Antioxidant and Antidiabetic Properties of Phlorotannins from Ascophyllum nodosum Seaweed Extracts.

Seaweeds have gained considerable attention in recent years due to their potential health benefits and high contents of bioactive compounds. This review focuses on the exploration of seaweed's health-promoting properties, with particular emphasis on phlorotannins, a class of bioactive compounds known for their antioxidant and antidiabetic properties. Various novel and ecofriendly extraction methods, including solid-liquid extraction, ultrasound-assisted extraction, and microwave-assisted extraction are examined for their effectiveness in isolating phlorotannins. The chemical structure and isolation of phlorotannins are discussed, along with methods for their characterization, such as spectrophotometry, nuclear magnetic resonance, Fourier transform infrared spectroscopy, and chromatography. Special attention is given to the antioxidant activity of phlorotannins. The inhibitory capacities of polyphenols, specifically phlorotannins from Ascophyllum nodosum against digestive enzymes, such as α-amylase and α-glucosidase, are explored. The results suggest that polyphenols from Ascophyllum nodosum seaweed hold significant potential as enzyme inhibitors, although the inhibitory activity may vary depending on the extraction conditions and the specific enzyme involved. In conclusion, seaweed exhibits great potential as a functional food ingredient for promoting health and preventing chronic diseases. Overall, this review aims to condense a comprehensive collection of high-yield, low-cost, and ecofriendly extraction methods for obtaining phlorotannins with remarkable antioxidant and antidiabetic capacities.

Influence of Oxidation and Dialysis of Phlorotannins on Bioactivity and Composition of Ultrasound-Assisted Extracts from Ascophyllum nodosum.

The isolation and chemical characterization of phlorotannins has gained special attention in recent years due to their specific health-promoting benefits. Flow-cell ultrasound-assisted extraction (90 W/cm2 of sonication power, 2 min of retention time and 20 g solvent/g algae of liquid-solid ratio) was carried out by using double-distilled water (WE) and acetone:water mixture (AWE) as extraction solvents. The AWE showed a higher total polyphenols content (TPC), carbohydrates (CHOs) and antioxidant activities than WE. However, when the WE was purified by using Amberlite XAD16 column, the purified WE (PWE) showed similar a TPC, decreased CHOs and increased antioxidant activity compared to WE. The oxidation of the PWE extract was evaluated under natural, forced and severe oxidation condition for 120 h. Only severe oxidation conditions were able to significantly reduce TPC and antioxidant activities. PWE was dialyzed (20, 10, 3.5 and 2 kDa). The main bioactive fraction of phlorotannins was obtained from 10 to 20 kDa. CHOs were distributed in fractions below 20 kDa. MALDI-TOF analysis was performed for PWE, PD20 and PD2 extracts to analyze the degree of polymerization of phlorotannins, which ranged from 4 to 17 phloroglucinol units/molecule. Fragmentation patterns allowed the proximate identification of several phlorotannins in Ascophyllum nodosum extracts.

In vitro inhibition of starch digestive enzymes by ultrasound-assisted extracted polyphenols from Ascophyllum nodosum seaweeds.

Seaweeds are gaining importance due to their antidiabetic characteristics. This study investigated the inhibitory effects of aqueous Ascophyllum nodosum extracts, obtained by ultrasound-assisted extraction with different sonication powers (70-90 W/cm2 ) and subjected to resin purification, against α-amylase and α-glucosidase enzymes. Different inhibition methodologies were carried out, preincubating the extract either with the enzyme or the substrate. Chemical characterization, in terms of proximate analysis, antioxidant capacity (2,2-diphenyl-1-picryl-hydrazyl-hydrate [DPPH] and FRAP), and polyphenols characteristics (reversed-phase high-performance liquid chromatography [RP-HPLC] and 1 H-NMR) were carried out to explain inhibitory activities of extracts. Sonication power did not influence the proximal composition nor antiradical activity of extracts, but increasing sonication power increased inhibition capacity (>15%) against both starch digestive enzymes. The extract purification largely improved the inhibition efficiency decreasing the IC50 of α-amylase and α-glucosidase by 3.0 and 6.1 times, respectively. Seaweed extracts showed greater inhibition effect when they were preincubated with the enzyme instead of the substrate. RP-HPLC together with 1 H-NMR spectra allowed relating the presence of uronic acids-polyphenols complexes and quinones in the extracts with the different inhibitory capacities of samples. PRACTICAL APPLICATION: The study confirms that ultrasound-assisted extracts from Ascophyllum nodosum can be used to inhibit digestive enzymes. This opens the alternative to be used in foods for modulating glycemic index.

Interactions between Ascophyllum nodosum Seaweeds Polyphenols and Native and Gelled Corn Starches.

The effect of several blending procedures between Ascophyllum nodosum seaweed flour (AF) and corn starch (CS) on the interactions between polyphenols and starch was studied in this paper. These methods comprised the blending of AF with native starch (NT) with previously gelled starch gel (GL) and promoting the gelling of corn starch in the presence of AF (CGL). Different AF-CS (g/g) ratios (from 1:0.5 to 1:25) were studied. The liquid phase was chemically characterized by polyphenols (TPC) and carbohydrates content. The antioxidant activity of the liquid phase after achieving the solid-liquid equilibrium was determined by DPPH, ABTS, and FRAP methods. The solid phase was characterized by FT-IR and SEM techniques. The Halsey model successfully fitted the equilibrium TPC in liquid and polyphenols adsorbed/retained by the solid phase of tested systems. NT samples showed lower polyphenols sorption than gelled samples. The differences found between samples obtained with GL and CGL methods suggested different interactions between polyphenols and starch. Specifically, physisorption is predominant in the case of the GL method, and molecular trapping of polyphenols in the starch gel structure is relevant for the CGL method. Results allowed us to determine the enhancement of the retention of polyphenols to achieve starchy foods with high bioactivity.

Analgesic and antiinflammatory effects of Nigella orientalis L. seeds fixed oil: Pharmacological potentials and molecular mechanisms.

Nigella species have been widely used in traditional medicine. The aim of this study was to evaluate the antiinflammatory and analgesic potentials of Nigella orientalis L. seeds fixed oil (NOO). The acetic acid writhing test and the formaldehyde-induced licking paw were performed to assess the analgesic activity of the oil. The antiinflammatory activity was first evaluated in vitro by the erythrocyte membrane stabilization then in vivo by xylene- and carrageenan-induced ear and paw edema, respectively. To further understand the molecular mechanism of action of the Nigella extract, lipopolysaccharide-activated RAW 264.7 macrophages were used. Nitric oxide (NO) production was measured by Griess reaction and cell viability by MTT assay. The gene and protein expression of inflammatory mediators were assessed by RT-PCR and western blot, respectively. NOO exerted a potent analgesic effect in in vivo models of writhing test and induced edema. The analyzed molecular mechanisms revealed a role for NO and prostaglandins as molecules mediating the pharmacological effects of the extract through a mechanism involving nuclear factor-κB and mitogen-activated protein kinases. This study demonstrates, for the first time, that the fixed oil of N. orientalis has strong antinociceptive and antiinflammatory properties and might be a promising agent for the treatment of certain inflammation-related diseases.

Understanding phenolic acids inhibition of α-amylase and α-glucosidase and influence of reaction conditions.

Phenolic acids are involved in modulating the activity of starch digestive enzymes but remains unclear if their interaction with enzymes or starch is governing the inhibition. The potential inhibition of nine phenolic acids against α-amylase and α-glucosidase was studied applying different methodologies to understand interactions between phenolic acids and either enzymes or substrates. Vanillic and syringic acids were prone to interact with α-amylase requiring low half-maximum inhibitory concentration (IC50) to inhibit starch hydrolysis. Nevertheless, the initial interaction of phenolic acids with starch somewhat obstructed their interaction with starch, requiring 10 times higher IC50, with the exception of chlorogenic and gallic acid. The study demonstrates that 10% of the phenolic acids were retained during starch gelatinization. Those effects were not really evident with α-glucosidase, likely due to the small molecular size of maltose substrate. Phenolic acids with > 1 hydroxyl group like caffeic and protocatechuic acids showed the lowest IC50 against α-glucosidase.

Impact of drying on the sodium alginate obtained after polyphenols ultrasound-assisted extraction from Ascophyllum nodosum seaweeds.

Ultrasound-assisted extraction (UAE) of polyphenols from the brown seaweeds Ascophyllum nodosum leaves a solid phase where alginates can be extracted. This study characterizes alginates extracted after the UAE process, with and without an intermediate drying stage at different temperatures (50 and 90 °C) producing sequentially two bioactive compounds from a unique raw material. FT-IR and 1H NMR analyses showed the high purity of alginates with features in the range of commercial alginates. Drying at high temperature decreased average block length and viscosity average molecular weight (Mv) of alginate from 428 to 133 kg/mol. Steady-shear curves (shear-thinning behaviour) and viscoelasticity (liquid like character) features depended clearly on Mv. Solutions of alginates with high Mv were more viscous and the elastic character was more relevant. Cox-Merz rule was only accomplished within the semi-dilute regimes of alginate concentration. Tested process conditions allow the production of alginates with different properties.

Determination of thermal transitions of gluten-free chestnut flour doughs enriched with brown seaweed powders and antioxidant properties of baked cookies.

A protocol for determining the characteristic temperatures of thermomechanical transitions on gluten-free flour doughs is proposed. This protocol is based on the mathematical analysis of experimental curve of storage modulus (G') vs temperature obtained by means of Dynamic Mechanical Thermal Analysis (DMTA) technique. Doughs at constant consistency of chestnut flour with different levels (3, 6 and 9% flour basis, f.b.) of brown seaweed (Bifurcaria bifurcata, Fucus vesiculosus and Ascophyllum nodosum) powders addition, 2% f.b. of guar gum and 1.8% f.b. of salt with different water absorption were used to test the proposed protocol. The ranges of temperatures corresponding to starch gelatinization (59-97 °C), amylopectin crystallites melting (82-101 °C), reversible dissociation of lipid-amylose complexes (107-128 °C) and amylose melting (133-171 °C) showed a strong dependence with water absorption of samples. Doughs with the same water absorption submitted to starch gelatinization during mixing were also analysed to corroborate the protocol suitability. Total polyphenols content and radical scavenging activity of extracts from chestnut flour-seaweed powder blends and seaweed-enriched chestnut cookies baked at 180 °C were determined. Extraction assisted with ultrasounds was carried out employing acetone-water (70:30 v/v) solution as solvent during 4 min with a liquid/solid ratio of 30 w/w. Seaweed powder addition had a positive effect on antioxidant properties of doughs before baking. However, the seaweed powder addition effect on baked products (cookies) is not clear due to antioxidant activity is overlapped by Maillard's products generated during baking.

Influence of natural extracts on the shelf life of modified atmosphere-packaged pork patties.

In this study four natural extracts from tea (TEA), grape (GRA), chestnut (CHE) and seaweed (SEA) with potential antioxidant activity were evaluated in pork patties. During 20 days of storage in modified atmosphere packs at 2°C, pH, colour, lipid oxidation and microbial spoilage parameters of raw minced porcine patties were examined and compared with a synthetic antioxidant (BHT) and control (CON) batch. Due to their higher polyphenol content, GRA and TEA extracts were the most effective antioxidants against lipid oxidation, also limiting colour deterioration. In addition, both natural extracts led to a decrease of total viable counts (TVC), lactic acid bacteria (LAB), Pseudomonas and psychotropic aerobic bacteria compared to the control. Among the four natural compounds tested, tea and grape extracts showed the most potential as alternatives to commercial antioxidants, for increasing the quality and extending the shelf-life of porcine patties.

Recovery and concentration of antioxidants from winery wastes.

Grape and wine byproducts have been extensively studied for the recovery of phenolic compounds with antioxidant activity and a variety of biological actions. The selective recovery and concentration of the phenolic compounds from the liquid phase separated from further diluted winery wastes has been proposed. Adsorption onto non ionic polymeric resins and further desorption with ethanolic solutions was studied. Several commercial food grade resins were screened with the aim of selecting the most suited for the practical recovery of phenolic compounds with radical scavenging activity. Under the optimized desorption conditions (using Sepabeads SP207 or Diaion HP20 as adsorbents and eluting with 96% ethanol at 50 °C) a powdered yellow-light brown product with 50% phenolic content, expressed as gallic acid equivalents, was obtained. The radical scavenging capacity of one gram of product was equivalent to 2-3 g of Trolox.

Effects of calf diet, antioxidants, packaging type and storage time on beef steak storage.

The effect of basal dietary supplemented with vegetable oils plus vitamin E (sunflower, soybean, linseed and a basal diet control), type of packaging (MAP or vacuum), addition of natural antioxidant (grape seed, rosemary) and storage time (0, 7, 14 and 21 days) on lipid oxidation, color stability, vitamin E content, and total aerobic bacterial counts in steaks of Longissimus thoracis was studied. The triple interaction diet × time × packaging affected oxidative stability, redness and yellowness of the meat. TBARS values did not increase with time in vacuum-packaged samples for all dietary treatments. However, samples from MAP and control showed the highest TBARS values after 21 days of storage (0.72 mg MDA/kg of meat, P<0.05). Both exogenous antioxidant extracts and MAP maintained low total aerobic counts in steaks until the 21st day. Calves should be fed a diet supplemented with L-VE, stored in MAP and treated with grape seed extract to extend the shelf life of their meat.

Extracts of Maqui ( Aristotelia chilensis ) and Murta ( Ugni molinae Turcz.): sources of antioxidant compounds and α-Glucosidase/α-Amylase inhibitors.

The objective of this work was to evaluate the antioxidant and antihemolytic activities of crude, aqueous, and organic-aqueous extracts of maqui ( Aristotelia chilensis ) and murta ( Ugni molinae Turcz.), together with their inhibiting effect on enzymes involved in the metabolism of carbohydrates. Radical scavenging activity, inhibition of linoleic acid oxidation in a micellar system, antihemolytic activity, and inhibition of α-amylases and α-glucosidases were analyzed. Crude extracts of maqui leaves and fruits were found to be important sources of polyphenolic compounds, showing 69.0 ± 0.9 and 45.7 ± 1.1 mg GAE/g dm, respectively. Polyphenols from maqui leaves were active as antioxidants and antihemolytic compounds (p < 0.05), showing a noncompetitive inhibiting effect on α-glucosidase. Flavan-3-ol polymers and glycosylated flavonols, such as quercetin glucoside and kaempferol glucoside, were tentatively identified in extracts. This preliminary observation provides the basis for further examination of the suitability of polyphenol-enriched extracts from maqui and murta as nutritional or medicinal supplements with potential human health benefits.

Antiradical activity, phenolics profile, and hydroxymethylfurfural in espresso coffee: influence of technological factors.

The influence of technological factors (decaffeination, brew volume, coffee species, and roast degree) on antiradical activity and phenolics content of espresso coffee is described. The screenings of phenolics profile and other compounds (caffeine and trigonelline), as well as the quantification of hydroxymethylfurfural, were performed by LC-DAD-ESI-MS. Significantly lower (p < 0.05) scavenging activities and phenolics contents were found in decaffeinated espressos when compared with regular ones (32 vs 38% and 324 vs 410 mg/30 mL cup, respectively). A long espresso (70 mL) offers more than twice the phenolics amount of a short one (20 mL). Robusta brews showed higher (p < 0.05) antiradical activity and phenolic contents than arabica ones, for all roast degrees (light, medium, and dark). No significant differences (p > 0.05) were observed for scavenging activities of differently roasted robusta brews, whereas an increase in medium-dark brews was observed for arabica samples. Total phenolics in robusta espressos decreased (p < 0.05) with the increase of roast degree, but no significant differences (p > 0.05) were found between arabica espressos from different roasts. By LC-DAD-ESI-MS, 23 hydroxycinnamic derivatives were found, including chlorogenic acids, lactones, and cinnamoyl-amino acid conjugates. The amount of each compound was differently affected by species and roast. Robusta brews presented superior levels of caffeine and chlorogenic acids, whereas arabica ones contained more trigonelline. Hydroxymethylfurfural contents in the brew (30 mL) varied from 2.60 to 0.84 mg for light- and dark-roasted arabicas and from 1.29 to 0.68 mg for light- and dark-roasted robustas, respectively.

Identification of polymeric procyanidins from pine bark by mass spectrometry.

Pine bark is an important source of polyphenolic compounds, mainly procyanidins, with reported protective effects against disease. In previous works, barks of two varieties of pine (P. pinaster and P. radiata) were extracted with ethanol, and partially purified to obtain the aqueous fractions (FA), that contained mainly polymeric procyanidins. The mean degree of polymerization was 7.9 for radiata (rFA) and 10.6 for pinaster (pFA). FAs were chromatographed on Sephadex LH-20 by using a gradient of methanol, water and acetone, to render a series of sub-fractions. In this work, the procyanidin compositions of these sub-fractions were analyzed using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). The mass spectra of sub-fractions from FA of P. pinaster showed signals of procyanidin polymers up to tridecamers, whereas for those from P. radiata the maximum degree of polymerization was 15. For this latter case, the MALDI-TOF mass spectra detected the presence of prodelphinidins in a small amount.

Separation and HPLC-MS identification of phenolic antioxidants from agricultural residues: almond hulls and grape pomace.

Almond hulls and grape pomace are residues abundantly generated by agricultural industries, which could be processed to obtain bioactive products. To this purpose, crude ethanol extracts from both agricultural byproducts were attained and subsequently fractionated in order to obtain an organic/water fraction (FOW). Extracts and fractions were analyzed for antioxidant power and their phenolic components tentatively identified by HPLC-MS. Chromatographic peaks of almond hull extracts showed the occurrence of hydroxybenzoic and cinnamic acid derivatives, with minor presence of flavan-3-ols (ECG, EGCG), whereas the FOW fraction offered the additional presence of epicatechin (EC) and glycosylated flavonols. In the composition for extracts of white and red grape pomace several of these compounds were also detected but basically consisted of glycosylated flavonols (quercetin, kaempferol). As a difference between both grape pomaces, myricetin glycosyde was found in that from the red variety, whereas flavan-3-ols (EC, afzelechin) were only identified in white pomace. When their FOW fractions were analyzed, gallic acid and some hydroxybenzoic acids were additionally detected. Antioxidant activity was assessed by DPPH and TBARS assays. Almond hulls showed inhibition percentages lower than 50% in both assays, while the inhibition percentage ranged from 80% to 90% in pomace extracts. Red grape pomace extract was the most efficient antioxidant, with an EC50 value of 0.91 g/L for TBARS and 0.20 g/L for DPPH. Even appearing as two quite different vegetal matrixes, the composition of phenolics in grape pomace and almond hulls is quite similar, the main difference being the major occurrence of flavonols in grape pomace. This fact could presumably explain the lower antiradical activity of hull extracts.

Processing of Rosa rubiginosa: extraction of oil and antioxidant substances.

In this work, a study about the effect of various operational conditions on the quantity of oil and soluble solids capable of being extracted from rosa mosqueta rosehip seeds is undertaken. Both the particle sizes assayed (0.6mm, 0.6-1mm, and 1-2mm) and the solvent-to-solid ratios (15:1, 25:1, and 50:1) showed a remarkable influence on the extraction efficiency. Extracted substances obtained by using the minor particle size or the maximum solvent-to-solid ratio doubled, at least, those attained by working under any other conditions. A major weight of kinetics upon equilibrium factors can be inferred from the short extraction times and high effective diffusivity values (being the lower one 1.97x10(-11)m(2)s(-1)) assessed for any condition. The antioxidant power of extracts was evaluated by ability to scavenge the DPPH radical. Results noteworthy depended on the solvent used to extract; whilst an approximately 80% DPPH inhibition percentage was reached in ethanol extracts, values of 52.2% or 41% were found in methanol and aqueous extracts, respectively. Even so, antioxidant capacity of Rosa rubiginosa extracts was much higher than that reported for other agricultural matrixes.

Murta leaves (Ugni molinae Turcz) as a source of antioxidant polyphenols.

Extracts from Murta leaves are used by Chilean natives for their benefits on health and cosmetic properties, which are mainly due to the presence of polyphenolic compounds. Extraction of such compounds is strongly influenced by several variables, the effects of which are studied in this work; the antioxidant power of the resulting extracts was measured by two different methods [2,2-diphenyl-1-picrylhydrazyl (DPPH) and thiobarbituric acid reactive substances (TBARS)]. On the whole, maximum values of polyphenolic yields and antiradical power (DPPH method) were attained at 50 degrees C (from 25 to 50 degrees C) and a solvent-to-solid ratio (v/w) of 15:1 (15:1-25:1). The solvents assayed were ethanol, methanol, and water. The highest polyphenolic yield values (2.6% expressed as gallic acid) were reached with methanol, whereas maximum EC50 was attained by the ethanol extract (0.121 mol gallic acid/mol DPPH). Contact time was shown to have only a slight influence in alcoholic extraction, while in water a remarkable effect of increasing contact times (30-90 min) was observed. Just water was the solvent that offered the best result when the antioxidant power was measured by the TBARS method. High-performance liquid chromatography-mass spectrometry analysis revealed the presence of polyphenols, basically flavonols and flavanols, sometimes glycosilated; myricetin and quercetin glycosides were detected in all extracts, whereas epicatechin was present in alcoholic extracts and gallic acid was only present in water.

Effect of solvent, temperature, and solvent-to-solid ratio on the total phenolic content and antiradical activity of extracts from different components of grape pomace.

Grape byproducts were subjected to an extraction process under various different experimental conditions (namely, solvent type, temperature, solvent-to-solid ratio, time contact, and raw material) in order to study the effect of these conditions on the yield of phenolic compounds and the corresponding antiradical activity of extracts. Although the order of decreasing capacity to extract soluble materials was ethanol > methanol > water, methanol was the most selective for extracting phenolic compounds. Temperature and solvent-to-solid ratio were found to have a critical role in extraction efficiency; values of 50 degrees C (between 25 and 50 degrees C) and 1:1 (between 1:1 and 5:1) maximized the antiradical activity of phenolic extracts. In addition, extracts from grape samples previously subjected to distillation reached higher antiradical values in comparison to those coming directly from pressing; in both cases, seed extracts showed better results than those of stem when ethanol or water was employed, whereas the opposite occurred in the case of methanol. These differences were attributed to the different phenolic compositions of the considered fractions.