Search

Fruit enzymatic browning (EB) inhibition continues to be a challenge in the Food Industry. This physiological disorder results mainly from the oxidation of natural phenolic compounds by polyphenoloxidase (PPO) and peroxidase (POX) leading to the formation of brown pigments. EB can be controlled with the application of antioxidants, reducing/inhibiting the activity of these oxidative enzymes. In this study, strawberry tree (leaves and branches) and apple byproduct were the natural-based extracts (NES) selected, as potential tissue browning inhibitors, within a first screening of fifteen natural-based extracts with antioxidant properties. Phenolic profile, total phenolic content and antioxidant activity of the selected extracts were also performed as well as their depletion effect on the oxidative enzyme&rsquo, s activity and browning inhibiton in fresh-cut pears. Strawberry tree extracts (leaves and branches) revealed higher total phenolic content (207.97 &plusmn, 0.01 mg GAE.gNES&minus, 1 and 104.07 &plusmn, 16.38 mg GAE.gNES&minus, 1, respectively), confirmed by the plethora of phenolic compounds identified by LC-ESI-UHR-QqTOF-HRMS and quantified by HPLC. This phytochemical composition was reflected in the low IC50 against PPO and POX obtained. Despite the lower phenolic content (6.76 &plusmn, 0.11 mg GAE.gNES&minus, 1) and antioxidant activity (IC50 = 45.59 &plusmn, 1.34 mg mL&minus, 1), apple byproduct extract showed potential in delaying browning. This study highlights the opportunity of byproducts and agricultural wastes extracts as novel anti-browning agents.

The lipophilic composition of Allium triquetrum L. bulbs, flowers and leaves was studied for the first time by GC-MS. Sixty compounds were firstly identified in A. triquetrum L. Fatty acids represented the major lipophilic family among the studied extracts, with (9Z,12Z,15Z)-octadeca-9,12,15-trienoic and (9Z,12Z)-octadeca-9,12-dienoic acids being the major constituents of this family. A long chain aliphatic ketone, namely hentriacontan-16-one, was mainly found in flowers and leaves. Flowers and leaves were also found to be rich in long chain aliphatic alkanes and alcohols, respectively. Sterols, monoglycerides, aromatic compounds and long chain aliphatic aldehydes were found in lower amounts. The antibacterial activity of A. triquetrum bulb, flower and leaf extracts against methicillin-resistant Staphylococcus aureus (MRSA) growth was in vitro assessed. Bulb and flower extracts showed significant MRSA growth inhibition. Overall, these valuable findings can contribute to the valorization of A. triquetrum L. as a source of value-added phytochemicals, specifically as antibacterial agents and for nutraceutical applications.

Salix (Salicaceae) species bark extracts are traditionally consumed due to their anti-inflammatory and analgesic benefits, mainly attributed to phenolic compounds. However, this biomass could be further exploited calling upon other extractive components, namely the lipophilic fraction. Hence, the present study highlights, for the first time, the chemical characterisation and the inhibitory effect of S. viminalis L., S. atrocinerea Brot. and S. fragilis L. bark lipophilic dichloromethane extracts against the Gram-negative bacterium Escherichia coli. Gas chromatography-mass spectrometry allowed the identification and quantification of 63 compounds, from which 36 were reported for the first time in these Salix species, namely 15 aromatic compounds, 4 fatty acids, 4 long chain aliphatic alcohols, 1 diterpene, 4 pentacyclic triterpenes, 4 tocopherols, 3 long chain aliphatic aldehydes and 1 sterol. Long chain aliphatic aldehydes represent the prevalent family, with triacontanal as the major component in S. fragilis L. and S. atrocinerea Brot. barks. Additionally, β-sitosterol was the major component identified in S. viminalis L. bark lipophilic extract, followed by lupeol. This last extract exhibited the highest inhibitory effect against E. coli viability, being probably related with these bioactive components. In contrast, aromatic compounds were detected at high abundances in S. atrocinerea Brot. and S. fragilis L. barks, with piceol as the predominant component. These findings can contribute to valorise bark of the three endogenous Portuguese Salix species, based on their chemical composition and biological properties.

Macroalgae of the genus Ulva have long been used as human food. Local environmental conditions, among other factors, can have an impact on their nutrient and phytochemical composition, as well as on the value of the seaweed for food and non-food applications. This study is the first to initiate a comparison between commercial Ulva spp. from different European origins, France (FR, wild-harvested Ulva spp.), and Portugal (PT, farm-raised Ulva rigida), in terms of proximate composition, esterified fatty acids (FA), and polar lipids. The ash content was higher in PT samples, while FR samples had higher levels of proteins, lipids, and carbohydrates and other compounds. The profile of esterified FA, as well as FA-containing polar lipids at the class and species levels were also significantly different. The FR samples showed about three-fold higher amount of n-3 polyunsaturated FA, while PT samples showed two-fold higher content of monounsaturated FA. Quantification of glycolipids and phospholipids revealed, respectively, two-fold and three-fold higher levels in PT samples. Despite the differences found, the polar lipids identified in both batches included some lipid species with recognized bioactivity, valuing Ulva biomass with functional properties, increasing their added value, and promoting new applications, namely in nutraceutical and food markets. UIDB/50011/2020+UIDP/50011/2020, UID/QUI/00062/2019, UIDB/50006/2020, UIDB/50017/2020+UIDP/50017/2020, LISBOA-01-0145-FEDER-402-022125, POCI-01-0145-FEDER-030962, BPD/UI51/5041/2017, BPD/UI51/5042/2018; EC/H2020/727892/EU info:eu-repo/semantics/publishedVersion

The main goal of this study was to chemically characterize an aqueous S. nigra flower extract and validate it as a bioactive agent. The elderflower aqueous extraction was performed at different temperatures (50, 70 and 90 °C). The extract obtained at 90 °C exhibited the highest phenolic content and antiradical activity. Therefore, this extract was analyzed by GC-MS and HPLC-MS, which allowed the identification of 46 compounds, being quercetin and chlorogenic acid derivatives representative of 86% of the total of phenolic compounds identified in hydrophilic fraction of the aqueous extract. Naringenin (27.2%) was the major compound present in the lipophilic fraction. The antiproliferative effects of the S. nigra extract were evaluated using the colon cancer cell lines RKO, HCT-116, Caco-2 and the extracts antigenotoxic potential was evaluated by the Comet assay in RKO cells. The RKO cells were the most susceptible to S. nigra flower extract (IC50=1250 µg mL1). Moreover, the extract showed antimicrobial activity against Gram-positive bacteria, particularly Staphylococcus aureus and S. epidermidis. These results show that S. nigra-based extracts can be an important dietary source of bioactive phenolic compounds that contribute to health-span improving life quality, demonstrating their potential as nutraceutical, functional foods and/or cosmetic components for therapeutic purposes., This research was funded by the Portuguese Foundation for Science and Technology (FCT) under the scope of the strategic funding of UIDB/04469/2020 unit and for Scientific Employment Stimulus 2017 (CEECIND/01507/2017) provided to Ana M. Sousa., info:eu-repo/semantics/publishedVersion

The Manila clam (Ruditapes philippinarum) is one of the most traded bivalves in the world. Knowing its harvesting location is therefore paramount to guarantee the safety of consumers. The present study employs fatty acid (FA) profiles of the adductor muscle (AM) to reveal the most likely harvesting location of four batches of Manila clams suspected of having been illegally sourced from the Tagus estuary. In this ecosystem, where the collection of Manila clams is currently prohibited for food safety reasons, illegal, unreported and unregulated (IUU) capture is known to occur. In order to trace the geographic origin of these four batches of Manila clams, a reference model based on the FA profiles of the AM was developed with specimens originating from the two most representative ecosystems supplying the trade-chain of this species in mainland Portugal (the Tagus estuary and Ria de Aveiro), as well as Ria de Vigo, a production area outside Portugal and that is also an important supplier. The ability of this model to allocate clams to its origin ecosystem was evaluated using independent datasets, with an allocation success of 100% (all samples were correctly assigned to its origin ecosystem, thus validating the model). Based on the reference model established, the harvesting location of the four batches suspected of originating from ongoing IUU in the Tagus estuary was investigated. Specimens from 3 of the 4 batches screened were classified, as most likely originating from the Tagus estuary (with a likelihood ranging from 90% up to 100%). These results highlight the potential of this approach to fight the IUU capture of Manila clams, as this practice endangers important habitats and threatens public health.

The utilization of natural compounds, such as phenolic acids and biopolymers, in the healthcare domain is gaining increasing attention. In this study, bacterial nanocellulose (BC) membranes were loaded with ionic liquids (ILs) based on phenolic acids. These ionic compounds, with improved solubility and bioavailability, were prepared by combining the cholinium cation with anions derived from caffeic, ellagic and gallic acids. The obtained BC-ILs membranes were homogeneous, conformable and their swelling ability agreed with the solubility of each IL. These membranes revealed a controlled ILs dissolution rate in the wet state and high antioxidant activity. In vitro assays performed with Raw 264.7 macrophages and HaCaT keratinocytes revealed that these novel BC-ILs membranes are non-cytotoxic and present relevant anti-inflammatory properties. Diffusion studies with Hanson vertical diffusion cells showed a prolonged release profile of the ILs from the BC membranes. Thus, this work, successfully demonstrates the potential of BC-ILs membranes for skin treatment.

The brown macroalgae Bifurcaria bifurcata have gained special attention due to their ability to biosynthesize linear diterpenes (rarely found in other species). However, the conventional extraction methods normally used to extract these compounds involve organic solvents and often high temperatures, leading to the degradation of thermo-labile compounds. In this context, the main objective of this work was to study and optimize for the first time the extraction of diterpenes from B. bifurcata through an environmentally friendly methodology, namely, high pressure extraction (HPE) using ethanol : water. This was compared with conventional Soxhlet extraction, using dichloromethane. Box–Behnken design was employed to evaluate the linear, quadratic, and interaction effects of 3 independent variables (pressure (X1), ethanol percentage (X2), and time of extraction (X3)) on response variables (extraction yield and diterpenes content (mg g−1 of extract and mg kg−1 of dry weight)) and the optimal extraction conditions (X1: 600 MPa; X2: 80%; X3: 5 min) were estimated by response surface methodology (RSM). B. bifurcata extract obtained under HPE optimal conditions showed a diterpenes content (612.2 mg g−1 of extract) 12.2 fold higher than that obtained by conventional extraction (50.1 mg g−1 of extract). The HPE extract, obtained under optimal conditions, showed antioxidant and antibacterial (against Staphylococcus aureus) activities considerably higher than the Soxhlet extract, and also presented a promising synergic effect with antibiotics, improving the antibiotic efficacy against S. aureus. In conclusion, these results indicate that HPE is a promising methodology, compared to conventional methodologies to obtain linear diterpene rich extracts from B. bifurcata with great potential to be exploited in pharmaceutical or biomedical applications.

Acacia dealbata biomass, either from forest exploitation or from the management of invasive species, can be a strategic topic, namely as a source of high-value compounds. In this sense, the present study aimed at the detailed characterization of the lipophilic components of different morphological parts of A. dealbata and the evaluation of their cytotoxicity in cells representative of different mammals&rsquo, tissues. The chemical composition of lipophilic extracts from A. dealbata bark, wood and leaves was evaluated using gas chromatography-mass spectrometry (GC&ndash, MS). Terpenic compounds (representing 50.2%&ndash, 68.4% of the total bark and leaves extracts, respectively) and sterols (60.5% of the total wood extract) were the main components of these extracts. Other constituents, such as fatty acids, long-chain aliphatic alcohols, monoglycerides, and aromatic compounds were also detected in the studied extracts. All the extracts showed low or no cytotoxicity in the different cells tested, demonstrating their safety profile and highlighting their potential to be used in nutraceutical or pharmaceutical applications. This study is therefore an important contribution to the valorization of A. dealbata, demonstrating the potential of this species as a source of high value lipophilic compounds.

Homogeneous, translucent and flexible films of chitosan (CH) and ellagic acid (EA) were prepared by solvent casting. Various concentrations of EA (0.5, 1.0, 2.5 and 5.0% w/w relative to CH) were used in order to evaluate their UV-blocking properties. In addition, the photochemical stability of the films was also studied via artificial solar light irradiation. These set of films display high mechanical properties (Young’s modulus = 3.21–3.57 GPa), thermal stability up to 215–220 °C, UVA- and UVB-barrier properties, moderate water vapor permeability (WVP = 2.82–3.70 g mm m−2 day−1 kPa−1) and maximum antioxidant activity around 28% (DPPH scavenging activity). Furthermore, all CH/EA films show antimicrobial activity against food-borne pathogens such as Gram-positive (Staphylococcus aureus) and Gram-negative (Pseudomonas aeruginosa) bacteria due to the CH antimicrobial effectiveness. These bioactive UV-blocking CH/EA films open the way to materials with potential for eco-friendly active packaging.

Scabiosa stellata L. is the less-studied plant of the species belonging to the genus Scabiosa, but the fact that several Scabiosa species are used in traditional medicine is an incentive to study this species. The profile of the S. stellata hexane extract was established by gas chromatography–mass spectrometry and allowed to conclude that fatty acids and their derivatives (87%) are the major chemical families of this extract. From the identified components, linoleic (19%), palmitic (20%) and linolenic (34%) acids are the major ones. Additionally, triterpenoids, namely β-sitosterol, stigmasterol, oleanolic and ursolic acids were also found. Simultaneously, the phytochemical study of this extract allowed the isolation and full characterization using 1D and 2D NMR experiments (1H and 13C NMR, HSQC, COSY, HMBC) of interesting metabolites such as 1,3-O-dilinoleoyl-2-O-palmitoyl glycerol and 1-O-linolenoyl-2-O-linoleoyl-3-O-oleoyl glycerol. This first assessment of S. stellata less polar constituents allowed the identification of several important compounds among which, ursolic and stearic acids, 1,3-O-dilinoleoyl-2-O-palmitoyl glycerol and 1-O-linolenoyl-2-O-linoleoyl-3-O-oleoyl glycerol, were found, for the first time in Scabiosa genus. The results reported, index of atherogenicity (AI = 0.55), index of thrombogenicity (TI = 0.23) and the fatty acid ratio (ω-6/ω-3 = 0.55), point out the nutritional value of S. stellata.

Nowadays, the “green synthesis” of different types of nanostructures, e.g. metallic nanoparticles (NPs), using plant extracts, emerged as a powerful, sustainable and economical design tool due to the panoply of plants available. However, the main challenge in this emerging area is still the strict control of the morphology (shapes) and dimensions of the NPs that is fundamental for the implementation at large scale of these cleaner synthetic methodologies. Here, an Eucalyptus globulus Labill. bark aqueous extract was used as a model extract and we systematically investigated the effect of different reaction parameters, namely temperature, pH, extract concentration and reaction time, on the morphology and size of gold NPs, by Ultraviolet–visible (UV–vis) spectroscopy, transmission electron microscopy (TEM), and dynamic light scattering (DLS). The obtained results demonstrated that the extract concentration has a major role in the size of the gold NPs (interestingly for very low concentrations a “size plateau” can be reached) and the pH of the medium slightly affects their morphology. Temperature does not present a significant effect in both size and morphology of spherical nanostructures however a clear impact in the size of anisotropic structures was evidenced. Reaction time has also a poor effect in both size and morphology of the NPs, except when varying extract concentration. This study presents for the first time an unequivocally and clear establishment of the reduction conditions of these eco-friendly approaches that should be selected to control the size and morphology of gold NPs prepared in view of their final application.

The Strecker aldehydes formed during the reaction between α-amino acids (phenylalanine or methionine) and either gallic acid, caffeic acid or (+)-catechin ortho-quinones were evaluated in wine-model systems. It was demonstrated that phenylacetaldehyde was formed by quinone intermediates at wine pH. The highest amounts of phenylacetaldehyde during the 10 days of experiment (69 ± 5 µg/L/day; 7x > Control) were obtained from (+) catechin, followed by gallic acid (61 ± 4 µg/L/day; 6x > Control) and caffeic acid (41 ± 4 µg/L/day; 4x > Control). The intermediate structures delivered from the reaction of ortho-quinones with α-amino acids were demonstrated by MSn.

Purpose Studies associate specific fatty-acids (FA) with the pathophysiology of inflammation. We aimed to analyze the impact of exercise on adipose tissue FA profile in response to a high-fat diet (HFD) and to ascertain whether these exercise-induced changes in specific FA have repercussions on obesity-related inflammation. Methods Sprague-Dawley rats were assigned into sedentary, voluntary physical-activity (VPA) and endurance training (ET) groups fed a standard (S, 35kcal% fat) or high-fat (71kcal% fat) diets. VPA-animals had unrestricted access to wheel-running. After 9-wks, ET-animals engaged a running protocol for 8-wks, while maintained dietary treatments. The FA content in epididymal white-adipose tissue (eWAT) triglycerides was analyzed by gas-chromatography and the expression of inflammatory markers was determined using RT-qPCR, Western and slot blotting. Results Eight-wks of ET reversed obesity-related anatomical features. HFD increased plasma tumor necrosis factor (TNF)-α content and eWAT monocyte chemoattractant protein (MCP)-1 protein expression. HFD decreased eWAT content of saturated FA and monounsaturated FA, while increased linoleic acid and prostaglandin E2 (PGE2) levels in eWAT. VPA decreased visceral adiposity, adipocyte size and MCP-1 in HFD-fed animals. The VPA and ET interventions diminished palmitoleic acid and increased linoleic acid in HFD-fed groups. Moreover, both interventions increased PGE2 levels in standard diet-fed groups and decreased in HFD. ET increased eWAT fatty acid desaturase 1 (FADS1) and elongase 5 (ELOVL5) protein content in both diet types. ET reduced eWAT inflammatory markers (TNF-α, IL-6), macrophage recruitment (MCP-1 and F4/80) and increased IL-10/TNF-α ratio in plasma and in eWAT in both diet types. Conclusions Exercise induced FA-specific changes independently of dietary FA composition, but only ET attenuated the inflammatory response in VAT of HFD-fed rats. Moreover, the exercise-induced FA changes did not correlate with the inflammatory response in VAT of rats submitted to HFD.

Salix spp. have been exploited for energy generation, along with folk medicine use of bark extracts for antipyretic and analgesic benefits. Bark phenolic components, rather than salicin, have demonstrated interesting bioactivities, which may ensure the sustainable bioprospection of Salix bark. Therefore, this study highlights the detailed phenolic characterization, as well as the in vitro antioxidant, anti-hypertensive, Staphylococcus aureus growth inhibitory effects, and biocompatibility of Salix atrocinerea Brot., Salix fragilis L., and Salix viminalis L. bark polar extracts. Fifteen phenolic compounds were characterized by ultra-high-performance liquid chromatography-ultraviolet detection-mass spectrometry analysis, from which two flavan-3-ols, an acetophenone, five flavanones, and a flavonol were detected, for the first time, as their bark components. Salix bark extracts demonstrated strong free radical scavenging activity (5.58&ndash, 23.62 &micro, g mL&minus, 1 IC50 range), effective inhibition on angiotensin-I converting enzyme (58&ndash, 84%), and S. aureus bactericidal action at 1250&ndash, 2500 &micro, 1 (6&ndash, 8 log CFU mL&minus, 1 reduction range). All tested Salix bark extracts did not show cytotoxic potential against Caco-2 cells, as well as S. atrocinerea Brot. and S. fragilis L. extracts at 625 and 1250 &micro, 1 against HaCaT and L929 cells. These valuable findings can pave innovative and safer food, nutraceutical, and/or cosmetic applications of Salix bark phenolic-containing fractions.

Obesity is a public health problem and a risk factor for pathologies such type 2 diabetes mellitus, cardiovascular diseases, and nonalcoholic fatty liver disease. Given these clinical implications, there is a growing interest to understand the pathophysiological mechanism of obesity. Changes in lipid metabolism have been associated with obesity and obesity-related complications. However, changes in the lipid profile of obese children have been overlooked. In the present work, we analyzed the serum phospholipidome of overweight and obese children by HILIC-MS/MS and GC-MS. Using this approach, we have identified 165 lipid species belonging to the classes PC, PE, PS, PG, PI, LPC, and SM. The phospholipidome of overweight (OW) and obese (OB) children was significantly different from normal-weight children (control). Main differences were observed in the PI class that was less abundant in OW and OB children and some PS, PE, SM, and PC lipid species are upregulated in obese and overweight children. Although further studies are needed to clarify some association between phospholipid alterations and metabolic changes, our results highlight the alteration that occurs in the serum phospholipid profile in obesity in children. published

Retama sphaerocarpa is a shrub widely used in traditional medicine. Owing to the huge demand for bioactive natural components, it is fundamental to study in detail the composition of this kind of plants. In this vein, the phenolic fraction of grains and stems from R. sphaerocarpa grown in Algeria was thoroughly investigated by ultra-high-performance liquid chromatography coupled to mass spectrometry (UHPLC–MS). The extracts obtained by methanol:water (50:50) extraction were also evaluated for their antioxidant and antibacterial activities. The UHPLC–MS analysis allowed the identification of forty two compounds, with twenty one identified in grains and twenty six in stems extracts. Thirty one of these components are referenced for the first time as constituents of R. sphaerocarpa. Stems showed to contain a considerably higher amount of phenolic compounds (11.40 g kg−1 of dry weight). Piscidic acid was identified as the major component, followed by quinic acid and morin/quercetin-di-O-rhamnoside. A taxifolin isomer, isorhamnetin-O-hexoside and an apigenin-6,8-di-C-hexoside isomer were found to be the major phenolic compounds in R. sphaerocarpa grains. The studied samples exhibited moderated antioxidant activities, with stems extract showing the most promising results. This fraction of R. sphaerocarpa also exhibited relevant inhibition against the bacteria Staphylococcus aureus and Pseudomonas aeruginosa. These results are a relevant contribution to the valorization of R. sphaerocarpa as a valuable source of natural bioactive compounds, with recognized nutraceutical applications.

The composition of the lipophilic and phenolic fractions of the wood of Eucalyptus grandis cultivated in Portugal, Brazil and South Africa, was studied. The lipophilic fraction of the studied E. grandis wood is mainly composed of sterols, fatty acids and phenolic compounds. Three triterpenic acids were detected for the first time in the wood extracts from Brazil. E. grandis wood from Portugal presents the largest lipophilic content (1.67 g kg−1 of dry wood), followed by South Africa (1.56 g kg−1 of dry wood) and Brazil (1.05 g kg−1 of dry wood). 51 Phenolic compounds were identified in E. grandis wood MeOH:H2O extracts, from which 11 are reported for the first time as E. grandis constituents and 4 phenolic compounds are firstly reported as Eucalyptus genus components. E. grandis wood from Brazil shows the highest phenolic content (∼2.36 g kg−1 of dry wood), followed by South Africa (∼1.90 g kg−1 of dry wood) and Portugal (∼1.30 g kg−1 of dry wood), demonstrating the influence of the geographic origin over E. grandis wood extractives composition and abundance, as well as on the antioxidant activities of the phenolic fractions. The detailed knowledge of these E. grandis extracts can contribute on the one hand to prevent their impact in the bleaching process, and, on the other demonstrates the potential of this species as a source of bioactive phytochemicals for nutraceutical applications.

Currently available proanthocyanidins extraction methods rely on dedicated crops and have low specificity and yield which limits their industrial application. Consequently, the development of novel methodologies and the use of sustainable sources is of great importance. Eutectic solvents have been proposed has good alternatives for conventional solvents due to their low price, easiness of preparation, biocompatibility and ability of being custom made to a specific application. Herein the effective extraction of proanthocyanidins from grape pomace and the possibility of tuning the extract&rsquo, s characteristics such as mean degree of polymerization and galloylation percentage is explored by means of varying the composition of a quaternary eutectic solvent composed by choline chloride, glycerol, ethanol and water. It was found that mean degree of polymerization values can vary from 6.0 to 7.37 and galloylation percentage can vary from 32.5% to 47.1% while maintaining extraction yield above 72.2 mg of proanthocyanidins per g of biomass. Furthermore, the increase of temperature up to 100 &deg, C has showed a significant effect on the extraction yield being possible to increase it by 238% when compared to the conventional extraction method.

Three different high performance liquid chromatography columns were accessed for phenolic compounds (PC) separation in the hydrophilic fraction of extra virgin olive oil (EVOO). Two fully porous C18 bonded silica phases and one partially porous biphenyl column were used. Biphenyl column allowed for an increase of more than 30% in peak capacity (nc), higher selectivity (&alpha, ) (1.045), and improved retention (k), with a reduction of 22.1% in the retention time. The higher resolution (Rs) was obtained by using the biphenyl column, with a fair separation of oleuropein aglycone isomers (OAI) and a good identification of caffeic acid (CA). Tyrosol (T), hydroxytyrosol (HT), and dihydroxyphenyl glycol (DHPG) were also well separated and identified. Moreover, the method using a biphenyl column was fully validated according to the requirements for new methods. For all parameters, the method applying the biphenyl column proved to be a reliable, accurate, and robust tool for separation, identification, and quantification of the main PCs in EVOOs.

The long-term effect of thermal pasteurization (TP) and high-pressure processing (HPP) of orange juices stored under refrigeration, on the bioactive components and antioxidant activity, was compared. Total phenolic content (TPC), flavonoid, anthocyanin, and carotenoid contents, the individual content of major phenolic components, and the antioxidant activity, were evaluated in TP- and HPP-treated juices over a 36-day period. At day 0, no significant differences in TPC, and a decrease in carotenoid content after both treatments, were observed. TP caused a decrease of flavonoid and anthocyanin contents, while HPP increased flavonoid content. Three major phenolic components were identified: apigenin-6,8-di-C-glucoside, naringenin-7-O-rutinoside, and hesperetin-7-O-rutinoside, the latter increasing ca. 45% immediately after HPP. During storage, a decrease in TPC, and in the anthocyanin and carotenoid contents of both treated juices was observed, with higher anthocyanin and phenolic contents in HPP juices. A significant increase of hesperetin-7-O-rutinoside content was observed in HPP juice. Both treatments caused a decrease (26% and 13%, respectively) of antioxidant activity. Most of the kinetic profiles followed zero-order patterns, with HPP juices showing a considerably higher half-life than TP ones. These results clearly demonstrate the advantages of HPP for orange juice preservation allowing, also, their nutritional benefits to be enhanced by increasing the content of some bioactive components.

This study aimed to assess the effect of high pressure (300 and 600 MPa) and enzymatic extraction (pectinase and cellulase) on the phenolic compounds profile, antioxidant capacity and antimicrobial activity of extracts from pomegranate by-products. Antimicrobial activity against eight different strains of pathogenic and contaminant bacteria and against five beneficial bacteria including Lactobacillus and Bifidobacterium strains were determined. The maximum level of total phenolic content, as well as antioxidant capacity were observed at 300 MPa, however enzymatic extraction did not improve the extraction yields. Punicalagin isomers and bis-hexahydroxydiphenoyl-glucoside isomer were the most abundant phenolic compounds found in the extracts. All pomegranate peel extracts demonstrated selective antimicrobial activity against all pathogenic bacteria without affecting beneficial ones. Pressurized extracts presented lower minimum inhibitory concentration against Bacillus cereus and Pseudomonas aeruginosa and lower minimum bactericidal concentration against B. cereus, while, enzymatic extracts presented lower minimum bactericidal concentration for Staphylococcus aureus, Methicillin-resistant Staphylococcus aureus and Listeria monocytogenes. Principal component analyses reveled that antioxidant activity and phenolic compounds content were strongly related with antimicrobial activity. Pomegranate peels extracts obtained by high pressure extraction could so be used as a source of high added-value bioactive compounds for antioxidant and antimicrobial applications.

This study aimed to assess the lipophilic and phenolic extractives composition of cork of Quercus suber L. grown in Algeria by gas chromatography-mass spectrometry (GC-MS) and ultra-high-performance liquid chromatograhy-mass spectrometry (UHPLC-MS), respectively. The phenolic cork oak extract was also evaluated for its scavenging activity towards DPPH radical, ABTS radical scavenging, reducing power and antibacterial activity against Staphylococcus aureus ATCC, Listeria innocua, Escherichia coil and Pseudomonas aeruginosa. The lipophilic fraction is mainly composed of thirty three compounds, with cerine, friedeline and betulinic acid as the major components. Furthermore, eighteen phenolic compouds were detected in the phenolic extract, with protocatechuic, ellagic and gallic acids as the major compounds. The methanol:water cork extract showed high DPPH scavenging ability with an ICso value of 5.69 mu g mL(-1) and an ABTS enhanced scavenging capacity when compared to BHT and trolox. A reducing power higher than BHA was also found. In addition, the phenolic fraction of cork was shown to inhibit the growth of Staphelococcus aureus (12.1 mm) and Pseudomonas aeroginisa (10.07 mm). These results indicate that algerian cork oak constitutes a good source of natutal bioactive compounds. Morever, this study is a relevant contribution to the valorization of algerian cork industrial residues, for which novel applications could be considered, namely the use of these extracts in food or nutraceutical industry. (C) 2015 Elsevier B.V. All rights reserved.

The chemical composition of the lipophilic extracts of the stems and grains of the shrub Retama sphaerocarpa was investigated by gas chromatography-mass spectrometry for the first time. Fatty acids is the major family of compounds in both morphological parts, representing between 37.1 and 85.1% of the total compounds detected, followed by sterols in stems and monoglycerides in grains. Considerable amounts of the alkaloids retamine (9.6 g kg(-1). of dry material) and cytisine (0.6 g kg(-1) of dry material) were also found in stems and grains, respectively. Before alkaline hydrolysis octadec-9-enoic (0.7-2.4 g kg(-1) of dry material), octadeca-9,12-dienoic (1.5-2.9 g kg(-1) of dry material) and hexadecanoic (1.1-2.0 g kg(-1) of dry material) acids are the most abundant lipophilic components in both morphological parts. After alkaline hydrolysis the contents of octade-9-enoic, octadeca-9,12-dienoic and octadeca-9,12,15-trienoic acids detected increased considerably ranging from 1.9 to 22.4, 3.6 to 40.1 and 0 to 8.6 g kg(-1) of dry material, respectively. Smaller amounts of long-chain aliphatic alcohols, alpha-tocopherol and beta-amyrin were also found. These data indicates that R. sphaerocarpa stems and grains are a potential source of valuable phytochemicals, with recognized nutritional and phytopharmaceutical applications. (C) 2015 Elsevier B.V. All rights reserved.

Macroalgae have been seen as an alternative source of molecules with promising bioactivities to use in the prevention and treatment of current lifestyle diseases. In this vein, the lipophilic fraction of short-term (three weeks) cultivated Bifurcaria bifurcata was characterized in detail by gas chromatography–mass spectrometry (GC-MS). B. bifurcata dichloromethane extract was composed mainly by diterpenes (1892.78 ± 133.97 mg kg−1 dry weight (DW)), followed by fatty acids, both saturated (550.35 ± 15.67 mg kg−1 DW) and unsaturated (397.06 ± 18.44 mg kg−1 DW). Considerable amounts of sterols, namely fucosterol (317.68 ± 26.11 mg kg−1 DW) were also found. In vitro tests demonstrated that the B. bifurcata lipophilic extract show antioxidant, anti-inflammatory and antibacterial activities (against both Gram-positive and Gram-negative bacteria), using low extract concentrations (in the order of µg mL−1). Enhancement of antibiotic activity of drug families of major clinical importance was observed by the use of B. bifurcata extract. This enhancement of antibiotic activity depends on the microbial strain and on the antibiotic. This work represents the first detailed phytochemical study of the lipophilic extract of B. bifurcata and is, therefore, an important contribution for the valorization of B. bifurcata macroalgae, with promising applications in functional foods, nutraceutical, cosmetic and biomedical fields.

Gold nanoparticles (AuNPs) are one of the most studied nanosystems with great potential for biomedical applications, including cancer therapy. Although some gold-based systems have been described, the use of green and faster methods that allow the control of their properties is of prime importance. Thus, the present study reports a one-minute microwave-assisted synthesis of fucoidan-coated AuNPs with controllable size and high antitumoral activity. The NPs were synthesized using a fucoidan-enriched fraction extracted from Fucus vesiculosus, as the reducing and capping agent. The ensuing monodispersed and spherical NPs exhibit tiny diameters between 5.8 and 13.4 nm for concentrations of fucoidan between 0.5 and 0.05% (w/v), respectively, as excellent colloidal stability in distinct solutions and culture media. Furthermore, the NPs present antitumoral activity against three human tumor cell lines (MNT-1, HepG2, and MG-63), and flow cytometry in combination with dark-field imaging confirmed the cellular uptake of NPs by MG-63 cell line.

Nanobiotechnology has emerged as a fundamental domain in modern science, and metallic nanoparticles (NPs) are one of the largest classes of NPs studied because of their wide spectrum of possible applications in several fields. The use of plant extracts as reducing and stabilizing agents in their synthesis is an interesting and reliable alternative to conventional methodologies. However, the role of the different components of such extracts in the reduction/stabilization of metal ions has not yet been understood clearly. Here we studied the behavior of the main components of a Eucalyptus globulus Labill. bark aqueous extract during metal-ion reduction followed by advanced chromatographic techniques, which allowed us to establish their specific role in the process. The obtained results showed that phenolic compounds, particularly galloyl derivatives, are mainly responsible for the metal-ion reduction, whereas sugars are essentially involved in the stabilization of the NPs.

The current interest of the scientific community for the exploitation of high-value compounds from macroalgae is related to the increasing knowledge of their biological activities and health benefits. Macroalgae phenolic compounds, particularly phlorotannins, have gained particular attention due to their specific bioactivities, including antioxidant, antiproliferative, or antidiabetic. Notwithstanding, the characterization of macroalgae phenolic compounds is a multi-step task, with high challenges associated with their isolation and characterization, due to the highly complex and polysaccharide-rich matrix of macroalgae. Therefore, this fraction is far from being fully explored. In fact, a critical revision of the extraction and characterization methodologies already used in the analysis of phenolic compounds from macroalgae is lacking in the literature, and it is of uttermost importance to compile validated methodologies and discourage misleading practices. The aim of this review is to discuss the state-of-the-art of phenolic compounds already identified in green, red, and brown macroalgae, reviewing their structural classification, as well as critically discussing extraction methodologies, chromatographic separation techniques, and the analytical strategies for their characterization, including information about structural identification techniques and key spectroscopic profiles. For the first time, mass spectrometry data of phlorotannins, a chemical family quite exclusive of macroalgae, is compiled and discussed.

The chemical composition of the lipophilic and phenolic extractives of the leaves, stems and roots of the salt marsh plant Halimione portulacoides from the Aveiro Lagoon was thoroughly investigated by gas chromatography-mass spectrometry (GC-MS) and ultra-high-performance liquid chromatography-mass spectrometry (UHPLC-MS), respectively. The lipophilic fraction of leaves and stems is mainly composed of long chain aliphatic acids and alcohols (both in the C16-C30 range) and smaller amounts of sterols, such as schottenol, beta-sitosterol and beta-sitostanol. The major component of roots extract is a triterpenic ketone, hop-17(21)-en-3-one, accounting for 2.8 g kg(-1) of dry material. Furthermore, thirteen phenolic compounds were firstly reported as constituents of this halophytic shrub. Among the studied plant tissues, leaves are the richest in phenolic compounds with 4.6 g kg(-1) of dry material, most of which correspond to sulfated flavonoids (3.1 g kg(-1) of dry material), particularly derivatives of isorhamnetin-sulfate. (C) 2013 Elsevier B.V. All rights reserved.

Phenolic composition, antioxidant and breast cancer antiproliferative activities of water and methanol/water derived extracts from olive pomace (OP) and dry olive mill residue (DOR), from Portuguese industries, were studied. DOR water (DORW) extracts showed the highest extraction yield; as well as the highest total phenolic content (TPC) and hydroxytyrosol (HT) (similar to 25 mg/g extract). HPLC-ESI-MS analysis identified HT in both OP and DOR, whereas HT-1-glucoside, tyrosol, oleuropein aglycone isomers, verbascoside and oleuropein were only detected in DOR. Additionally, a de(carboxymethyl)oleuropein aglycone isomer, in aldehyde form, was reported for the first time in DOR. DOR water extract also presented the most effective DPPH scavenging capacity and antiproliferative activity, comparatively to OP water (OPW) extract. Moreover, antioxidant potential of phenolic compounds present in DORW extract was comparable to HT, and to butylated hydroxyanisole (BHA), a widely used food industry antioxidant. Phenolic compounds present in DORW extract also showed comparable tumor antiproliferative activity on MDA-MB-231, relatively to HT and 5-fluorouracil (5-FU), a well-known cytostatic agent. MDA-MB-231 cell growth inhibition, upon 5-FU incubation was even incremented in the presence of DORW extract. These results demonstrate DOR extracts potential as source of phenolic compounds for nutraceutical applications, as food supplements, opening new strategies for its olive mill residues valorization. (C) 2013 Elsevier B.V. All rights reserved.

Besides being traditionally used to relieve hepatobiliary disorders, Cynara cardunculus L. has evidenced anticancer potential on triple-negative breast cancer (TNBC). This study highlights the antiproliferative effects of lipophilic extracts from C. cardunculus L. var. altilis (DC) leaves and florets, and of their major compounds, namely cynaropicrin and taraxasteryl acetate, against MDA-MB-231 cells. Our results demonstrated that MDA-MB-231 cells were much less resistant to leaves extract (IC50 10.39 µg/mL) than to florets extract (IC50 315.22 µg/mL), during 48 h. Moreover, leaves extract and cynaropicrin (IC50 6.19 µg/mL) suppressed MDA-MB-231 cells colonies formation, via an anchorage-independent growth assay. Leaves extract and cynaropicrin were also assessed regarding their regulation on caspase-3 activity, by using a spectrophotometric assay, and expression levels of G2/mitosis checkpoint and Akt signaling pathway proteins, by Western blotting. Leaves extract increased caspase-3 activity, while cynaropicrin did not affect it. Additionally, they caused p21Waf1/Cip1 upregulation, as well as cyclin B1 and phospho(Tyr15)-CDK1 accumulation, which may be related to G2 cell cycle arrest. They also downregulated phospho(Ser473)-Akt, without changing total Akt1 level. Cynaropicrin probably contributed to leaves extract antiproliferative action. These promising insights suggest that cultivated cardoon leaves lipophilic extract and cynaropicrin may be considered toward a natural-based therapeutic approach on TNBC.

Lipophilic compounds present in dichloromethane extracts of five brown macroalgae from the Portuguese coast were analyzed by gas chromatography-mass spectrometry (GC-MS). Their dicarboxylic acids, long-chain aliphatic alcohols, and monoglyceride profile are reported for the first time. Additionally, other new compounds were also first reported: 24-methylene-cholesterol in Himanthalia elongata, Laminaria ochroleuca, and Undaria pinnatifida; desmosterol and brassicasterol in H. elongata, L. ochroleuca, Sargassum muticum, and U. pinnatifida; fucosterol and campesterol in S. muticum; and cholest-5-en-3-ol-(3 beta)-3-phenyl-2-propenoate in Cystoseira tamariscifolia. Brown macroalgae dichloromethane extracts are mainly composed of fatty acids (463.4-3089.0 mg kg(-1) of dry material) and sterols (75.5-442.7 mg kg(-1) of dry material). High amounts of polyunsaturated fatty acids were found, with the omega-6/omega-3 ratios of all species lower than 3. Cystoseira tamariscifolia, H. elongata, and S. muticum showed to be also promising sources of fucosterol. These results seem to uphold the incorporation of these macroalgae in a more balanced diet, as well as their use in the nutraceutical industry, as long as they are coupled with sustainable management of these natural resources.

The supercritical fluid extraction (SFE) of phenolic compounds from Eucalyptus globulus bark was carried out along with detailed analysis of the extracts for the first time. The extracts were accessed in terms of (i) extraction yield (EY), (ii) total phenolic content by Folin-Ciocalteu method (TPC), (iii) phenolics quantified by high performance liquid chromatography (PC-HPLC), and (iv) antioxidant activity (AA). Preliminary runs were performed with pure and modified CO 2, using ethanol (EtOH), ethyl acetate, and water. The CO 2/EtOH mixture provided the best extraction yield, high total phenolic content and antioxidant activity. Results also demonstrated high selectivity of the CO 2/EtOH mixture to the extraction of flavanones, particularly eriodictyol and naringenin; and to the O-methylated flavonol isorhamentin, also found in abundance. To analyse the influence of temperature, ethanol content and flow rate on SFE at 300 bar using CO 2/EtOH, a full 2 3 design of experiments was accomplished. The most favourable conditions under the experimental range studied were found as 70 °C, 20% ethanol, and 10 g of CO 2 min -1, for which EY = 0.48%, TPC = 57.22 mg of gallic acid equivalents (GAE) g -1 of extract, PC-HPLC = 119.46 mg g -1 of extract, and AA = 49.74 mg of ascorbic acid equivalents (AAE) g -1 of extract. © 2012 Elsevier B.V. All rights reserved.

This study represents the first phytochemical research of phenolic components of Sercial and Tinta Negra Vitis vinifera L. The phenolic profiles of Sercial and Tinta Negra V. vinifera L. grape skins (white and red varieties, respectively) were established using high performance liquid chromatography–diode array detection–electrospray ionisation tandem mass spectrometry (HPLC–DAD–ESI-MS n ), at different ripening stages ( veraison and maturity). A total of 40 phenolic compounds were identified, which included 3 hydroxybenzoic acids, 8 hydroxycinnamic acids, 4 flavanols, 5 flavanones, 8 flavonols, 4 stilbenes, and 8 anthocyanins. For the white variety, in both ripening stages, hydroxycinnamic acids and flavonols were the main phenolic classes, representing about 80% of the phenolic composition. For red variety, at veraison , hydroxycinnamic acids and flavonols were also the predominant classes (71%), but at maturity, anthocyanins represented 84% of the phenolic composition. As far as we know, 10 compounds were reported for the first time in V. vinifera L. grapes, namely protocatechuic acid-glucoside, p -hydroxybenzoyl glucoside, caftaric acid vanilloyl pentoside, p -coumaric acid-erythroside, naringenin hexose derivate, eriodictyol-glucoside, taxifolin-pentoside, quercetin-glucuronide-glucoside, malylated kaempferol-glucoside, and resveratrol dimer. These novel V. vinifera L. grape components were identified based on their MS n fragmentation profile. This data represents valuable information that may be useful to oenological management and to valorise these varieties as sources of bioactive compounds.

The phenolic composition of Eucalyptus grandis , Eucalyptus urograndis ( E. grandis × E. urophylla ) and Eucalyptus maidenii bark is reported for the first time. High performance liquid chromatography–electrospray ionization mass spectrometry (HPLC–ESI-MS) and tandem mass spectrometry (MS n ) analysis of the methanol:water (50:50) extracts allowed to identify thirteen, twelve and twenty-four phenolic compounds in E. grandis , E. urograndis and E. maidenii bark extracts, respectively. Furthermore, ellagic acid-rhamnoside, dihydroxy-isopropylchromone-hexoside and dihydroxy-(methylpropyl)isopropylchromone-hexoside are referenced for the first time as constituents of Eucalyptus species. Epicatechin and quercetin-glucuronide are the major phenolic compounds in E. grandis and E. urograndis bark, followed by ellagic acid-rhamnoside and ellagic acid in E. grandis and by galloyl- bis -hexahydroxydiphenoyl (HHDP)-glucose and gallic acid in E. urograndis . Catechin, chlorogenic acid and methyl-ellagic acid-pentose are the major compounds in E. maidenii bark. The phenolic content of the three extracts shows a positive correlation with their antioxidant activities, evaluated by 2,2-diphenyl-2-picrylhydrazyl hydrate (DPPH) radical scavenging, showing activity values between those of two commercial antioxidants, ascorbic acid and butylated hydroxytoluene (BHT). These results, together with the phenolic composition, confirm the high potential of these species as source of biologically active phenolic compounds.

This study reports the identification of oligomeric alkenylperoxides by electrospray ionization mass spectrometry (ESI-MS) and tandem mass spectrometry (ESI-MS2), during the oxidation of oleic, linoleic and linolenic acids with Fenton's (Fe2+/H2O2) and Fe2+/O2 systems. The reactions were followed by ferrous oxidation-xylenol orange method together with GC-MS and GC-FID, allowing to observe that both oxidation systems are different in terms of hydroperoxide evolution, probably due to the presence of different intermediate reactive species: perferryl ion and OH· radical responsible for the decomposition of lipid hydroperoxides and formation of new compounds. The analysis of ESI-MS in the negative mode, obtained after oxidation of each fatty acid, confirmed the presence of the monomeric oxidation products together with other compounds at high mass region above m/z 550. These new ions were attributed to oligomeric structures, identified by the fragmentation pathways observed in the tandem mass spectra. Copyright © 2012 John Wiley & Sons, Ltd.

An integrated methodology for the identification and quantification of linoleic acid hydroperoxides (HPODEs) mixtures, obtained by the Fenton's reaction and by enzymatic oxidation, is reported. Unambiguous identification of the HPODEs formed (13-hydroperoxy-(9Z,11E)-octadecadienoic acid, 13-hydroperoxy-(9E,11E)-octadecadienoic acid and 9-hydroperoxyoctadecadienoic acid) was performed by HPLC–MS/MS analysis, while quantification was carried out by HPLC–UV using an external calibration, based on the collection of chromatographic peaks, and measuring of total hydroperoxides by ferrous oxidation-xylenol orange (FOX) method.

Worldwide, foodborne diseases are a growing public health problem. Among the infectious bacteria, non-typhoidal Salmonella enterica serovars (NTS) are the major cause of hospitalization and death, and the emergence and spread of their antibiotic-resistance is becoming a worldwide health issue. This, coupled with the restrictions of antibiotics use in agriculture and animal production, calls for alternative approaches to solve this problem. Plant-derived aqueous extracts compounds could provide novel straightforward approaches to control pathogenic bacteria. This review discusses the antimicrobial activity of aqueous plant extracts against Salmonella serovars, the possible mechanisms of action involved, which components/structures might be responsible for such activity, and the current challenges for the use of these extracts/components in Salmonella infection management and their application perspectives.

The phenolic fraction of cork from Quercus suber L. was obtained following two distinct fractionation schemes, namely methanol/water extraction followed by ethyl ether fractionation and sequential extraction with methanol and water. The extracts were studied in terms of total phenolics content, using Folin-Ciocalteu method, detailed chemical analysis by HPLC–MS, and antioxidant activity. The first method underestimates both total extractives, total phenolics as well as the amounts of identified compounds. The HPLC–MS, revealed that, apart from smaller components, all the extracts displayed the same qualitative composition; 15 phenolic components were identified, with ellagic acid, followed by gallic and protocatechuic acids as the most abundant compounds. Additionally some compounds identified were reported for the first time as cork components, namely salicylic acid, eriodictyol, naringenin, quinic acid and hydroxyphenyllactic acid. The antioxidant activity of the extracts, evaluated using the 2,2-diphenyl-2-picrylhydrazyl hydrate (DPPH) radical scavenging assay, showed to be considerably higher than that of BHT, and in the range of ascorbic acid. The antioxidant potential per mass unit of the three extracts is in the same range, but the high extraction yields obtained by water extraction open good perspectives for the exploitation of this extract in nutraceutical applications.

Metoprolol is a β-blocker highly prescribed for the treatment of heart diseases. It is not efficiently removed in wastewater treatment plants and it has been detected not only in the treated effluents, but also in natural waters. Thus, the knowledge of its fate in the environment is an important issue, and photodegradation is an important degradation pathway. While direct photodegradation of metoprolol by solar light is not relevant, there is evidence in the literature that it suffers indirect photodegradation and a few studies have been published showing the important role of dissolved humic matter as photo-sensitizer. However, the identification of the photoproducts formed in the presence of humic matter is very poor, since only 2 photoproducts had been identified. This study investigated the degradation of metoprolol under simulated solar radiation and in the presence of fulvic acids (FA) extracted from a river. During the photodegradation experiments we observed the formation of new compounds which were separated and tentatively identified by HPLC-UV-ESI-MSn. At least 16 compounds were tentatively identified, including the 2 compounds previously identified in the literature and 4 new compounds which had not been detected by other authors as degradation products of metoprolol, even when submitted to artificial degradation processes.

The lipophilic and phenolic extractives of the ripe mesocarp of four cherimoya cultivars ('Perry Vidal', 'Mateus I', 'Mateus III' and 'Funchal') from Madeira Island, were studied for the first time. The predominant lipophilic compounds are kaurene diterpenes (42.2-59.6%), fatty acids (18.0-35.6%) and sterols (9.6-23.7%). Kaur-16-en-19-oic acid is the major lipophilic component of all cultivars accounting between 554 and 1350 mg kg(-1) of dry material. The studied fruits also contain a high variety of flavan-3-ols, including galloylated and non-galloylated compounds. Five phenolic compounds were identified for the first time: catechin, (epi) catechin-(epi) gal locatechin, (epi) gallocatechin, (epi) afzelechin-(epi) catechin and procyanidin tetramer. 'Mateus I' and 'Mateus III' cultivars present the highest content of phenolic compounds (6299 and 9603 mg kg(-1) of dry weight, respectively). These results support the use of this fruit as a rich source of health-promoting components, with the capacity to prevent or delay the progress of oxidative-stress related disorders. (C) 2016 Elsevier Ltd. All rights reserved.

The Maillard reaction product 3-deoxyglucosone (3DG) was quantified in wines, by high-performance liquid chromatography-mass spectrometry analysis after derivatization with ortho-phenylenediamine. Both sweet red Port wines and dry white wines were analysed during natural and forced aging. In natural aging, and for dry white wines, 3DG is negatively correlated to age (r=0.939), while for sweet red Port wines, 3DG is positively correlated to age (r=0.782). The same tendency was observed during a wine forced aging protocol. For a dry white wine, with higher levels of alpha-amino acids, 3DG is consumed (k(consumption) 0.077-0.098 day(-1)) along the time protocol, while for a sweet red Port wine, with lower levels of alpha-amino acids, an accumulation of 3DG is observed with time (k(formation) 0.041-0.060 day(-1)). These results suggest that 3DG content can be used as an aging marker, as it has discriminated dry white and sweet red Port wines from different ages and cultivars. Analysis of wine-model solutions allowed verifying that the fructose content has a higher effect on 3DG formation than glucose, as well as that an increase on amino acids content does not lead to an increase of 3DG yields. (C) 2016 Elsevier Inc. All rights reserved.

A detailed study of the lipophilic composition of Codium tomentosum, Ulva lactuca, Gracilaria vermiculophylla and Chondrus crispus macroalgae cultivated in the Portuguese coast was carried out by gas chromatography-mass spectrometry before and after alkaline hydrolysis. Their long-chain aliphatic alcohols and monoglycerides compositions are reported for the first time. Additionally, other new compounds were also identified: phytol and neophytadiene in C. tomentosum, U. lactuca and G. vermiculophylla and stigmasterol, alpha-tocopherol and 24-methylenecholesterol in C tomentosum. The lipophilic fraction of the studied macroalgae are mainly constituted by fatty acids (110.1-1030.5 mg kg(-1) of dry material) and sterols (14.8-1309.1 mg kg(-1) of dry material). C. tomentosum showed to be a valuable source of stigmasterol (1229.0 mg kg(-1) of dry material) and alpha-tocopherol (21.8 mg kg(-1) of dry material). These results are a relevant contribution for the valorisation of these macroalgae species as sources of valuable phytochemicals. (C) 2015 Elsevier Ltd. All rights reserved.