Antioxidant Properties of Carotenoids In Vitro and In Vivo

Abstract

Carotenoids are a class of natural pigments familiar to all through the orange–red to yellow colors of many fruits, vegetables, and flowers, as well as for the provitamin A activity that some of them possess. A body of scientific evidence suggests that carotenoids may scavenge and deactivate free radicals, acting thereby as antioxidants both in food systems (in vitro) and in the human organism (in vivo). Overall, epidemiological evidence links higher carotenoid intakes and tissue concentrations with reduced cancer and cardiovascular disease risk. However, research has also shown that the antioxidant activity of carotenoids may shift to a prooxidant character depending mainly on the biological environment in which they act. A summary of the antioxidant potential of natural carotenoids both in oil model systems and in vivo is presented in this article.     

Polychromatic light‐emitting conjugated polymer prepared by controlling its structure through active free radical addition

BACKGROUND: The HOMO–LUMO energy level width of conjugated polymers can be manipulated by controlling the conjugation length of the polymeric materials in order to adjust their properties in terms of emission of different colors and realize polychromatic displays. In the work reported in this paper azobisisobutyronitrile (AIBN) was used to control the conjugation length of poly[2‐methoxy‐5‐(2′‐ethylhexyloxy)‐co‐(1,4‐phenylene vinylene)] (MEH‐PPV) by free radical addition. In this way a series of MEH‐PPV with various conjugation lengths was obtained. RESULTS: Characterization of MEH‐PPV using ¹H NMR and Fourier transform infrared spectroscopy demonstrated that the cyano groups of AIBN hydrolyzed into carboxyls. The carboxyl free radicals attacked the conjugated double bonds of MEH‐PPV, resulting in a decrease of trans‐vinylenes and in an increase of cis‐vinylenes as well as tert‐methyls on the backbone. Changing the conjugated structure of the polymer caused the peaks of UV and fluorescence spectra to shift to the blue. CONCLUSION: The resulting MEH‐PPV derivatives can emit orange‐red, green and blue light. It is expected that they could be used to prepare PPV‐based materials that could modulate white light emission, by simply blending the PPV derivatives emitting different colors. Copyright © 2008 Society of Chemical Industry     

Antioxidant formation by γ-irradiation of glucose–amino acid model systems

The efficacy of γ-irradiation for the formation of Maillard reaction products (MRPs) from glucose and lysine/glycine and the antioxidant potential of MRPs thus formed were examined. Formation of MRPs was observed by monitoring absorbance at 284 nm and 420 nm. Upon irradiation, there was a dose-dependent increase in absorbance (r² = 0.99) at both the wavelengths. Irradiation of glucose/lysine solution resulted in higher absorbance at 284 nm than did that of glucose/glycine solution. Similarly, increase in absorbance at 420 nm was observed upon irradiation in both the systems. No significant absorbance was observed with unirradiated solution of glucose and lysine/glycine. These findings thus clearly revealed the formation of intermediate products and brown complexes (of Maillard reaction) upon irradiation of glucose/amino acid solution. A fluorescence was also observed in irradiated glucose/amino acid solution, whereas, none was seen in non-irradiated solution. These observations further confirmed the formation of MRPs, as fluorescent compounds are known to be precursors of brown pigments formed during the Maillard reaction. These MRPs exhibited excellent antioxidant activity, as measured by 1,1-diphenyl-2-picrylhydrazyl (DPPH) and β-carotene bleaching assays. MRPs, formed at a 40 kGy dose, scavenged up to 62% of DPPH radical and 82% of β-carotene was protected from bleaching. Reducing power of MRPs, estimated using the ferricyanide, method was also increased as compared to non-irradiated solutions. Further, these MRPs were able to scavenge hydroxyl radical and superoxide anion radical to the extents of 33% and 58%, respectively. These MRPs could chelate iron to an extent of 32% under in vitro conditions. Thus, these studies clearly demonstrated that radiation technology could be employed for obtaining novel antioxidants from sugar and amino acid combinations.     

Chemical composition and antioxidative activity of Moldavian balm (Dracocephalum moldavica L.) extracts

Moldavian balm (Dracocephalum moldavica L., Lamiaceae) is a perennial herb native to central Asia and naturalized in eastern and central Europe. It is commonly consumed as a food-related product and as a herbal preparation because of its reputed medicinal properties. Despite its importance, few reports exist in the literature regarding the chemistry or antioxidant activity of this species. In this study, the aerial material of Moldavian balm collected from Iran was extracted by Soxhlet using seven solvents of different polarity, viz., petroleum ether, dichloromethane, acetonitrile, ethyl acetate, methanol, n-butanol and water. The qualitative-quantitative chemical composition of each extract was determined using high-performance liquid chromatography coupled to photodiode array detection. For each extract, the total phenolic content was estimated as was the in vitro antioxidant activity using the iron(III) reduction assay, the β-carotene-linoleic acid bleaching assay and the 1,1-diphenyl-2-picrylhydrazyl and 2,2′-azinobis(3-ethylbenzothiazoline-6-sulphonate) free radical scavenging assays. Hydroxylated cinnamic acids, their derivatives and flavonoids were identified and quantified within the extracts, with rosmarinic acid being the most abundant component identified. The extracts demonstrated different degrees of potency within each assay, however, the observed pattern was not necessarily replicated between assays indicating the importance of the use of more than one screening technique to estimate the antioxidant activity of plant extracts.     

Chemical composition and in vitro antioxidative activity of a lemon balm (Melissa officinalis L.) extract

The leaf material of lemon balm (Melissa officinalis L.) was extracted with 450 ml/l aqueous ethanol by medium pressure liquid-solid extraction. The total phenolic content of the extract was estimated as gallic acid equivalents by Folin-Ciocalteu reagent method and a qualitative-quantitative compositional analysis was carried out using high performance liquid chromatography coupled with photodiode array detection. The lemon balm extract contained hydroxycinnamic acid derivatives and flavonoids with caffeic acid, m-coumaric acid, eriodictyol-7-O-glucoside, naringin, hesperidin, rosmarinic acid, naringenin, hesperetin being identified based on their chromatographic behaviour and spectral characteristics. The extract was also investigated for potential in vitro antioxidant properties in iron(III) reduction, iron(II) chelation, 1,1-diphenyl-2-picrylhydrazyl, 2,2′-azinobis(3-ethylbenzothiazoline-6-sulphonate), superoxide anion and nitric oxide free-radical scavenging, and inhibition of β-carotene-linoleic acid bleaching assays. The extract demonstrated antioxidant activity in all the assays. However, it was not as potent as the positive controls except in the β-carotene-linoleic acid bleaching assay, where its activity was superior to that of gallic and caffeic acids and statistically indistinguishable from quercetin and BHA. The exceptionally high antioxidant activity and the fact that this assay is of biological relevance warrants further investigation of lemon balm extract in ex vivo and in vivo models of oxidative stress.     

Copper‐Catalyzed Aerobic Formation of Unstable Sulfinyl Radicals for the Synthesis of Sulfinates and Thiosulfonates

Copper‐catalyzed aerobic coupling of thiols and alcohols affords sulfinates and thiosulfonates. These products are assumed to form via sulfinyl radicals which are not commonly found in oxidative coupling reactions of thiols. A reaction mechanism involving sulfinyl radicals is proposed, and mass and electron paramagnetic resonance (EPR) experimental results are provided.

     

Adenosyl Radical: Reagent and Catalyst in Enzyme Reactions

Adenosine is undoubtedly an ancient biological molecule that is a component of many enzyme cofactors: ATP, FADH, NAD(P)H, and coenzyme A, to name but a few, and, of course, of RNA. Here we present an overview of the role of adenosine in its most reactive form: as an organic radical formed either by homolytic cleavage of adenosylcobalamin (coenzyme B₁₂, AdoCbl) or by single‐electron reduction of S‐adenosylmethionine (AdoMet) complexed to an iron–sulfur cluster. Although many of the enzymes we discuss are newly discovered, adenosine's role as a radical cofactor most likely arose very early in evolution, before the advent of photosynthesis and the production of molecular oxygen, which rapidly inactivates many radical enzymes. AdoCbl‐dependent enzymes appear to be confined to a rather narrow repertoire of rearrangement reactions involving 1,2‐hydrogen atom migrations; nevertheless, mechanistic insights gained from studying these enzymes have proved extremely valuable in understanding how enzymes generate and control highly reactive free radical intermediates. In contrast, there has been a recent explosion in the number of radical‐AdoMet enzymes discovered that catalyze a remarkably wide range of chemically challenging reactions; here there is much still to learn about their mechanisms. Although all the radical‐AdoMet enzymes so far characterized come from anaerobically growing microbes and are very oxygen sensitive, there is tantalizing evidence that some of these enzymes might be active in aerobic organisms including humans.     

Readily Accessible Oxazolidine Nitroxyl Radicals: Bifunctional Cocatalysts for Simplified Copper Based Aerobic Oxidation

Using a two‐step procedure a range of bifunctional oxazolidine nitroxyl radicals have been prepared. The application of these co‐catalysts to the copper‐based aerobic oxidation of alcohols was then investigated. From these studies it was found that the parent tetramethyloxazolidine nitroxyl radical L1 was competent for oxidation in the presence of 2,2′‐bipyridine, and the bifunctional pyridyl‐containing nitroxyl radicals L2 and L3 could be used in the absence of additional coordinating ligands. Following optimization, the scope of this simplified transformation was explored, demonstrating that a range of primary and secondary benzylic alcohols are readily oxidized. In addition, the oxidation of allylic alcohols and hydroquinone can be achieved.     

唐古特白刺提取物抗氧化作用的研究

采用邻二氮菲-Fe2 氧化法、邻苯三酚自氧化法测定了唐古特白刺提取物的抗氧化作用。结果表明,不同溶剂的唐古特白刺提取物对羟基自由基(·OH)和超氧自由基(O-·2)均有一定的清除作用,在相同干物质浓度下,对羟自由基(·OH)的清除率依次递减的顺序为:80%乙醇、甲醇、丙酮、含盐酸0.1%的95%乙醇;对超氧阴离子自由基(O-·2)的清除率依次递减的顺序为:80%乙醇、甲醇、含盐酸0.1%的95%乙醇、丙酮。该结果提示唐古特白刺提取物具有抗氧化的作用。