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PubMed2000

Protective effect of L-phenylalanine on rat brain acetylcholinesterase inhibition induced by free radicals.

OBJECTIVE: To investigate whether the preincubation of brain homogenates with L-phenylalanine (Phe) could reverse the free radical effects on brain acetylcholinesterase (AChE) activity, since it has been reported that Phe binds hydroxyl radicals ((*)OH). DESIGN AND METHODS: Two well established systems were used for production of free radicals: (a) FeSO(4) (84 microM) plus ascorbic acid (400 microM), and (b) FeSO(4), ascorbic acid and H(2)O(2) (1 mM) at 37 degrees C in homogenates of adult rat whole brain. Changes in brain AChE activity were studied in the presence of each system separately. RESULTS: AChE was inhibited (18-28%) by both systems of free radicals. This inhibition was reversed when the brain homogenate was preincubated with Phe 1.8 mM. CONCLUSIONS: In accordance with our previous reports, Phe could protect against the direct action of (*)OH radicals on brain AChE and in this way it might be useful in the prevention of certain cholinergic neural dysfunctions.

Acetylcholinesterase↗
PubMed1999

Enalapril and moexipril protect from free radical-induced neuronal damage in vitro and reduce ischemic brain injury in mice and rats.

Angiotensin-converting enzyme inhibitors have been demonstrated to protect spontaneously hypertensive rats from cerebral ischemia. The present study investigated the protective effect of enalapril and moexipril in models of permanent focal cerebral ischemia in normotensive mice and rats. To elucidate the mechanism of neuroprotection the influence of these angiotensin-converting enzyme inhibitors on glutamate-, staurosporine- or Fe2+/3+-induced generation of reactive oxygen species and neuronal cell death in primary cultures from chick embryo telencephalons was studied. Treatment with moexipril or enalapril dose-dependently reduced the percentage of damaged neurons, as well as mitochondrial reactive oxygen species generation induced by glutamate, staurosporine or Fe2+/3+. Furthermore, moexipril and enalapril attenuated staurosporine-induced neuronal apoptosis as determined by nuclear staining with Hoechst 33258. In mice, 1 h pretreatment with enalapril (0.03 mg/kg) or moexipril (0.3 mg/kg) significantly reduced brain damage after focal ischemia as compared to control animals. Additionally, moexipril (0.01 mg/kg) was able to reduce the infarct volume in the rat model after focal cerebral ischemia. The results of the present study indicate that the angiotensin-converting enzyme inhibitors enalapril and moexipril promote neuronal survival due to radical scavenging properties.

Angiotensin-Converting Enzyme Inhibitors↗
PubMed2003

6-Hydroxymelatonin converts Fe (III) to Fe (II) and reduces iron-induced lipid peroxidation.

Disorders of iron accumulation are known to produce hepatotoxicity. Agents, which can reduce Fe(3+) to a more usable form Fe(2+) could potentially limit such damage. Since it has been previously demonstrated that the pineal secretory product, melatonin, is able to bind iron, we decided to investigate the potential protective properties of the principal melatonin metabolite and degradant, 6-hydroxymelatonin (6-OHM). Using adsorptive cathode stripping voltammetry (AdCSV) we showed that Fe(3+) in the presence of 6-OHM is converted to Fe(2+). We further demonstrated that 6-OHM reduces the Fe(2+)-induced rise in lipid peroxidation in rat liver homogenates. The results imply that 6-OHM facilitates the conversion of Fe(3+) to Fe(2+) which is a more biologically usable form of iron. While such a conversion could also potentially make more Fe(2+) available for driving the Fenton reaction and the consequent generation of the dangerous hydroxyl radical, 6-OHM is able to quench these radicals, thereby providing tissue protection.

Animals↗
PubMed1997

Novel estrogens and their radical scavenging effects, iron-chelating, and total antioxidative activities: 17 alpha-substituted analogs of delta 9(11)-dehydro-17 beta-estradiol.

Antioxidant effects of N,N-dimethyl-p-toluidine, p-cresol, and p-(hydroxy)thioanisol 17 alpha-substituted analogs of 17 beta-estradiol and their delta 9(11)-dehydro homologs were investigated using four different in vitro models: rat synaptosomal lipid peroxidation induced by Fenton's reagent, Fe(II)-chelating activities, the formation of superoxide anion radicals, and total antioxidative activity. Whereas the classical estrogen 17 beta-estradiol as well as selected phenolic compounds was only moderately inhibiting iron-dependent lipid peroxidation and stimulating total antioxidative activity, besides delta 9(11)-dehydro-17 beta-estradiol (J 1213), novel estrogens such as C-17-oriented side chain analogs of 17 beta-estradiol (J 843, J 872, and J 897) and delta 9(11)-dehydro homologs (J 844, J 864, and J 898) directly altered the iron redox chemistry and diminished the formation of superoxide anion radicals generated by a xanthine/xanthine oxidase-dependent luminescence reaction to a great extent. These results suggest that definite modifications in the chemical structure of 17 beta-estradiol, e.g., the introduction of a delta 9(11)-double bond and/or p-cresol as well as p-(hydroxy)thioanisol C-17 substitution, may result in substantial changes in their antioxidant behavior. These compounds may be drug candidates for treating pathologies related to free radical formation.

Animals↗
PubMed2001

Colorimetric flow-injection analysis of dissolved iron in high DOC waters.

An iron flow-injection analysis system has been optimized for the analysis of iron in waters high in dissolved organic carbon. The method detects either dissolved iron(II) or total dissolved iron with a detection limit of 10 nM, precision of 0.65% at 1 microM, and a dynamic range of four orders of magnitude. There are minimal interferences (< 1%) from other metals at environmental concentrations. The iron(II) method measures iron(II) in the presence of excess iron(III) with less than 1% interference. When used with pre-acidified samples, the total dissolved iron method agrees well with electrothermal atomic absorption spectrometry for a variety of natural waters with a range of dissolved organic carbon (3-36 mg C/L) and iron (1-28 microM) concentrations. When used with samples at their ambient pH, the total dissolved iron method detects dissolved iron, but not colloidal iron (size fraction 0.05-0.45 micron).

Carbon↗
PubMed2003

Sonolysis of alkylphenols in aqueous solution with Fe(II) and Fe(III).

The sonolytic degradation of alkylphenols (APs), such as butylphenol, pentylphenol, octylphenol, and nonylphenol (NP), in water was investigated at a sound frequency of 200 kHz with an acoustic intensity of 6 W cm(-2) under argon, oxygen, and air atmospheres. The sonolytic degradation rate of the APs under the conditions of the present study depended upon their alkyl chain length. The decrease in the degradation rate by the radical scavenging effect was in the range of about 48-82% for APs in the presence of 3 mM 2-methyl-2-propanol. The free radicals play a significant role in the sonolytic degradation process of the APs. In the presence of Fe(II) and Fe(III), the pseudo-first-order rate constants for the sonolytic degradation of 30 microM NP as a function of the concentration of Fe(II) and Fe(III) were estimated under argon and oxygen. The maximum rate constants were observed at 50 microM Fe(II) (0.139 +/- 0.008 min(-1)) and 100 microM Fe(III) (0.103 +/- 0.001 min(-1)) under oxygen. The total organic carbon concentration (TOC) was investigated under same conditions. TOC decreased in the range of about 50-70% during the sonication in the presence of Fe(II) and Fe(III) under argon and oxygen. The sonochemical effects by the addition of Fe(II) and Fe(III) as catalyst during the sonication under the proper atmosphere result in a remarkable enhancement of degradation and mineralization.

Argon↗
PubMed2003

Reduction of Ag(I), Au(III), Cu(II), and Hg(II) by Fe(II)/Fe(III) hydroxysulfate green rust.

Green rusts are mixed Fe(II)/Fe(III) hydroxides that are found in many suboxic environments where they are believed to play a central role in the biogeochemical cycling of iron. X-ray absorption fine structure analysis of hydroxysulfate green rust suspensions spiked with aqueous solutions of AgCH(3)COO, AuCl(n)(OH)(4-n), CuCl(2), or HgCl(2) showed that Ag(I), Au(III), Cu(II), and Hg(II) were readily reduced to Ag(0), Au(0), Cu(0), and Hg(0). Imaging of the resulting solids from the Ag(I)-, Au(III)-, and Cu(II)-amended green rust suspensions by transmission electron microscopy indicated the formation of submicron-sized particles of Ag(0), Au(0), and Cu(0). The facile reduction of Ag(I), Au(III), Cu(II), and Hg(II) to Ag(0), Au(0), Cu(0), and Hg(0), respectively, by green rust suggests that the presence of green rusts in suboxic soils and sediments can have a significant impact on the biogeochemistry of silver, gold, copper, and mercury, particularly with respect to their mobility.

Electron Probe Microanalysis↗
PubMed2003

Experimental design of Fenton and photo-Fenton reactions for the treatment of cellulose bleaching effluents.

Multivariate experimental design was applied to the treatment of a cellulose conventional bleaching effluent in order to evaluate the use of the Fenton reagent under solar light irradiation. The effluent was characterised by the general parameters total organic carbon (TOC), chemical oxygen demand and color, and it was analysed for chlorinated low molecular weight compounds using GC-MS. The main parameters that govern the complex reactive system: Fe(II) and H(2)O(2) initial concentration, and temperature were simultaneously studied. Factorial experimental design allowed to assign the weight of each variable in the TOC removal after 15 min of reaction. Temperature had an important effect in the organic matter degradation, especially when the ratio of Fenton reagents was not properly chosen. Fenton reagent under solar irradiation proved to be highly effective for these types of wastewaters. A 90% TOC reduction was achieved in only 15 min of treatment. In addition, the GC-MS analysis showed the elimination of the chlorinated organic compounds initially detected in the studied bleaching effluents.

Chlorine Compounds↗
PubMed2000

Iron uptake by fungi: contrasted mechanisms with internal or external reduction.

Almost all iron uptake by fungi involves reduction from Fe(III) to Fe(II) in order to facilitate ligand exchange. This leads to two mechanisms: uptake before reduction, or reduction before uptake. Many fungi secrete specific hydroxamate siderophores when short of iron. The mechanism with uptake before reduction is described in the context of siderophore synthesis and usage, since it applies to many (but not all) siderophores. The hydroxamate functional group is synthesized from ornithine by N5 hydroxylation and acylation. In most fungal siderophores, two or three modified ornithines are joined together by a non-ribosomal peptide synthetase. The transcription of these genes is regulated by an iron activated repressor. There is evidence that the iron-free siderophore may be stored in intracellular vesicles until secretion is required. After loading with iron, re-entry is likely to be via a proton symport. In some fungi, siderophores are used for iron storage. The iron is liberated by an NADPH-linked reductase. The second mechanism starts with Fe(III) reduction. In yeast, this is catalysed by an NADPH-linked transmembrane reductase, which has homology with the NADPH oxidase of neutrophils. There are two closely similar reductases with overlapping roles in Fe(III) and Cu(II) reduction, while the substrates for reduction include Fe(III)-siderophores. External reductants, which may be important in certain fungi, include 3-hydroxyanthranilic acid, melanin, cellobiose dehydrogenase and 2,5-dimethylhydroquinone. In yeast, a high-affinity iron uptake pathway involves reoxidation of Fe(II) to Fe(III), probably to confer specificity for iron. This is catalysed by a copper protein which has homology with ceruloplasmin, and is closely coupled to Fe(III) transport. The transcription of these genes is regulated by an iron-inhibited activator. Because of its copper requirement, the high-affinity pathway is blocked by disruption of genes for copper metabolism. A low-affinity uptake transports Fe(II) directly and is important in anoxic growth. In many fungi, mechanisms with internal or external reduction are both important. The external reduction is applicable to almost any Fe(III) complex, while internal reduction is more efficient at low iron but requires a siderophore permease through which toxins might enter. Both mechanisms require close coupling of Fe(III) reduction and Fe(II) utilization in order to minimize production of active oxygen.

Biological Transport↗
PubMed2001

Selenium geochemistry of paddy soils in Yangtze River Delta.

Selenium (Se) content both in total and bioavailable forms were very low (25-35 and 9.5 micrograms/kg, respectively) in waterlogged paddy soils in the central Yangtze River Delta. This was due to changes in geochemistry and the inherent properties of the parent materials of these lowland paddy soils. The very low Se content (23 micrograms/kg) in the parent material resulted in low total Se content in the soil. The main chemical changes under long-term waterlogged conditions are depletion of molecular oxygen, decrease of redox potential, and reduction of Fe (III) to Fe (II) and SeO3(2-) to Se0. This led to low availability of Se in soils, and subsequently low Se content (29 micrograms/kg) in brown rice grain produced in this region. It has been suspected that low Se content in staple food might be one of the major reasons for a high infection rate of the intestine and stomach cancers and the higher death rate caused by these diseases in the region. Foliage spray of Na2SeO3 at early heading stage of rice plant growth improved the Se content of brown rice grain, hull, and straw, and would improve human and animal health.

Biological Availability↗
PubMed1997

Equilibrium and kinetic studies of iron(II) and iron(III) complexes of some alpha (N)-heterocyclic thiosemicarbazones. Reduction of the iron(III) complexes of 2-formylpyridine thiosemicarbazone and 2-acetylpyridine thiosemicarbazone by cellular thiol-like reducing agents.

alpha (N)-heterocyclic thiosemicarbazones have been shown to possess antitumor properties in mammalian cells through the inhibition of DNA synthesis; the ability to provide the inhibitory action is probably due to coordination of iron. This paper deals with equilibrium and kinetic studies involving 2-formylpyridine thiosemicarbazone (HFPT) and 2-acetylpyridine thiosemicarbazone (HAPT) coordinated to Fe(II) and Fe(III) cations in aqueous solution. The formation constants of all species present in equilibrium were determined. Kinetic measurements of the reduction of the Fe(III) complex of both ligands by thiolic reducing agents, that can act as structural models of cellular thiols, i.e., N-acetyl-L-cysteine (ACCIS) and dithiothreitol (DTT), were carried out. The experimental data lead to a rate law of the type v = k1[A] + k2[A] [B], where [A] represents the concentration of the complex and [B] that of the reducing agent, indicating the coexistence of two reaction pathways. One pathway depends only on the complex concentration and occurs even in the absence of the reducing agent, and the other involves both the complex and ACCIS or DTT.

DNA Replication↗
PubMed1997

Effects of additional iron-chelators on Fe(2+)-initiated lipid peroxidation: evidence to support the Fe2+ ... Fe3+ complex as the initiator.

The addition of chelated Fe2+ ions in a liposomal system often results in a short lag period before peroxidation starts. The addition of a second chelator at the end of the lag period results in an inhibition of the lipid peroxidation. The degree of inhibition depends on the stability constants of the chelator in ligating Fe2+ and/or Fe3+. A more striking inhibitory effect was observed for the chelators with higher stability constant for either or both Fe(2+)- and Fe(3+)-complex, but much less inhibition was found for those with lower stability constants for both complexes. Assuming that the "initiator" for iron-dependent lipid peroxidation is formed through the redox process of iron ion and finally emerged at the end of the latent period, the inhibitory effect of the second chelator may be explained as the abstraction of either Fe2+ or Fe3+ from the initiator by an additional free chelator, which results in the decomposition of the initiator. This study supports the hypothesis that a Fe2+ ... Fe3+ complex is responsible for iron-initiated lipid peroxidation.

Adenosine Diphosphate↗
PubMed2000

Complexation of iron(III) and iron(II) by citrate. Implications for iron speciation in blood plasma.

Estimates of the concentrations and identity of the predominant complexes of iron with the low-molecular-mass ligands in vivo are important to improve current understanding of the metabolism of this trace element. These estimates require a knowledge of the stability of the iron-citrate complexes. Previous studies on the equilibrium properties of the Fe(III)-citrate and Fe(II)-citrate are in disagreement. Accordingly, in this work, glass electrode potentiometric titrations have been used to re-determine the formation constants of both the Fe(III)- and Fe(II)-citrate systems at 25 degrees C in 1.00 M (Na)Cl and the reliability of these constants has been evaluated by comparing the measured and predicted redox potentials of the ternary Fe(III)-Fe(II)-citrate system. The formation constants obtained in this way were used in computer simulation models of the low-molecular-mass iron fraction in blood plasma. Redox equilibria of iron are thus included in large models of blood plasma for the first time. The results of these calculations show the predominance of Fe(II)-carbonate complexes and a significant amount of aquated Fe(II) in human blood plasma.

Citric Acid↗
PubMed1997

Characterization of Fe2+ and Fe3+ transport by iron-loaded cardiac myocytes.

Plasma iron overload causes cardiac iron accumulation leading to toxicity and organ failure. In order to understand the basis of iron acquisition, we examined mechanisms of Fe3+ and Fe2+ uptake in control and iron-loaded cardiomyocyte cultures. Iron loading increased rates of Fe3+ and Fe2+ uptake, primarily by increasing Vmax. Inhibition of Fe3+ transport by impermeable Fe2+ chelators and the presence of a cell surface ferricyanide reductase activity are consistent with a role for redox cycling in Fe3+ uptake. However, flavoproteins and copper-dependent oxidases known to be required for redox-active iron transport in yeast do not appear to be involved in iron uptake by cardiac myocytes, nor do the abundant cardiac L-type Ca2+ channels. The data suggest that both redox states of iron contribute to cardiac iron accumulation in iron overload.

Animals↗
PubMed2001

Regulation of glutamine synthetase by metal-catalyzed oxidative modification in the marine oxyphotobacterium Prochlorococcus.

The inactivation of glutamine synthetase (GS; EC 6.3.1.2) by metal-catalyzed oxidation (MCO) systems was studied in several Prochlorococcus strains, including the axenic PCC 9511. GS was inactivated in the presence of various oxidative systems, either enzymatic (as NAD(P)H+NAD(P)H-oxidase+Fe(3+)+O(2)) or non-enzymatic (as ascorbate+Fe(3+)+O(2)). This process required the presence of oxygen and a metal cation, and is prevented under anaerobic conditions. Catalase and peroxidase, but not superoxide dismutase, effectively protected the enzyme against inactivation, suggesting that hydrogen peroxide mediates this mechanism, although it is not directly responsible for the reaction. Addition of azide (an inhibitor of both catalase and peroxidase) to the MCO systems enhanced the inactivation. Different thiols induced the inactivation of the enzyme, even in the absence of added metals. However, this inactivation could not be reverted by addition of strong oxidants, as hydrogen peroxide or oxidized glutathione. After studying the effect of addition of the physiological substrates and products of GS on the inactivation mechanism, we could detect a protective effect in the case of inorganic phosphate and glutamine. Immunochemical determinations showed that the concentration of GS protein significantly decreased by effect of the MCO systems, indicating that inactivation precedes the degradation of the enzyme.

Anaerobiosis↗
PubMedDate not supplied

Nonagenarians from the Swedish NONA Immune Study have increased plasma antioxidant capacity and similar levels of DNA damage in peripheral blood mononuclear cells compared to younger control subjects.

The results of previous work from our laboratories have suggested that free radical damage to T cells as they age may contribute to the age-related decline in the T cell-mediated immune response. The aims of this investigation were to assess the efficiency of in vivo antioxidant capacity through determining the antioxidant capacity of plasma using the ferric reducing ability of plasma assay, and to assess the levels and types of DNA damage (as a measure of in vivo antioxidant efficiency) using the alkaline comet assay and two enzymatic modifications of the comet assay, in peripheral blood mononuclear cells (PBMCs) from nonagenarian subjects drawn from the Swedish NONA Immune Study. The results obtained were compared with those from middle-aged (40-60 years) controls to identify potential anti-immunosenescent effects of in vivo antioxidants. The results revealed a significantly higher plasma antioxidant capacity in NONA subjects compared to controls, and these results support a relationship between longevity and intact immune function, which may be underpinned by antioxidant defences which reduce free radical damage to PBMC, thus helping to maintain cell function. The NONA subjects were found to have similar levels of DNA damage in their PBMCs to those found in middle aged controls.

Adult↗
PubMed1997

Flow-injection biamperometric determination of epinephrine.

A flow-injection manifold is proposed for the determination of epinephrine. The experimental procedure is based on the indirect biamperometric detection of the drug by using Fe(III)-Fe(II) as an indicating redox system and a flow-through detector with two polarized Pt wire electrodes. The calibration graph is linear over the range 0.3-20 micrograms ml-1 of epinephrine. The relative standard deviation for the determination of 10 micrograms ml-1 of epinephrine is 1.5% (n = 25) and the sample throughput is 153 h-1. The method was applied to the determination of epinephrine in two commercially available pharmaceutical preparations.

Electrochemistry↗