The Link between Polyphenol Structure, Antioxidant Capacity and Shelf-Life Stability in the Presence of Fructose and Ascorbic Acid.

Polyphenols play an important role in the sensorial and health-promoting properties of fruits and vegetables and display varying structure-dependent stability during processing and shelf-life. The current work aimed to increase the fundamental understanding of the link between the stability of polyphenols as a function of their structure, presence of ascorbic acid and fructose and total antioxidant capacity (TAC), using a multi-component model system. Polyphenol extract, used as the multi-component model system, was obtained from freeze-dried, high polyphenol content strawberry (Fragaria × ananassa 'Nerina') and twenty-one compounds were identified using high-performance liquid chromatography-mass spectrometry (HPLC-MS). The TAC and the first-order degradation kinetics were obtained, linking the polyphenol stability to its chemical structure, with and without the presence of fructose and ascorbic acid. The TAC (measured by oxygen radical absorption capacity (ORAC) and ferric reducing antioxidant potential (FRAP) assays) was not dramatically affected by storage temperatures and formulation, while polyphenol stability was significantly and structure dependently affected by temperature and the presence of ascorbic acid and fructose. Anthocyanins and phenolic acids were more unstable in the presence of ascorbic acid, while flavonol stability was enhanced by its presence. Shelf life study performed at 37 °C revealed significantly higher stability of purified polyphenols vs. the stability of the same polyphenols in the strawberry extract (multi-component system).

Stability and Bioaccessibility of Lignans in Food Products.

Lignans are a group of plant phenolic compounds with various technofunctional and health-promoting properties. They can be found in oilseeds (291.7-2513 mg/100 g), nuts, vegetables, fruits, and alcoholic and nonalcoholic drinks. The most common structural representative feature of lignans' backbone is a dimeric phenylpropanoid, which consists of two C6-C3 units joined by a central carbon. Compared to other phenolics, such as flavonoids, the literature on lignan stability and bioaccessibility is limited. This Mini-Review aims to present an overview of recent literature, draw connecting lines to the known regarding polyphenols, and suggest the main knowledge gaps. Processing methods and processing conditions influence the stability of lignans with several thermal treatments explored. Roasting, as a major studied processing step, displayed varying effects as a function of the lignan structure and matrix. The content of specific and even total lignans was shown to increase in some cases even after intense thermal treatment. Lignans were also reported to present a stabilizing effect against oxidation to oils when added externally. Different fermentation methods presented inconclusive outcomes on the content of lignans, likely stemming from the various matrices and microorganisms studied in a relatively limited pool of studies. The bioaccessibility of lignans in in vitro studies was usually low (from less than 1% in fermented flaxseed to 30% for microwaved artichokes). Yet, a clear conclusion regarding the digestive fate of lignans as a function of processing and structure cannot be currently suggested, and significant additional effort in this direction is needed.

In vitro bioaccessibility of polyphenolic compounds: The effect of dissolved oxygen and bile.

Polyphenols are acknowledged as health-promoting compounds, yet also known for their low bioavailability. Thus, the evaluation of their bioaccessibility, as a principle parameter for bioavailability, is important. In-vitro digestion is a common method for assessing polyphenol bioaccessibility, however, the method conditions don't address the potential influence of two important factors: dissolved oxygen (DO) and bile. This study explored the bioaccessibility of seven polyphenols as influenced by those factors, based on standard protocol as control. The results revealed a structure-dependant bioaccessibility, with up-to 54 % higher bioaccessibility in 0 % DO compared to control (100 % DO). However, bile has a larger influence, where intestinal bioaccessible pelargonidin-3-O-glucoside was higher by 123.91 ± 0.06 % without bile compared to the standard protocol (p < 0.05). These findings may partially refute the assumption of massive anthocyanin degradation in the intestinal conditions as the reason for poor anthocyanin bioavailability, and be used to develop a more specific method for in-vitro polyphenols digestion studies.

The Effect of Storage and Pasteurization (Thermal and High-Pressure) Conditions on the Stability of Phycocyanobilin and Phycobiliproteins.

The utilization of natural blue pigments in foods is difficult as they are usually unstable during processing and the commonly applied pH. The current study focuses on natural blue pigment, possessing antioxidant properties, found in Arthrospira platensis (spirulina), and phycobiliproteins (PBP). These pigments are a complex of conjugated protein and non-protein components, known as phycocyanobilin. PBP has low stability during pasteurization (high-pressure or heat treatments), resulting in protein denaturation and color deterioration that limits the application. The phycocyanobilin pigment might also be liable to oxidation during pasteurization and storage, resulting in color deterioration. Yet, the instability of the pigment phycocyanobilin during the pasteurization process and storage conditions was never studied before, limiting the comprehensive understanding of the reasons for PBP instability. In this study, the stability of phycocyanobilin under high-pressure and high-temperature conditions was compared to the stability of phycobiliproteins. We revealed that phycobiliproteins have a higher color deterioration rate at 70-80 °C than at high-pressure (300-600 MPa) whereas phycocyanobilin remained stable during high-pressure and heat processing. During storage at pH 7, phycocyanobilin was oxidized, and the oxidation rate increased with increasing pH, while at lower pH phycocyanobilin had low solubility and resulted in aggregation.

Differential cytostatic and cytotoxic action of Metallocorroles against human cancer cells: potential platforms for anticancer drug development.

A gallium(III)-substituted amphiphilic corrole noncovalently associated with a targeting protein was previously found by us to confer promising cytotoxic and antitumor activities against a breast cancer cell line and a mouse xenograft breast cancer model. To further explore potential anticancer applications, the cytostatic and cytotoxic properties of six nontargeted metallocorroles were evaluated against seven human cancer cell lines. Results indicated that toxicity toward human cancer cells depended on the metal ion as well as corrole functional group substitution. Ga(III)-substituted metallocorrole 1-Ga inhibited proliferation of breast (MDA-MB-231), melanoma (SK-MEL-28), and ovarian (OVCAR-3) cancer cells primarily by arrest of DNA replication, whereas 2-Mn displayed both cytostatic and cytotoxic properties. Confocal microscopy revealed extensive uptake of 1-Ga into the cytoplasm of melanoma and ovarian cancer cells, while prostate cancer cells (DU-145) displayed extensive nuclear localization. The localization of 1-Ga to the nucleus in DU-145 cells was exploited to achieve a 3-fold enhancement in the IC(50) of doxorubicin upon coadministration. Time-course studies showed that over 90% of melanoma cells incubated with 30 µM 1-Ga internalized metallocorrole after 15 min. Cellular uptake of 1-Ga and 1-Al was fastest and most efficient in melanoma, followed by prostate and ovarian cancer cells. Cell cycle analyses revealed that bis-sulfonated corroles containing Al(III), Ga(III), and Mn(III) induced late M phase arrest in several different cancer cell lines, a feature that could be developed for potential therapeutic benefit.

Fine tuning the reactivity of corrole-based catalytic antioxidants.

In order to determine the electronic factors that may affect the catalytic antioxidant activity of water-soluble metallocorroles a series of 10-aryl-5,15-pyridinium manganese(III) corroles was prepared. These complexes were examined regarding the effect of the C(10) substituent on the Mn(IV)/Mn(III) redox potentials, catalytic rate constants for decomposition of HOONO, prevention of tyrosine nitration, and superoxide dismutase activity. This structure-activity relationship investigation provides new insight regarding the mechanism by which manganese(III) corroles act as catalytic antioxidants. It also discloses the superiority of the C(10)-anysil-substituted complex in all examined aspects.

Structure dependent stability and antioxidant capacity of strawberry polyphenols in the presence of canola protein.

Polyphenol stability in processed food affects sensorial and health-promoting properties. Thus, understanding the effects of various food components on polyphenols degradation, as a function of their chemical structure, can contribute to optimal product engineering. The current study focuses on the impact of polyphenol structure on polyphenol-protein interactions in correlation with their stability and total antioxidant capacity (TAC) during shelf-life. A strawberry polyphenol extract (SPE) and canola protein extract (CPE) were used as multicomponent polyphenol and plant-based protein models. A non-covalent interaction of SPE and CPE was observed at pH = 3. Among CPE proteins cruciferin was the most involved in interactions, and the polyphenols with the highest relative binding were flavonols (45 ± 3%-68 ± 2%), while anthocyanins presented lower values (0 ± 0.4%-27 ± 1%). The presence of the proteins enhanced mostly the anthocyanins' stability, yet the extent of the impact was not correlated with the relative binding. TAC was not better preserved by the presence of CPE.

Metallocorroles as cytoprotective agents against oxidative and nitrative stress in cellular models of neurodegeneration.

Water-soluble iron, and manganese(III) complexes of corroles and porphyrins were examined with regard to their neuroprotective/neurorescue activities by using various neuronal cytotoxic models of oxidative and nitrative stress. The present study demonstrates that the metallocorroles significantly protect human neuroblastoma SH-SY5Y and mouse motor neuron-neuroblastoma fusion NSC-34 cell lines against neurotoxicity induced by either the peroxynitrite donor 3-morpholinosydnonimine or the parkinsonism-related neurotoxin 6-hydroxydopamine. The neuronal survival effect is further reflected by the prevention of 3-morpholinosydnonimine-induced protein nitration, inhibition of caspase 3 activation, as well as attenuation of 6-hydroxydopamine-mediated decrease in growth associated protein-43 levels. The iron(III) corrole, but not manganese (III) corrole, also significantly promotes neuronal survival of hydrogen peroxide (H(2)O(2))-impaired SH-SY5Y and NSC-34 cells. A substantial superiority of the metallocorroles relative to the corresponding porphyrin complexes is revealed in all examined aspects. These results highlight the large potential of corrole complexes as novel agents for therapeutic approaches in degenerative disorders of the central and peripheral nervous systems, where oxidative and nitrative stresses are involved.

Comparison of Thermal and High-Pressure Gelation of Potato Protein Isolates.

Potato protein isolate (PPI), a commercial by-product of the starch industry, is a promising novel protein for food applications with limited information regarding its techno-functionality. This research focused on the formation of both thermal and high-pressure gels at acidic and neutral pH levels. Our results reveal that physical gels are formed after 30 min by heat at pH 7 and pH 3, while pressure (300-500 MPa) allows the formation of physical gels only at pH 3, and only when the system crosses 30 °C by adiabatic heating during pressurization. Texture profile analysis (TPA) revealed that gel hardness increased with both gelation temperature and pressure, while water-holding capacity was lower for the pressure-induced gels. The proteins released in the water-holding test suggested only partial involvement of patatin in the gel formation. Vitamin C as a model for a thermally liable compound verified the expected better conservation of such compounds in a pressure-induced gel compared to a thermal one of similar textural properties, presenting a possible advantage for pressure-induced gelation.

The Influence of Chemical Structure and the Presence of Ascorbic Acid on Anthocyanins Stability and Spectral Properties in Purified Model Systems.

The loss of color pigment is an important quality factor of food products. This work aimed to systematically study, in purified model systems, the influence of anthocyanins' structure (by increasing the size of the conjugated sugar) and the presence of ascorbic acid on their stability and spectral properties during storage at two pH levels relevant to medium and high acid foods (6.5 and 4.5, respectively). Anthocyanins (cyanidin (Cy), cyanidin 3-O-ß-glucoside (Cy3G) and cyanidin 3-O-ß-rutinoside (Cy3R)) displayed first-order degradation rates, presenting higher stability in acidic medium and enhanced stability with increasing size of conjugated sugar. The addition of ascorbic acid resulted in significantly enhanced degradation. Changes in ultra violet visible (UV-VIS) spectral properties presented a decrease in typical color intensity and pointed towards formation of degradation products. Identification and kinetics of formation for cyanidin degradation products were obtained by high performance liquid chromatography system-mass spectrometry (HPLC-MS).

Cellular uptake and organ accumulation of amphipolar metallocorroles with cytoprotective and cytotoxic properties.

We report here an investigation that focuses on the organ distribution of metal complexes that are chelated by the amphipolar corrole whose macrocycle is decorated by two sulphonic acid head groups, which are emerging potential therapeutics against cancer (the cytotoxic Ga chelate) and diseases that are characterized by excessive production of ROS and RNS (the cytoprotective Mn and Fe derivatives). We show that the intraperitoneally injected fluorescent gallium(III) derivative accumulates in tissues sections of the kidney, liver, lung, heart, and pancreas. It also reaches the brain blood vessels, but does not cross the blood brain barrier. These findings are of prime importance for future in vivo studies on disease models, as they point toward a large utility of this kind of corrole chelates for treating cancer, neurodegenerative diseases characterized by "leaking BBB", cardiovascular diseases and diabetes.

Manganese corroles prevent intracellular nitration and subsequent death of insulin-producing cells.

Reactive oxygen species are heavily involved in the pathogenesis of diabetes mellitus (DM) because the insulin-producing beta cells are particularly vulnerable to free-radical-mediated cytotoxicity. Catalytic anti-oxidants have been successfully applied for attenuation of DM and its consequences, but most recent research revealed that preventing the nitration of vital proteins/enzymes might be an even more powerful strategy. We now report an unprecedented efficiency of manganese(III) corroles regarding the protection of rat pancreatic beta cells against intracellular nitration by peroxynitrite and subsequent cell death. A comparison between analogous corroles and porphyrin metal complexes reveals significant superiority of the former in all examined aspects. This is particularly true for the positively-charged manganese(III) corrole, which decomposes peroxynitrite fast enough and through a unique catalytic mechanism that is devoid of potentially nitrating reaction intermediates.

Superoxide dismutase activity of corrole metal complexes.

The first report regarding SOD activity of metallocorroles, investigated via the combination of the cytochrome C assay, pulse radiolysis, and electrochemistry, is used for identifying the main criteria needed for achieving good performance, as well as for elucidating mechanistic aspects of their action.