The Potential of Plum Seed Residue: Unraveling the Effect of Processing on Phytochemical Composition and Bioactive Properties.

Bioactive compounds extracted from plum seeds were identified and quantified, aiming to establish how the brandy manufacturing process affects the properties and possible cascade valorization of seed residues. Extraction with n-hexane using Soxhlet has provided oils rich in unsaturated fatty acids (92.24-92.51%), mainly oleic acid (72-75.56%), which is characterized by its heart-healthy properties. The fat extracts also contain tocopherols with antioxidant and anti-inflammatory properties. All the ethanol-water extracts of the defatted seeds contain neochlorogenic acid (90-368 µg·g-1), chlorogenic acid (36.1-117 µg·g-1), and protocatechuate (31.8-100 µg·g-1) that have an impact on bioactive properties such as antimicrobial and antioxidant. Anti-amyloidogenic activity (25 mg·mL-1) was observed in the after both fermentation and distillation extract, which may be related to high levels of caffeic acid (64 ± 10 µg·g-1). The principal component analysis showed that all plum seed oils could have potential applications in the food industry as edible oils or in the cosmetic industry as an active ingredient in anti-aging and anti-stain cosmetics, among others. Furthermore, defatted seeds, after both fermentation and distillation, showed the greatest applicability in the food and nutraceutical industry as a food supplement or as an additive in the design of active packaging.

Unravelling the in vitro and in vivo potential of selenium nanoparticles in Alzheimer's disease: A bioanalytical review.

Alzheimer's disease (AD) is a devastating neurodegenerative disorder characterized by progressive cognitive decline and the accumulation of beta-amyloid plaques and tau tangles in the brain. Current therapies have limited efficacy, prompting the search for novel treatments. Selenium nanoparticles (SeNPs) have emerged as promising candidates for AD therapy due to their unique physicochemical properties and potential therapeutic effects. This review provides an overview of SeNPs and their potential application in AD treatment, as well as the main bioanalytical techniques applied in this field. SeNPs possess antioxidant and anti-inflammatory properties, making them potential candidates to combat the oxidative stress and neuroinflammation associated with AD. Moreover, SeNPs have shown the ability to cross the blood-brain barrier (BBB), allowing them to target brain regions affected by AD pathology. Various methods for synthesizing SeNPs are explored, including chemical, physical and biological synthesis approaches. Based on the employment of algae, yeast, fungi, and plants, green methods offer a promising and biocompatible alternative for SeNPs production. In vitro studies have demonstrated the potential of SeNPs in reducing beta-amyloid aggregation and inhibiting tau hyperphosphorylation, providing evidence of their neuroprotective effects on neuronal cells. In vivo studies using transgenic mouse models and AD-induced symptoms have shown promising results, with SeNPs treatment leading to cognitive improvements and reduced amyloid plaque burden in the hippocampus. Looking ahead, future trends in SeNPs research involve developing innovative brain delivery strategies to enhance their therapeutic potential, exploring alternative animal models to complement traditional mouse studies, and investigating multi-targeted SeNPs formulations to address multiple aspects of AD pathology. Overall, SeNPs represent a promising avenue for AD treatment, and further research in this field may pave the way for effective and much-needed therapeutic interventions for individuals affected by this debilitating disease.

Valorization of Defatted Cherry Seed Residues from Liquor Processing by Matrix Solid-Phase Dispersion Extraction: A Sustainable Strategy for Production of Phenolic-Rich Extracts with Antioxidant Potential.

The integrated valorization of food chain waste is one of the most promising alternatives in the transition to a sustainable bioeconomy. Thus, an efficient solid-phase matrix dispersion extraction method, using experimental factorial design and response surface methodology, has been developed and optimized for the recovery of polyphenols from defatted cherry seeds obtained after cherry liquor manufacture and subsequent fatty acid extraction, evaluating the effect of each processing step on the composition and phenolic content of sweet cherry residues. The phenolic extracts before fermentation showed the highest content of total polyphenols (TPC) and flavonoids (TFC) (3 ± 1 mg QE·g-1 and 1.37 ± 0.08 mg GAE·g-1, respectively), while the highest antioxidant capacity was obtained in the defatted seed extracts after both fermentation and distillation. In addition, high-performance liquid chromatography coupled to a quadrupole time-of-flight mass spectrometer (HPLC-ESI-QTOF-MS) was used to determine the phenolic profile. Dihydroxybenzoic acid, neochlorogenic acid, caffeic acid, and quercetin were the main phenolics found, showing differences in concentration between the stages of liquor production. The results underline the prospective of cherry by-products for obtaining phenol-rich bioactive extracts for possible use in different industrial sectors, offering a feasible solution for the cascade valorization of cherry agri-food waste.

Valorization of Prunus Seed Oils: Fatty Acids Composition and Oxidative Stability.

Prunus fruit seeds are one of the main types of agri-food waste generated worldwide during the processing of fruits to produce jams, juices and preserves. To valorize this by-product, the aim of this work was the nutritional analysis of peach, apricot, plum and cherry seeds using the official AOAC methods, together with the extraction and characterization of the lipid profile of seed oils using GC-FID, as well as the measurement of the antioxidant activity and oxidative stability using the 2,2-diphenyl-1-picrylhydrazyl (DPPH) free-radical scavenging method. Chemometric tools were required for data evaluation and the obtained results indicated that the main component of seeds were oils (30-38%, w). All seed oils were rich in oleic (C18:1n9c) and linoleic (C18:2n6c) acids and presented heart-healthy lipid indexes. Oil antioxidant activity was estimated in the range IC50 = 20-35 mg·mL-1, and high oxidative stability was observed for all evaluated oils during 1-22 storage days, with the plum seed oil being the most antioxidant and stable over time. Oxidative stability was also positively correlated with oleic acid content and negatively correlated with linoleic acid content. Therefore, this research showed that the four Prunus seed oils present interesting healthy characteristics for their use and potential application in the cosmetic and nutraceutical industries.

Valorization of Citrus reticulata Blanco Peels to Produce Enriched Wheat Bread: Phenolic Bioaccessibility and Antioxidant Potential.

The fortification of foods with bioactive polyphenols aims to improve their functional properties and to provide health benefits. Yet, to exert their benefits, phenolic compounds must be released from the food matrix and absorbed by the small intestine after digestion, so assessing their bioaccessibility is crucial to determine their potential role. This work aims to incorporate Citrus reticulata Blanco peel extracts into wheat bread as a promising opportunity to increase their bioactive potential, along with supporting the sustainable management of citrus-industry waste. A control and a wheat bread enriched at 2% and 4% (w/v) with a phenolic extract from mandarin peels were prepared and analyzed for antioxidant activity and phenolic composition using LC-MS and UV-Vis spectrophotometry. In addition, in vitro digestion was performed, and the digested extracts were analyzed with HPLC-MS/MS. The results showed a significant increase in total flavonoid content (TFC, 2.2 ± 0.1 mg·g-1), antioxidant activity (IC50 = 37 ± 4 mg·g-1), and contents of quercetin, caffeic acid, and hesperidin in the 4% (w/v) enriched bread. Yet, most polyphenols were completely degraded after the in vitro digestion process, barring hesperidin (159 ± 36 µg·g-1), highlighting the contribution of citrus enrichment in the development of an enriched bread with antioxidant potential.

Cytotoxicity, uptake and accumulation of selenium nanoparticles and other selenium species in neuroblastoma cell lines related to Alzheimer's disease by using cytotoxicity assays, TEM and single cell-ICP-MS.

Alzheimer's disease (AD) is the most prevalent neurodegenerative disease, representing 80% of the total dementia cases. The "amyloid cascade hypothesis" stablishes that the aggregation of the beta-amyloid protein (Aß42) is the first event that subsequently triggers AD development. Selenium nanoparticles stabilized with chitosan (Ch-SeNPs) have demonstrated excellent anti-amyloidogenic properties in previous works, leading to an improvement of AD aetiology. Here, the in vitro effect of selenium species in AD model cell line has been study to obtain a better assessment of their effects in AD treatment. For this purpose, mouse neuroblastoma (Neuro-2a) and human neuroblastoma (SH-SY5Y) cell lines were used. Cytotoxicity of selenium species, such as selenomethionine (SeMet), Se-methylselenocysteine (MeSeCys) and Ch-SeNPs, has been determined by 3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) and flow cytometry methods. Intracellular localisation of Ch-SeNPs, and their pathway through SH-SY5Y cell line, have been evaluated by transmission electron microscopy (TEM). The uptake and accumulation of selenium species by both neuroblastoma cell lines have been quantified at single cell level by single cell- Inductively Coupled Plasma with Mass Spectrometry detection (SC-ICP-MS), with a previous optimisation of transport efficiency using gold nanoparticles (AuNPs) ((69 ± 3) %) and 2.5 mm calibration beads ((92 ± 8) %). Results showed that Ch-SeNPs would be more readily accumulated by both cell lines than organic species being accumulation ranges between 1.2 and 89.5 fg Se cell-1 for Neuro-2a and 3.1-129.8 fg Se cell-1 for SH-SY5Y exposed to 250 µM Ch-SeNPs. Data obtained were statistically treated using chemometric tools. These results provide an important insight into the interaction of Ch-SeNPs with neuronal cells, which could support their potential use in AD treatment.

Effect of Storage and Drying Treatments on Antioxidant Activity and Phenolic Composition of Lemon and Clementine Peel Extracts.

Obtaining polyphenols from horticultural waste is an emerging trend that enables the valorization of resources and the recovery of value-added compounds. However, a pivotal point in the exploitation of these natural extracts is the assessment of their chemical stability. Hence, this study evaluates the effect of temperature storage (20 and -20 °C) and drying methods on the phenolic composition and antioxidant activity of clementine and lemon peel extracts, applying HPLC-DAD-MS, spectrophotometric methods, and chemometric tools. Vacuum-drying treatment at 60 °C proved to be rather suitable for retaining the highest antioxidant activity and the hesperidin, ferulic, and coumaric contents in clementine peel extracts. Lemon extracts showed an increase in phenolic acids after oven-drying at 40 °C, while hesperidin and rutin were sustained better at 60 °C. Hydroethanolic extracts stored for 90 days preserved antioxidant activity and showed an increase in the total phenolic and flavonoid contents in lemon peels, unlike in clementine peels. Additionally, more than 50% of the initial concentration was maintained up to 51 days, highlighting a half-life time of 71 days for hesperidin in lemon peels. Temperature was not significant in the preservation of the polyphenols evaluated, except for in rutin and gallic acid, thus, the extracts could be kept at 20 °C.

Neuroprotective activity of selenium nanoparticles against the effect of amino acid enantiomers in Alzheimer's disease.

Alzheimer's disease (AD), the most prevalent neurodegenerative disease, is characterized by extracellular accumulation of amyloid-beta protein (Aß), which is believed to be the very starting event of AD neurodegeneration. In this work, D-Phe, D-Ala, and D-Glu amino acids, which are the non-occurring enantiomeric form in the human body, and also D-Asp and DL-SeMet, have proved to be amyloidogenic regarding Aß42 aggregation in TEM studies. These amyloidogenic amino acid enantiomers also widened Aß42 fibrils up to 437% regarding Aß42 alone, suggesting that Aß42 aggregation is enantiomerically dependent. To inhibit enantiomeric-induced amyloid aggregation, selenium nanoparticles stabilized with chitosan (Ch-SeNPs) were successfully synthesized and employed. Thus, Ch-SeNPs reduced and even completely inhibited Aß42 aggregation produced in the presence of some amino acid enantiomers. In addition, through UV-Vis spectroscopy and fluorescence studies, it was deduced that Ch-SeNPs were able to interact differently with amino acids depending on their enantiomeric form. On the other hand, antioxidant properties of amino acid enantiomers were evaluated by DPPH and TBARS assays, with Tyr enantiomers being the only ones showing antioxidant effect. All spectroscopic data were statistically analysed through experimental design and response surface analysis, showing that the interaction between the Ch-SeNPs and the amino acids studied was enantioselective and allowing, in some cases, to establish the concentration ratios in which this interaction is maximum.

A combined analytical-chemometric approach for the in vitro determination of polyphenol bioaccessibility by simulated gastrointestinal digestion.

In this study, an integrated characterisation through polyphenol and caffeine content and antioxidant activity was combined with chemometric analysis to assess the effects of simulated in vitro gastrointestinal digestion on the bioaccessibility of these bioactive compounds from nine different tea infusions. Tea infusions were characterised based on total flavonoids, total polyphenols and antioxidant activity, together with the determination of individual polyphenol content. Fourteen phenolic compounds, including phenolic acids, stilbenes and flavonoids, were selected based on their reported bioactivity and high accessibility, attributed to their low molecular weight. Both polyphenols and caffeine were initially monitored in raw tea infusions and through the different digestion stages (salivary, gastric and duodenal) by capillary high performance liquid chromatography coupled to diode array detection (cHPLC-DAD) and/or HPLC coupled to a triple quadrupole mass analyser (HPLC-MS/MS). Multivariate analysis of the studied bioactives, using principal component analysis and cluster analysis, revealed that the decaffeination process seems to increase the stability and concentration of the compounds evaluated during digestion. The greatest transformations occurred mainly in the gastric and duodenal stages, where low bioactivity indices (IVBA) were shown for resveratrol and caffeic acid (IVBA = 0%). In contrast, the polyphenols gallic acid, chlorogenic acid and quercetin gave rise to their availability in white, green and oolong infusion teas (IVBA > 90%). Furthermore, highly fermented black and pu-erh varieties could be designated as less bioaccessible environments in the duodenum with respect to the tested compounds.

Characterization of AgNPs and AuNPs in sewage sludge by single particle inductively coupled plasma-mass spectrometry.

This study develops for the first time an analytical method for the characterization of silver and gold nanoparticles in sewage sludge. The evaluation of the effect of temperature, extracting agent and centrifugation speed and time on the extraction yield was carried out through a multifactorial analysis of variance which allows us to select 289 g, 5 min and 20 mM sodium pyrophosphate tetrabasic as optimal extraction conditions. Under these conditions, the analysis of the extract by single particle inductively coupled plasma-mass spectrometry provided recovery percentages of 70 ± 2% and 56 ± 1% for silver and gold nanoparticles, respectively. Moreover, the complementary results obtained upon analysis of these extracts by transmission electron microscopy and single particle inductively coupled plasma-mass spectrometry showed that the developed method did not modify the original size and shape of these nanoparticles during the extraction procedure. Size detection limits of 23 nm and 16 nm as well as number concentration limits of 3.12 × 109 particles kg-1 and 1.38 × 109 particles kg-1 were obtained for silver and gold nanoparticles, respectively. Moreover, a stability study of silver and gold nanoparticles in sewage sludge for 12 months showed differences between the two nanoparticle types. Although the sizes were not affected during the 12 months, silver nanoparticles underwent an oxidation process from 6 months onwards, which was reflected in an increase in the percentage of ionic silver from 14 ± 1% at 6 months to 24 ± 2% at 12 months. The developed methodology represents a simple, reliable and fast tool for detecting, quantifying and assessing the stability of nanoparticles in an important environmental sample such as sewage sludge.

A combined approach based on matrix solid-phase dispersion extraction assisted by titanium dioxide nanoparticles and liquid chromatography to determine polyphenols from grape residues.

A simple and efficient low-cost matrix solid phase dispersion (MSPD) extraction assisted by TiO2 nanoparticles and diatomaceous earth has been developed for the extraction of phenolic compounds from grape and grape pomace wastes. Experimental conditions for MSPD extraction were optimized by a factorial design and a surface response methodology. The simultaneous identification and quantification of eight main natural polyphenols (caffeic, p-coumaric, dihydroxybenzoic and gallic acid, rutin, resveratrol, quercetin and catechin) was possible by combining MSPD and capillary liquid chromatography coupled to a diode array detection and a mass simple quadrupole analyzer (cLC-DAD-MS). Good linearity and acceptable LOD (0.05-62 µg·g-1) and LOQ (0.2-207 µg·g-1) were obtained. The quantities of extracted polyphenols were within 2.4 and 333 µg·g-1, with catechin and rutin the most abundant compounds in grape pomace and grape wastes, respectively. Furthermore, considering the prospective uses of the winery bioresidues, the extracts have been characterised in terms of bioactive properties (several antioxidant activities and bacterial inhibition against Staphylococcus aureus, Escherichia coli and Pseudomona aeruginosa) and parameters such as total polyphenol and total flavonoid content. The high antioxidant activity (IC50 5.0 ± 0.4 µg ·g-1 against DPPH radical) and antibacterial activity (2.2 ± 0.3 mg·mL-1) suggests that the methodology developed is efficient, rapid and promising for the extraction of phenolic compounds with potential application as bioactive ingredients in food and cosmetic industries.

Anti-inflammatory activity of ethyl acetate and n-butanol extracts from Ranunculus macrophyllus Desf. and their phenolic profile.

ETHNOPHARMACOLOGICAL RELEVANCE: The members of the genus Ranunculus have counter-irritating properties and thus, they are traditionally used for treating anti-inflammatory disorders and other skin conditions. Ranunculus macrophyllus Desf. is a wild medicinal plant growing in Algeria and traditionally used to treat some cutaneous skin disorders. AIM: The aim of this study was to characterize the composition of the ethyl acetate and n-butanol extracts from Ranunculus macrophyllus Desf. as well as to elucidate and to compare their effect against acute skin inflammation. Moreover, both the antioxidant activity and the acute toxicity of the plant extracts were also studied. MATERIALS AND METHODS: Spectrophotometric and chromatographic methods were employed to identify and quantify phenolic compounds and triterpenoids from R. macrophyllus Desf. fractions. The antioxidant activity was estimated using the phosphomolebdenum, DPPH, reducing power and ß-carotene bleaching assays. The ethyl acetate and n-butanol extracts were screened for their anti-inflammatory activities using ex-vivo membrane stabilizing assays and in-vivo acute skin inflammation model. RESULTS: Ethyl acetate fraction showed the highest amounts of total phenolic compounds (413 ± 4 µg GAE/mg extract) and triterpenoids (70.4 ± 1.8 µg UAE/mg extract). Rutin, hesperidin, myricetin and kaempferol were the major compounds identified in the different fractions. Ethyl acetate fraction exhibited strong DPPH• radical scavenging ability (IC50 1.6 ± 0.2 µg/mL), high total antioxidant capacity (447 ± 7 µg AAE/mg extract) and reducing power (514 ± 8 µg AAE/mg extract). Ethyl acetate fraction inhibited (73.4 ± 0.3) % of linoleic acid peroxidation. Ethyl acetate and n-butanol fractions did not have any visible toxicity at 2000 mg/kg and presented excellent membrane stabilizing ability. The inhibition of xylene induced ear inflammation was (38 ± 4) % and (46 ± 1) % for RM-B and RM-EA, respectively. CONCLUSIONS: The high content of both phenolic compounds and triterpenoids combined with the remarkable anti-inflammatory effect and antioxidant activity of ethyl acetate and n-butanol extracts from R. macrophyllus Desf. support the wide spread use of this traditional plant on some skin disorders (inflammatory skin disorders).

Valorisation of black mulberry and grape seeds: Chemical characterization and bioactive potential.

Grape (Vitis vinifera L. var. Albariño) and mulberry (Morus nigra L.) seeds pomace were characterized in terms of tocopherols, organic acids, phenolic compounds and bioactive properties. Higher contents of tocopherols (28 ± 1 mg/100 g fw) were obtained in mulberry, whilst grape seeds were richer in organic acids (79 ± 4 mg/100 g fw). The phenolic analysis of hydroethanolic extracts characterised grape seeds by catechin oligomers (36.0 ± 0.3 mg/g) and mulberry seeds by ellagic acid derivatives (3.14 ± 0.02 mg/g). Both exhibited high antimicrobial activity against multiresistant Staphylococcus aureus MIC = 5 mg/mL) and no cytotoxicity against carcinogenic and non-tumour primary liver (PLP) cells. Mulberry seeds revealed the strongest inhibition (p < 0.05) against thiobarbituric reactive substances (IC50 = 23 ± 2 µg/mL) and oxidative haemolysis (IC50 at 60 min = 46.0 ± 0.8 µg/mL). Both seed by-products could be exploited for the developing of antioxidant-rich ingredients with health benefits for industrial application.

In vivo quantification of volatile organoselenium compounds released by bacteria exposed to selenium with HS-SPME-GC-MS. Effect of selenite and selenium nanoparticles.

Quantification of volatile organoselenium species released by Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus), after their growth in the presence of 1 and 2 mg Se·L-1 as both selenite and chitosan-modified selenium nanoparticles (Ch-SeNPs), was achieved by the application of a method based on headspace solid-phase microextraction (HS-SPME) and in-fiber internal standardization, combined with gas chromatography coupled to mass spectrometry (GC-MS). This method consisted of an initial extraction of the released volatile organoselenium compounds on the SPME fiber, followed by the extraction of internal standard (IS), deuterated dimethyl sulfide (d6-DMS), on the same fiber before its desorption at the injection port of GC-MS. The results showed that the biotransformation of selenite and Ch-SeNPs into volatile organoselenium compounds was dependent on both the type of bacterial species and the chemical form of selenium (Se) administered. In this sense, E. coli was able to biotransform both selenite and Ch-SeNPs into dimethylselenium (DMSe) and dimethyldiselenium (DMDSe) while S. aureus, biotransformed selenite into DMSe and DMDSe and, Ch-SeNPs only into DMDSe. Additionally, the formation of a volatile mixed sulfur/selenium compound, dimethyl selenenyl sulfide (DMSeS), from Se in nanoparticulated form has been detected for the first time.

Insights into the accumulation and transformation of Ch-SeNPs by Raphanus sativus and Brassica juncea: Effect on essential elements uptake.

Selenium (Se) at very low doses has important functions for humans. Unfortunately, the low levels of Se in soils in various regions of the world have implemented the agronomic biofortification of crops by applying Se-enriched fertilizers (mainly based on selenate). Lately, the use of nanofertilizers is growing in interest as their low size reduces the amount of chemicals and minimizes nutrient losses in comparison with conventional bulk fertilizers. However, the knowledge on their fate and environmental impact is still scarce. This study aims to evaluate the biotransformation of chitosan-modified Se nanoparticles (Ch-SeNPs) as well as their effect on the metabolism of essential metals (Fe, Cu, Zn and Mo) when applied to hydroponic cultivation of R. sativus and B. juncea. In house-synthesized Ch-SeNPs were characterized in both synthesis and hydroponic culture media by transmission electron microscopy (TEM), dynamic light scattering (DLS) and nanoparticle tracking analysis (NTA). The composition of one-tenth strength Hoagland's solution did not affect the size, shape and concentration in number of particles per mL of Ch-SeNPs. The plants were grown inside a box at 25 °C during the months of May-July in 2018. After a week of treatment with Ch-SeNPs, plants were harvested and divided into roots and aerial part. The biotransformation of Ch-SeNPs was evaluated through a process of enzymatic hydrolysis and subsequent analysis by HPLC-ICP-MS and HPLC-ESI-MS/MS. The results confirmed the transformation of Ch-SeNPs to seleno-amino acids: Selenomethionine (SeMet), Semethylselenocysteine (SeMetSeCys) and É£-glutamyl-Se-MetSeCys. Moreover, Multiple-way analysis of variance (ANOVA) and principal component analysis (PCA) showed that, regardless the plant species, Ch-SeNPs supplementation affected the absorption of Zn.

Ability of selenium species to inhibit metal-induced Aß aggregation involved in the development of Alzheimer's disease.

Extracellular accumulation of amyloid beta peptide (Aß) is believed to be one of the main factors responsible for neurodegeneration in Alzheimer's disease (AD). Metals could induce Aß aggregation, by their redox activity or binding properties to amyloid ß fibrils, leading to their accumulation and deposition outside neurons. For this reason, metal chelation may have an acknowledged part to play in AD prevention and treatment. In the current work, the role of different selenium species, including selenium nanoparticles, in Aß aggregation, was studied by evaluating their metal-chelating properties and their ability both to inhibit metal-induced Aß1-42 aggregation fibrils and to disaggregate them once formed. Transition biometals such as Fe(II), Cu(II), and Zn(II) at 50 µM were selected to establish the in vitro models. The DPPH assay was used to determine the antioxidant capacity of the evaluated selenium species. Selenium nanoparticles stabilized with chitosan (Ch-SeNPs) and with both chitosan and chlorogenic acid polyphenol (CGA@ChSeNPs) showed the highest antioxidant properties with EC50 of 0.9 and 0.07 mM, respectively. UV-Vis and d1(UV-Vis) spectra also revealed that selenium species, in particular selenomethionine (SeMet), were able to interact with metals. Regarding Aß1-42 incubation experiments, Fe(II), Cu(II), and Zn(II) induced Aß aggregation, in a similar way to most of the evaluated selenium species. However, Ch-SeNPs produced a high inhibition of metal-induced Aß aggregation, as well as a high disaggregation capacity of Aß fibrils in both the presence and absence of biometals, in addition to reducing the length and width (20% of reduction in the presence of Zn(II)) of the generated Aß fibrils. Graphical abstract.

Extraction of polyphenols and synthesis of new activated carbon from spent coffee grounds.

A valorization process of spent coffee grounds (SCG) was studied. Thus, a two-stage process, the first stage of polyphenols extraction and synthesis of a carbonaceous precursor and a subsequent stage of obtaining activated carbon (AC) by means of a carbonization process from the precursor of the previous stage, was performed. The extraction was carried out with a hydro-alcoholic solution in a pressure reactor, modifying time, temperature and different mixtures EtOH:H2O. To optimize the polyphenols extraction, a two-level factorial experimental design with three replicates at the central point was used. The best results were obtained by using a temperature of 80 °C during 30 min with a mixture of EtOH:H2O 50:50 (v/v). Caffeine and chlorogenic acid were the most abundant compounds in the analysed extracts, ranging from 0.09 to 4.8 mg∙g-1 and 0.06 to 9.7 mg∙g-1, respectively. Similarly, an experimental design was realized in order to analyze the influence of different variables in the AC obtained process (reaction time, temperature and KOH:precursor ratio). The best results were 1 h, 850 °C, and a mixture of 2.5:1. The obtained activated carbons exhibit a great specific surface (between 1600 m2∙g-1 and 2330 m2∙g-1) with a microporous surface. Finally, the adsorption capacity of the activated carbons was evaluated by methylene blue adsorption.

Extraction, identification and quantification of polyphenols from spent coffee grounds by chromatographic methods and chemometric analyses.

A solid-liquid extraction method using ethanol-water mixtures was combined with cLC-DAD, LC-MS/MS and chemometric analyses for establishing the optimum extraction conditions of valuable polyphenols from spent coffee grounds. Chlorogenic and p-coumaric acids were the most abundant polyphenols found, ranging from 0.02 to 4.8 mg g-1 and 0.173-0.50 mg g-1, respectively. In addition, total polyphenol content (9-29 mg GAE g-1 DW), total flavonoid content (11-27 mg QE g-1 DW), total antioxidant activity (0.3-7 mg GAE g-1 DW) and free radical scavenging ability (DPPH assay, 64-927 µg extract g-1 at EC50) of obtained extracts were determined. Response surface methodology allowed obtaining predictive models for the extraction of each individual polyphenol. On the other hand, multifactorial ANOVA was used to establish differences between coffee and spent coffee ground extracts. Principal component analysis was also employed to relate antioxidant activities, total polyphenol and total flavonoid contents with both the polyphenols extracted and the residue coffee type. The overall results suggested that spent coffee grounds could be reused as a promising, inexpensive and natural source of bioactive polyphenols with potential industrial applications, thus minimizing the waste disposal and environmental impact.

In-vivo solid phase microextraction for quantitative analysis of volatile organoselenium compounds in plants.

A new calibration method based on the use of headspace solid-phase microextraction (HS-SPME) and in-fiber internal standardization, combined with gas chromatography coupled to mass spectrometry (GC/MS) was developed for quantifying Se volatile organic species released by plants exposed to chitosan-modified selenium nanoparticles (Cs-SeNPs). The effect of several parameters affecting extraction and separation of the selected organic species of selenium (dimethylselenium (DMSe), diethylselenium (DESe) and dimethyldiselenium (DMDSe)) and deuterated dimethyl sulphide (d6-DMS) employed as internal standard were studied and optimized using an experimental design. The developed methodology was applied for quantifying the volatile selenium compounds produced over time by the plant species Raphanus sativus and Brassica juncea grown in hydroponic solution containing 5 mg Se L-1 in the form Cs-SeNPs. The procedure employed consisted in two steps. Volatile selenium species released from the plants were first extracted in the SPME fiber located at the headspace of a box with a fixed volume. Subsequently, the internal standard placed in a vial subjected to the same conditions as plants was extracted on the same fiber than the one previously used for extracting selenium compounds. Finally the extracted compounds were separated and analyzed by GC/MS. Results evidenced Cs-SeNPs biotransformation into DMSe and DMDSe by both plants species during growing stage, in amounts of the order of ng. Additionally, the resulting data were submitted to multifactorial ANOVA to evaluate the influence of plant type and time of exposure to Cs-SeNPs on the production of volatile selenium compounds.

Citrus peels waste as a source of value-added compounds: Extraction and quantification of bioactive polyphenols.

A method combining solid-liquid extraction based on ethanolic aqueous solution, cLC-DAD and chemometrics, was performed to extract and quantify polyphenols from citrus peels. LC-MS/MS was also employed for chemical profiling. The effect of extraction variables on the recovery was examined by experimental factorial design. Data were evaluated using multifactorial-ANOVA, response surface analysis and Principal Component Analysis. trans-Ferulic and p-coumaric antioxidants were found in lower quantities (<1.4 mg·g-1) in all peel extracts. Narangin flavonoid was also identified in all samples, while rutin flavonol was determined in the concentration range of 3.3-4.7 mg·g-1. The most abundant polyphenol in the extracts obtained from all evaluated citrus samples was the flavanone hesperidin (280-673 mg·g-1). Furthermore, peel extracts were evaluated in terms of total polyphenol and flavonoid content, total antioxidant activity and DPPH free radical scavenging. The obtained results suggested that evaluated citrus peel by-products could be reused as a source of polyphenols and transformed into value-added products.