Time-resolved EPR investigation of oxygen and temperature effects on synthetic eumelanin

Synthetic eumelanin produced using 5,6-dihydroxyindole-2-carboxylic acid as precursor and H2O2/horseradish peroxidase as oxidative reagent, in form of dry powder, has been investigated under photoexcitation by TR-EPR spectroscopy. The formation of spin polarized radical pairs from triplet excited states of melanin has been observed both in absence and in presence of oxygen and has been followed as a function of the temperature in the range 140–290 K. The triplet mechanism explains the observed polarization pattern in net emission. In the presence of oxygen new radical pairs are formed by interaction of melanin with molecular oxygen

Resveratrol-based benzoselenophenes with an enhanced antioxidant and chain breaking capacity

The structural modification of the resveratrol scaffold is currently an active issue in the quest for more potent and versatile antioxidant derivatives for biomedical applications. Disclosed herein is an expedient and efficient entry to a novel class of resveratrol derivatives featuring an unprecedented 2-phenylbenzoselenophene skeleton. The new compounds were obtained in good yields by direct selenenylation of resveratrol with Se(0) and SO2Cl2 in dry THF. Varying the [Se:SO2Cl2:resveratrol] ratio resulted in the formation of the parent benzoselenophene (1) and/or mono (2) and/or dichloro (3) benzoselenophene derivatives. All the benzoselenophene derivatives proved to be more efficient than resveratrol in the 2,2-diphenyl-1-picrylhydrazyl (DPPH) and ferric reducing/antioxidant power (FRAP) assays, with 1 showing an activity nearly comparable to that of Trolox. 1-3 also proved to be more efficient inhibitors than the parent resveratrol in kinetic experiments of styrene autoxidation. DFT calculations of the O-H bond dissociation enthalpy (BDE) revealed that the introduction of the Se-atom causes a significant decrease of the BDE of 3-OH and 5-OH, with just a small increase of the 4′-OH BDE. Compounds 1-3 showed no cytotoxicity at 5 μM concentrations on human keratinocyte (HaCaT) and intestinal (CaCo-2) cell line

improving the health quality of fried falafel middle eastern food by using transglutaminase and or pectin coating

The most disadvantage of the fried falafel balls are the highest level of acrylamide formed during Maillard reaction. Falafel balls are one of the largest deep fat frying fast food in the Middle East made basically of chickpeas. The main aim of this study was to investigate the effect of adding transglutaminase (TG, E.C. 2.3.2.13) to the falafel dough followed or not by dipping into pectin (PEC 1%) coating solution. Acrylamide, oil and water content of the fried falafel balls treated or not by TG (5 or 20U/g of chickpea proteins) and coated or not with PEC-containing film forming solutions were evaluated. In addition, the texture profile analyses were carried out. We observed, by TOF LC/MS, that the acrylamide content was reduced, compared to control sample, by 10.8% and 34.4% in the samples set up by adding 5 and 20 U TG/g respectively. In PEC-coated samples, acrylamide reduction was about by 59%, 65.3% and 84.5%, in falafel balls prepared either without of TG or containing 5U or 20 U of the enzyme, respectively, suggesting that TG-mediated crosslinks increase the water content inside the falafel balls, thus, reducing the rate of Maillard reaction. However, TG treatment does not affect oil content, while the PEC coating reduces the oil uptake about 23.5%. Finally, no difference was observed between the control sample and the one dipped in PEC regarding their texture properties hardness, chewiness and gumminess, while these properties were influenced in samples set up in the presence of the enzyme

Antioxidant activity of film forming systems based on melanins from 5,6-dihydroxyindole derivatives

The development of innovative dip-coating technologies for surface functionalization has been a very active issue over the past decade following the discovery of the adhesion properties of polydopamine, a eumelanin-like material. New opportunities have derived from the discovery that hexamethylenediamine (HMDA) markedly enhances film deposition from a variety of catechol, including the key eumelanin precursor 5,6-dihydroxyindole (DHI). The remarkable antioxidant properties of synthetic eumelanins from the other main melanogenic precursor 5,6-dihydroxyindole-2-carboxylic acid (DHICA) and its methyl ester (MeDHICA) have recently been described. In this work the film forming properties of MeDHICA melanin generated in the presence of HMDA or other diamines/monoamines and the antioxidant activity of the resulting films were investigated. Further to a systematic investigation, the most promising results were obtained running the aerobic oxidative polymerization of MeDHICA in aqueous buffers at pH 9.0 at 1 mM in the presence HMDA at 1:1.5 molar ratio. Under these conditions a dark yellow pigment is formed over 24 h exhibiting good film forming properties on different supports. HPLC analysis of the film solubilized in organic solvents indicated a mixture of oligomers of MeDHICA up to hexamers. Further polymerization of the film was obtained by exposure to ammonia vapors. The films showed high antioxidant activities in the 2,2-diphenyl-1-picrylhydrazyl and Ferric Reducing Antioxidant Power assays. Biocompatibility of MeDHICA/HMDA films was assessed on HaCat cells

Deposition of Antioxidant and Cytocompatible Caffeic Acid-Based Thin Films onto Ti6Al4V Alloys through Hexamethylenediamine-Mediated Crosslinking

A promising approach for advanced bone implants is thedepositionon titanium surfaces of organic thin films with improved therapeuticperformances. Herein, we reported the efficient dip-coating depositionof caffeic acid (CA)-based films on both polished and chemically pre-treatedTi6Al4V alloys by exploiting hexamethylenediamine (HMDA) crosslinkingability. The formation of benzacridine systems, resulting from theinteraction of CA with the amino groups of HMDA, as reported in previousstudies, was suggested by the yellow/green color of the coatings.The coated surfaces were characterized by means of the Folin-Ciocalteumethod, fluorescence microscopy, water contact angle measurements,X-ray photoelectron spectroscopy (XPS), zeta-potential measurements,and Fourier transform infrared spectroscopy, confirming the presenceof a uniform coating on the titanium surfaces. The optimal mechanicaladhesion of the coating, especially on the chemically pre-treatedsubstrate, was also demonstrated by the tape adhesion test. Interestingly,both films exhibited marked antioxidant properties (2,2-diphenyl-1-picrylhydrazyland ferric reducing antioxidant power assays) that persisted overtime and were not lost even after prolonged storage of the material.The feature of the coatings in terms of the exposed groups (XPS andzeta potential titration evidence) was apparently dependent on thesurface pre-treatment of the titanium substrate. Cytocompatibility,scavenger antioxidant activity, and antibacterial properties of thedeveloped coatings were evaluated. The most promising results wereobtained in the case of the chemically pre-treated CA/HMDA-based coatedsurface that showed good cytocompatibility and high reactive oxygenspecies' scavenging ability, preventing their intracellularaccumulation under pro-inflammatory conditions; moreover, an anti-foulingeffect preventing the formation of 3D biofilm-like bacterial aggregateswas observed by scanning electron microscopy. These results open newperspectives for the development of innovative titanium surfaces withthin coatings from naturally occurring phenols for bone contact implants

Eumelanin broadband absorption develops from aggregation-modulated chromophore interactions under structural and redox control

Eumelanins, the chief photoprotective pigments in man and mammals, owe their black color to an unusual broadband absorption spectrum whose origin is still a conundrum. Excitonic effects from the interplay of geometric order and disorder in 5,6-dihydroxyindole (DHI)-based oligomeric/polymeric structures play a central role, however the contributions of structural (scaffold-controlled) and redox ( €-electron-controlled) disorder have remained uncharted. Herein, we report an integrated experimental-theoretical entry to eumelanin chromophore dynamics based on poly(vinyl alcohol)-controlled polymerization of a large set of 5,6-dihydroxyindoles and related dimers. The results a) uncover the impact of the structural scaffold on eumelanin optical properties, disproving the widespread assumption of a universal monotonic chromophore; b) delineate eumelanin chromophore buildup as a three-step dynamic process involving the rapid generation of oxidized oligomers, termed melanochromes (phase I), followed by a slow oxidant-independent band broadening (phase II) leading eventually to scattering (phase III); c) point to a slow reorganization-stabilization of melanochromes via intermolecular redox interactions as the main determinant of visible broadband absorption

Pectin-Based Formulations for Controlled Release of an Ellagic Acid Salt with High Solubility Profile in Physiological Media

Among bioactive phytochemicals, ellagic acid (EA) is one of the most controversial because its high antioxidant and cancer-preventing effects are strongly inhibited by low gastrointestinal absorption and rapid excretion. Strategies toward an increase of solubility in water and bioavailability, while preserving its structural integrity and warranting its controlled release at the physiological targets, are therefore largely pursued. In this work, EA lysine salt at 1:4 molar ratio (EALYS), exhibiting a more than 400 times increase of water solubility with respect to literature reports, was incorporated at 10% in low methoxylated (LM) and high methoxylated (HM) pectin films. The release of EA in PBS at pH 7.4 from both film preparations was comparable and reached 15% of the loaded compound over 2 h. Under simulated gastric conditions, release of EA from HM and LM pectin films was minimal at gastric pH, whereas higher concentrations-up to 300 μM, corresponding to ca. 50% of the overall content-were obtained in the case of the HM pectin film after 2 h incubation at the slightly alkaline pH of small intestine environment, with the enzyme and bile salt components enhancing the release. EALYS pectin films showed a good prebiotic activity as evaluated by determination of short chain fatty acids (SCFAs) levels following microbial fermentation, with a low but significant increase of the effects produced by the pectins themselves. Overall, these results highlight pectin films loaded with EALYS salt as a promising formulation to improve administration and controlled release of the compound.This research was funded by the European Union’s Horizon 2020 research and innovation program through the Stance4Health project (Grant No. 816303).Ye

Natural Phenolic Compounds for Health, Food and Cosmetic Applications

Based on their potent antioxidant properties, natural phenolic compounds have gained more and more attention for their possible exploitation as food supplements, as well as functional ingredients in food and in the cosmetic industry [...

A SUPERIOR ALL-NATURAL ANTIOXIDANT MATERIAL FROM SPENT COFFEE GROUNDS FOR APPLICATION IN ACTIVE PACKAGING AND FOOD SUPPLEMENTATION

Spent coffee grounds (SCG) represent the main by-products of the coffee industry as they are obtained both during instant coffee production and as a result of coffee beverage consumption in restaurants and coffee shops. We report herein the up to 30 times enhancement of the intrinsic antioxidant potency of SCG following overnight treatment with 6 M HCl, at 100 °C [1], leading to a versatile multifunctional material (hydrolyzed spent coffee grounds, HSCG). Spectral and morphological analysis suggested that the remarkable potentiation of the antioxidant activity is due to efficient removal of the hydrolyzable components, mainly carbohydrates, making the polyphenol-rich component available for interaction with free radicals and oxidizing species. Based on these results, the possible exploitation of HSCG as an active component in functional food packaging, e.g. for food lipid preservation and stabilization of polymers, or as a food supplement was then invesitgated. HSCG efficiently delays lipid peroxidation in fish and soybean oils. Moreover, films made of polyethylene/2% HSCG blends display greater stability to thermal and photo-oxidative degradation. Regarding the possible use as a food supplement, in other experiments HSCG was subjected to a simulated digestion-fermentation treatment in vitro [2]. The potentially bioaccessible (soluble) fractions obtained exhibit high chemoprotective activity in human hepatocellular carcinoma (HepG2) cells against oxidative stress. Structural analysis of both the indigestible (insoluble) and soluble material revealed partial hydrolysis and release of the lignin components in the potentially bioaccessible fraction following simulated digestion-fermentation. A high prebiotic activity as determined from the increase in Lactobacillus spp. and Bifidobacterium spp. as well as the production of short chain fatty acids following microbial fermentation of HSCG is also observed. HSCG may thus represent an easily accessible and sustainable alternative to currently available antioxidant materials for biomedical, food and technological applications