species of Citrus sinensis 'Ovale Calabrese' by UHPLC-UV-ESI-HRMS.

Consumers are aware of diet causing health problems and therefore there is an increased demand for natural ingredients that are expected to be safe and health-promoting. Many of these compounds belong to the class of flavonoids and can be divided into these five groups: flavanones, flavones, flavonols, flavanols, isoflavones and anthocyanidins. Extracts from citrus fruits are usually used as functional ingredients for several products. The aim of this paper was to develop an UHPLC-UV-ESI-HRMS method to define the metabolite profile of different parts of citrus fruit, of a particular cultivar called 'Ovale Calabrese', and in its main by-products. The high resolution mass spectrometry analysis allowed the identification of 27 compounds belonging to the classes of flavonoids and terpenoids. The high contents of phytochemical compounds, reveal the potential use of the 'Ovale Calabrese' as a rich source of nutraceutical compounds.

Occurrence of aflatoxin M1 in milk samples from Italy analysed by online-SPE UHPLC-MS/MS.

The occurrence of aflatoxin M1 in 69 milk samples collected in a south region of Italy in 2016 was evaluated. The samples were analysed using an automated method based on online SPE coupled with UHPLC tandem mass spectrometry. After a salt induced liquid-liquid extraction with acetonitrile to remove protein from milk, the extract was diluted with water and analysed using an automated online SPE MS/MS method. Among the analysed samples no one had AFM1 higher than the legally allowable limits whereas 71.4% of the other analysed samples were above the LOD of the method. The highest contamination level of AFM1 was found in pasteurised milk (44.39 ng kg-1). The results show the worrying and widespread of AFM1 contamination, highlighting the necessity of monitoring studies in order to evaluate the reduction of the maximum legal limit.

Insights into the Analysis of Phenolic Secoiridoids in Extra Virgin Olive Oil.

Extra virgin olive oils (EVOOs) containing more than 5 mg/20 g tyrosol, hydroxytyrosol, and their secoiridoids can be recognized by health claims related to the protection of blood lipids from oxidative stress. Therefore, a reliable, accurate, and standardized analytical procedure is needed to determine these markers of EVOO quality. In order to overcome the limitations of current methods, a detailed investigation of sample preparation and chromatographic conditions was performed by UHPLC-UV-HRMS. The use of a C18 fused-core column and nonacidified gradient elution provided single, sharp peaks for oleocanthal and oleacein, allowing their reliable quantitation in UV profiles. Positive- and negative-UHPLC-HRMS/MS characterization of methanolic extracts revealed the presence of dimethyl acetal, methyl hemiacetal, and monohydrate derivatives of all secoiridoids. These artifacts were formed in aqueous methanol, which is usually employed to extract and analyze EVOO phenols, making the HPLC profiles more complex and the measurements less accurate and reproducible. Acetonitrile proved to be a suitable solvent to avoid the formation of secoiridoid dimethyl acetals and methyl hemiacetals and to efficiently extract EVOO bioactive phenols. Finally, the phenolic contents of Italian EVOO samples were determined by UHPLC-UV analysis of acetonitrile extracts before (direct method) and after acid hydrolysis (indirect method). The results indicated that the use of tyrosol and hydroxytyrosol as reference standards allowed more accurate quantitative data to be obtained. Direct and indirect methods provided comparable levels of EVOO phenols, highlighting the usefulness of acid hydrolysis in routine analyses. The improved procedure defines the most reliable conditions to provide an analytical method with suitable accuracy and repeatability in the analysis of healthy and functional EVOO phenols.

Metabolite profiling of licorice (Glycyrrhiza glabra) from different locations using comprehensive two-dimensional liquid chromatography coupled to diode array and tandem mass spectrometry detection.

Profiling of the main metabolites from several licorice (Glycyrrhiza glabra) samples collected at different locations is carried out in this work by using comprehensive two-dimensional liquid chromatography (LC × LC) coupled to diode array (DAD) and mass spectrometry (MS) detectors. The optimized method was based on the application of a HILIC-based separation in the first dimension combined with fast RP-based second dimension separation. This set-up was shown to possess powerful separation capabilities allowing separating as much as 89 different metabolites in a single sample. Identification and grouping of metabolites according to their chemical class were achieved using the DAD, MS and MS/MS data. Triterpene saponins were the most abundant metabolites followed by glycosylated flavanones and chalcones, whereas glycyrrhizic acid, as expected, was confirmed as the main component in all the studied samples. LC × LC-DAD-MS/MS was able to resolve these complex licorice samples providing with specific metabolite profiles to the different licorice samples depending on their geographical origin. Namely, from 19 to 50 specific compounds were exclusively determined in the 2D-chromatograms from the different licorice samples depending on their geographical origin, which can be used as a typical pattern that could potentially be related to their geographical location and authentication.

Determination of phenolic compounds in honey using dispersive liquid-liquid microextraction.

Honey is a valuable functional food rich in phenolic compounds with a broad spectrum of biological activities. Analysis of the phenolic compounds in honey is a very promising tool for the quality control, the authentication and characterization of botanical origin, and the nutraceutical research. This work describes a novel approach for the rapid analysis of five phenolic acids and 10 flavonoids in honey. Phenolic compounds were rapidly extracted and concentrated from diluted honey by dispersive liquid-liquid microextraction (DLLME) and then analyzed using high performance liquid chromatography with UV absorbance detection (HPLC-UV). Some important parameters, such as the nature and volume of extraction and dispersive solvents, pH and salt effect were carefully investigated and optimized to achieve the best extraction efficiency. Under the optimal conditions, an exhaustive extraction for twelve of the investigated analytes (recoveries >70%), with a precision (RSD<10%) highly acceptable for complex matrices, and detection and quantification limits at ppb levels (1.4-12 and 4.7-40ngg(-1), respectively) were attained. The proposed method, compared with the most widely used method in the analysis of phenolic compounds in honey, provided similar or higher extraction efficiency, except in the case of the most hydrophilic phenolic acids. The capability of DLLME to the extraction of other honey phytochemicals, such as abscisic acid, was also demonstrated. The main advantages of developed method are the simplicity of operation, the rapidity to achieve a very high sample throughput and low cost.

The potential of e-nose aroma profiling for identifying the geographical origin of licorice (Glycyrrhiza glabra L.) roots.

Licorice roots cultivated commercially in distinct geographical areas such as China, Iran, Italy (Abruzzo, Basilicata, Calabria and Sicily) and Turkey were classified using an artificial olfactive system (e-nose) based on metal oxide semiconductor sensors (MOS). The resultant instrumental data were processed using a multivariate statistical analysis method in order to classify the raw samples according to its origin. The e-nose odourprintings were obtained by a canonical discriminant analysis carried out with the aim of relating the specific data-sets corresponding to whole licorice roots aroma with the e-nose reference dataset. E-nose results were compared to those obtained by SPME/GC-MS. The HS-SPME/GC/MS analysis was used as a control system to check for the actual existence of differences in the chemical composition of sample headspace. These results imply the possibility to use an electronic nose as a tool for a quick, effective and non-destructive authentication of licorice roots.

Non-destructive flavour evaluation of red onion (Allium cepa L.) ecotypes: an electronic-nose-based approach.

This work reports preliminary results on the potential of a metal oxide sensor (MOS)-based electronic nose, as a non-destructive method to discriminate three "Tropea Red Onion" PGI ecotypes (TrT, TrMC and TrA) from each other and the common red onion (RO), which is usually used to counterfeit. The signals from the sensor array were processed using a canonical discriminant function analysis (DFA) pattern recognition technique. The DFA on onion samples showed a clear separation among the four onion groups with an overall correct classification rate (CR) of 97.5%. Onion flavour is closely linked to pungency and thus to the pyruvic acid content. The e-nose analysis results are in good agreement with pyruvic acid analysis. This work demonstrated that artificial olfactory systems have potential for use as an innovative, rapid and specific non-destructive technique, and may provide a method to protect food products against counterfeiting.