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PubMed1997

Ascorbic acid and dehydroascorbic acid interconversion without net oxidation or reduction.

The interconversion of ascorbic acid and dehydroascorbic acid was examined in aqueous solution using unlabeled dehydroascorbic acid and nonlabile, stable isotope-labeled ascorbic acid by gas chromatographic/mass spectrometric analysis. Although the formation of unlabeled ascorbic acid from unlabeled dehydroascorbic acid or labeled dehydroascorbic acid from labeled ascorbic acid did not occur to any significant extent when either solutions of unlabeled dehydroascorbic acid or labeled ascorbic acid were incubated alone, significant amounts of both labeled dehydroascorbic acid and unlabeled ascorbic acid formed when unlabeled dehydroascorbic acid was incubated with labeled ascorbic acid at acid pH. At alkaline pH, interconversion did not occur to any appreciable extent. Likewise, interconversion did not appear to occur in plasma at physiologic concentrations of ascorbic acid, but did occur with pharmacologic concentrations. These data show that ascorbic acid and dehydroascorbic acid interconvert in acidic solution, suggesting the reducing hydrogen atoms are delocalized when ascorbic acid is paired with dehydroascorbic acid under these circumstances. Alkaline pH and plasma inhibit the interconversion.

Ascorbic Acid↗
PubMed1983

Further characterization of the potentiometric behavior of cytochrome oxidase. Cytochrome alpha stays low spin during oxidation and reduction.

An improved device for potentiometry using magnetic circular dichroism spectroscopy has been developed and used to characterize the potentiometric behavior of solubilized beef heart cytochrome oxidase. In the absence of inhibitors, the electron affinity of cytochromes alpha and alpha 3 are indistinguishable and adequately described by the allosteric model of Nicholls and Peterson (Nicholls, P., and Peterson, L. C. (1972) Biochim. Biophys. Acta 357, 462-467). All of the cytochrome alpha can be accounted for as low spin heme throughout the titration. Cytochrome c present at 1:1, 2:1, and 4:1 stoichiometry with cytochrome alpha did not significantly affect the potentiometric behavior of alpha or chondroitinase alpha 3; at the 1:1 ratio the midpoint potential of cytochrome c was lowered by about 30 mV. In the presence of formate, azide and cyanide cytochrome alpha assumed approximately n = 1 behavior. However, the response of alpha 3 differed with each reagent and was particularly complex in the presence of azide. Fluoride produced very small changes in the potentiometric behavior suggesting that it may not be a ligand to cytochrome alpha 3. Possible deficiencies in the allosteric model are examined.

Animals↗
PubMed1976

Active site of ribonucleoside diphosphate reductase from Escherichia coli. Inactivation of the enzyme by 2'-substituted ribonucleoside diphosphates.

Ribonucleoside diphosphate reductase is an allosteric enzyme consisting of two nonidentical subunits, proteins B1 and B2. B1 contains dithiols which participate in the oxidation-reduction reactions of electron transport, while B2 contains a free radical essential for activity. Ribonucleoside diphosphates are bound to B1 but not to B2. Addition of 2'-deoxy-2'-chloro ribonucleoside diphosphates to ribonucleotide reductase irreversibly inactivates B1 without affecting B2. The reaction is specific since (a) it requires the presence of active B2, (b) it is controlled by allosteric effectors, (c) B1 is protected against inactivation by the normal substrates, and (d) the chloro-substituted nucleoside monophosphates have no effect. The inactivation of B1 is caused by a modification of the oxidation-reduction dithiols. The chloro derivatives decompose into free base, chloride ion, and 2-deoxyribose 5-diphosphate as a consequence of reaction with the enzyme. 2'-Deoxy-2"-azido ribonucleoside diphosphates cause an irreversible inactivation of B2 without affecting B1. The reaction is specific by the above criteria, indicating that the azido derivatives also bind to the active site of the enzyme. On reduction by ribonucleotide reductase, the azido derivatives function as radical scavengers and selectively destroy the free radical of B2, indicating that this radical participates in ribonucleotide reduction directly. On the basis of these results, a model of the active site of ribonucleotide reductase is proposed in which the site is formed from both B1 and B2. In the site the electron-donating oxidation-reduction active dithiols of B1 are in close contact with the free radical of B2. The azido derivative also inactivates the adenosylcobalamin-dependent ribonucleoside triphosphate reductase from Lactobacillus leichmannii and a ribonucleotide reductase preparation from calf thymus, indicating a general involvement of free radical intermediates in enzyme-catalyzed ribonucleotide reduction.

Escherichia coli↗
PubMed1976

[The significance of the bacterial steroid degradation for the etiology of large bowel cancer. IV. Deconjugation of glycocholic acid, oxidation, and reduction of cholic acid by saccharolytic Bacteroides species (author's transl)].

A total of 36-38 strains (depending on the test series) of the strictly anaerobic Bacteroides species V. bulgatus, B. fragilis, B. thetaiotamicron, and B. distasonis was tested for the ability of splitting the acide amide linkage of glycocholate and for a further degradation of cholate. We found 23 of 38 strains (60 per cent) to be able to deconjugate glycocholate, but as many as 18 (46 per cent) resulted in an intensive to complete degradation. On the other hand 32 of 36 strains (89 per cent) were able to degrade cholate when cultivated anaerobically. They normally formed 1 transformation product, however, occasionally 2-3. Using the aerobic incubation of resting cells as test system we observed 30 active strains of 37 (81 per cent), which as well produced 1 degradation product generally, but sometimes 2-4 compounds. 3 strains transformed cholate during growth only. Thin layer-, gas chromatography, and combined gas chromatography-mass spectrometry were used for the identification of transformation products. We proved the main degradation product of all active strains to be 3alpha,12alpha-dihydroxy-7-oxo-5beta-cholanoate, by anaerobic cultivation as well as by aerobic incubation of cell suspensions. Deoxycholate (3alpha,12alpha-dihydroxy-5beta-cholanoate), in vivo the main product of cholate transformation, was hitherto found to be formed by 3 strains only as main degradation product, it may probably be a by-product of the degradation with other strains. All these strains, however, may also oxidise the 7alpha-hydroxyl group beside dehydroxylating cholate. For this reason we assume that the conditions for the formation of deoxycholate are in general not existent in our experiments. The third degradation product, formed under anaerobic conditions, is probably a monohydroxy-monooxo-cholanoate, derived from deoxycholate. Structures of additional transformation products, occasionally found under aerobic incubation, which are all less polar than 3alpha,12alpha-dihydroxy-7-oxo-5beta-cholanoic acid, could not be elucidated on account of minor amounts available. Bacteroides species are unable to transform the side chain of cholate, either as anaerobically growing cultures, or as aerobically incubated resting cells.

Aerobiosis↗
PubMed1990

Effects of oxidants and reductants on the efficiency of excitation transfer in green photosynthetic bacteria.

The efficiency of energy transfer in chlorosome antennas in the green sulfur bacteria Chlorobium vibrioforme and Chlorobium limicola was found to be highly sensitive to the redox potential of the suspension. Energy transfer efficiencies were measured by comparing the absorption spectrum of the bacteriochlorophyll c or d pigments in the chlorosome to the excitation spectrum for fluorescence arising from the chlorosome baseplate and membrane-bound antenna complexes. The efficiency of energy transfer approaches 100% at low redox potentials induced by addition of sodium dithionite or other strong reductants, and is lowered to 10-20% under aerobic conditions or after addition of a variety of membrane-permeable oxidizing agents. The redox effect on energy transfer is observed in whole cells, isolated membranes and purified chlorosomes, indicating that the modulation of energy transfer efficiency arises within the antenna complexes and is not directly mediated by the redox state of the reaction center. It is proposed that chlorosomes contain a component that acts as a highly quenching center in its oxidized state, but is an inefficient quencher when reduced by endogenous or exogenous reductants. This effect may be a control mechanism that prevents cellular damage resulting from reaction of oxygen with reduced low-potential electron acceptors found in the green sulfur bacteria. The redox modulation effect is not observed in the green gliding bacterium Chloroflexus aurantiacus, which contains chlorosomes but does not contain low-potential electron acceptors.

Bacteria↗
PubMed2003

Reduction of Salmonella enterica on alfalfa seeds with acidic electrolyzed oxidizing water and enhanced uptake of acidic electrolyzed oxidizing water into seeds by gas exchange.

Alfalfa sprouts have been implicated in several salmonellosis outbreaks in recent years. The disinfectant effects of acidic electrolyzed oxidizing (EO) water against Salmonella enterica both in an aqueous system and on artificially contaminated alfalfa seeds were determined. The optimum ratio of seeds to EO water was determined in order to maximize the antimicrobial effect of EO water. Seeds were combined with EO water at ratios (wt/vol) of 1:4, 1:10, 1:20, 1:40, and 1:100, and the characteristics of EO water (pH, oxidation reduction potential [ORP], and free chlorine concentration) were determined. When the ratio of seeds to EO water was increased from 1:4 to 1:100, the pH decreased from 3.82 to 2.63, while the ORP increased from +455 to +1,073 mV. EO water (with a pH of 2.54 to 2.38 and an ORP of +1,083 to +1,092 mV) exhibited strong potential for the inactivation of S. enterica in an aqueous system (producing a reduction of at least 6.6 log CFU/ml). Treatment of artificially contaminated alfalfa seeds with EO water at a seed-to-EO water ratio of 1:100 for 15 and 60 min significantly reduced Salmonella populations by 2.04 and 1.96 log CFU/g, respectively (P < 0.05), while a Butterfield's buffer wash decreased Salmonella populations by 0.18 and 0.23 log CFU/g, respectively. After treatment, EO water was Salmonella negative by enrichment with or without neutralization. Germination of seeds was not significantly affected (P > 0.05) by treatment for up to 60 min in electrolyzed water. The uptake of liquid into the seeds was influenced by the internal gas composition (air, N2, or O2) of seeds before the liquid was added.

Chlorine↗
PubMed2005

Effects of antioxidant supplementation on postprandial oxidative stress and endothelial dysfunction: a single-blind, 15-day clinical trial in patients with untreated type 2 diabetes, subjects with impaired glucose tolerance, and healthy controls.

BACKGROUND: Increased generation of reactive oxygen species (ROS) and oxidative stress may be of crucial importance in the pathogenesis of endothelial damage. Furthermore, there is understood to be a relationship between endothelial damage, glycemic control, disorders of lipid metabolism, and coagulative hemostatic disorders. OBJECTIVE: This study investigated within- and between-group changes in various circulating markers of oxidation-reduction balance and endothelial function after a balanced moderate-fat meal with and without antioxidant supplementation in patients with early-stage, untreated type 2 diabetes mellitus; subjects with impaired glucose tolerance (IGT); and healthy controls. METHODS: In this single-blind, controlled clinical study, groups of patients with type 2 diabetes and subjects with IGT were identified and compared with a group of healthy controls. All groups followed a controlled, well-balanced diet for 10 days before and throughout the study. Before and after consumption of a standardized moderate-fat meal, plasma levels of oxidants (malondialdehyde, 4-hydroxynonenal, oxidized low-density lipoprotein), the antioxidant glutathione peroxidase, and markers of endothelial function (NO, endothelin-1, von Willebrand factor [vWF], vascular cell adhesion molecule-1 [VCAM-1]) were determined. These measures were then reassessed after 15 days of standard antioxidant treatment consisting of a thiol-containing antioxidant (N-acetylcysteine 600 g/d), a bound antioxidant (vitamin E 300 g/d), and an aqueous phase antioxidant (vitamin C 250 mg/d). The efficacy of antioxidant treatment in reversing abnormalities in oxidation-reduction balance after a moderate-fat meal was assessed by evaluating changes in plasma levels of ROS on the morning of the 16th day following an overnight fast. Safety was monitored in terms of adverse events, vital signs, physical findings, and laboratory values. RESULTS: The study included 46 patients with type 2 diabetes (23 men, 23 women; mean [SD] age, 41 [3] years; mean body mass index [BMI], 24 [2] kg/m(2)), 46 with IGT (23 men, 23 women; mean age, 39 [3] years; mean BMI, 23 [3] kg/m(2)), and 46 control subjects (23 men, 23 women; mean age, 40 [1] years; mean BMI, 22 [1] kg/m(2)). Before supplementation, all 3 groups had significantly increased levels of oxidants, vWF, and VCAM-1 (all, P < 0.001) and significantly decreased levels of antioxidants and NO (both, P < 0.001) after consumption of a moderate-fat meal. After 15 days of antioxidant treatment, significant improvements in these measures were seen in all groups (P < 0.05). CONCLUSIONS: This study showed changes in oxidation-reduction balance, NO bioavailability, and nonthrombogenic endothelial factors after a moderate-fat meal in patients with type 2 diabetes and those with IGT, but these postprandial changes were reverse in all subjects after 15 days of standard antioxidant supplementation. These findings suggest that the use of anti-oxidants may have decreased oxidative stress in these subjects.

Acetylcysteine↗
PubMed2002

Transmission electron microscopy studies of the nanoscale structure and chemistry of Pt50Ru50 electrocatalysts.

The structural and chemical heterogeneity of 2.5-nm Pt50Ru50 electrocatalysts was studied by transmission electron microscopy using selected area diffraction, lattice imaging, electron-energy loss spectroscopy, and energy-dispersive X-ray spectroscopy. The catalysts with the highest methanol oxidation activities exhibit oxidation-induced phase separation on the nanoscale to from Pt-rich metal embedded in Ru-rich hydrous and anhydrous oxide. Reduction of the oxide-on metal samples produces a true bimetallic face-centered cubic Pt50Ru50 alloy, with 275 times lower oxidation activity.

Alloys↗
PubMed1988

Mechanism of inhibition of reverse transcriptase by quinone antibiotics. II. Dependence on putative quinone pocket on the enzyme molecule.

Inhibition of avian myeloblastosis virus (AMV) reverse transcriptase by natural and synthetic quinones including antibiotics could be accounted for by an oxidation-reduction reaction. The quinones were shown to function as electron acceptors as revealed by the catalytic oxidation of NADH by Clostridium kluyveri diaphorase which was in excellent agreement with enzyme inhibition activity. The kinetics of inhibition of AMV reverse transcriptase by three synthetic quinones with different core structures, i.e., 6-methoxy-5,8-dihydroquinoline-5,8- dione, 5,8-dihydroisoquinoline-5,8-dione and 1,4-naphthoquinone, were studied. These quinones inhibited reverse transcriptase in the same manner as streptonigrin (STN) and were shown to act at a single class of reaction site(s) on the enzyme molecule. In contrast, the quinones with bulky substituents, i.e., 7-(2-nitrophenethylamino)-5,8-dihydroisoquinoline-5,8-dione and 7-methoxy-6-methyl-3-piperidino-5,8-dihydroisoquinoline-5,8-dione, were inactive as inhibitors of reverse transcriptase, whereas they retained competent catalytic activities in the oxidation of NADH by C. kluyveri diaphorase. Based on these observations, the existence of a specific site of interaction on the enzyme molecule, referred to as a quinone pocket, was proposed. The quinone pocket might play a crucial role in the early sequence of events leading to the inhibition of reverse transcriptase by quinones including STN and sakyomicin A (SKM). Access of SKM to a quinone pocket might be restricted due to its bulky structure in the vicinity of the quinone group. This is inferred from unsuccessful inhibition of reverse transcriptase by the quinones with bulky substituents, resulting in much poorer inhibition of reverse transcriptase in spite of more potent electron acceptor activity in the oxidation-reduction system as compared with those of STN.

Animals↗
PubMed1999

Opposing changes in 3alpha-hydroxysteroid dehydrogenase oxidative and reductive activities in rat leydig cells during pubertal development.

The enzyme 3alpha-hydroxysteroid dehydrogenase (3alpha-HSD) has an important role in androgen metabolism, catalyzing the interconversion of dihydrotestosterone (DHT) and 5alpha-androstane-3alpha,17beta-diol (3alpha-DIOL). The net direction of this interconversion will affect the amount of biologically active ligand available for androgen receptor binding. We hypothesize that in Leydig cells, differential expression of 3alpha-HSD enzymes favoring one of the two directions is a mechanism by which DHT levels are controlled. In order to characterize 3alpha-HSD in rat Leydig cells, the following properties were analyzed: rates of oxidation (3alpha-DIOL to DHT) and reduction (DHT to 3alpha-DIOL) and preference for the cofactors NADP(H) and NAD(H) (i.e., the oxidized and reduced forms of both pyridine nucleotides) in Leydig cells isolated on Days 21, 35, and 90 postpartum. Levels of 3alpha-HSD protein were measured by immunoblotting using an antibody directed against the liver type of the enzyme. Levels of 3alpha-HSD protein and rates of reduction were highest on Day 21 and lowest on Day 90. The opposite was true for the rate of 3alpha-HSD oxidation, which was barely detectable on Day 21 and highest on Day 90 (59.08 +/- 6.35 pmol/min per 10(6) cells, mean +/- SE). Therefore, the level of 3alpha-HSD protein detectable by liver enzyme was consistent with reduction but not with oxidation. There was a clear partitioning of NADP(H)-dependent activity into the cytosolic fraction of Leydig cells, whereas on Days 35 and 90, Leydig cells also contained a microsomal NAD(H)-activated 3alpha-HSD. We conclude that 1) the cytosolic 3alpha-HSD in Leydig cells on Day 21 behaves as a unidirectional NADPH-dependent reductase; 2) by Day 35, a microsomal NAD(H)-dependent enzyme activity is present and may account for predominance of 3alpha-HSD oxidation over reduction and the resultant high capacity of Leydig cells on Day 90 to synthesize DHT from 3alpha-DIOL.

3-Hydroxysteroid Dehydrogenases↗
PubMed1976

Oxidation and reduction of copper ions in catalytic reactions of Rhus laccase.

1) It was demonstrated by colorimetric as well as EPR measurements that the native (aerobic, resting state) Rhus vernicifera laccase contains both Cu2+ and Cu+ (total Cu content was 4.0 gram atoms/mole). The ratio of Cu2+ to total Cu in laccase varied (42-90%) in samples of latex collected from various districts. The absorption maximum at 615 nm was proportional to the content of total Cu in the enzyme sample. Laccase activity was found to almost parallel the content of the Cu2+ form. The oxidized minus reduced difference absorbance of the enzyme at 330 nm shoulder was proportional to the amount of Cu2+. 2) Steady state level of oxidation of laccase copper during the laccase copper catalytic action, the rates of reduction by substrates and the oxidation by O2 were determined by following absorbance changes at 615 and 330 nm by the stopped flow method. 3) All the results from titrimetric and kinetic experiments were consistent with the laccase model previously proposed by Makino and Ogura in which a laccase molecule contains 1 Cu(615) and 3 Cu(330). Our expanded model states that a laccase sample originally contains active as well as inactive enzymes. In the active enzyme, Cu ions are reactive to O2 but in the inactive enzyme, Cu can be oxidized only by oxidizing agents such as H2O2 or ferricyanide, or by a slow intermolecular electron transfer from Cu(615) to the active enzyme. In both species of enzyme rapid reduction of Cu2+ ions by substrate takes place. In comparative studies of the reactivities of Cu ions in various copper proteins, we would like to suggest that oxidatic activity of a copper protein is due to the Cu+ form of the enzyme ions with O2.

Anaerobiosis↗
PubMed2004

Influence of packing media on nitrogen removal in a subsurface infiltration system.

Influence of packing media on nitrogen removal in a subsurface infiltration system was studied. System A was filled with loamy soil and system B was filled with mixed soil of 75% red clay with 25% cinder. Both systems were fed with sewage at the same hydraulic loading of 2 cm/d at continuous operation mode. The same excellent removal performances of COD and T-P could be achieved in both infiltration systems with removal rates about 85% and 98%, respectively. In system A, NH4+ -N removal rate was as high as 96.5% and T-N removal rate was relatively much lower as 55.7%. And in system B, NH4+ -N removal rate was as low as 75.4% and T-N removal rate was relatively much higher as 75.5% . The difference was attributed to different soil oxidation-reduction condition that was greatly influenced by soil texture in subsurface infiltration system. Loamy soil led to oxidative condition that was favorable to nitrification and disadvantageous to denitrification. The results were just adverse to the system filled with clay. Intermittent operation was adopted to improve nitrogen removal in system B. NH4+ -N removal rate could be increased to about 95% and T-N removal rate could be increased to about 90% at intermittent operation mode in system B. Analysis of nitrogen removal mechanisms indicated that nitrification-denitrification was the primary nitrogen removal path in subsurface infiltration system and crop uptake was another important nitrogen removal way. It was the key to improve the total N removal performance that a suitable packing soil was available to present favorable oxidation-reduction condition for simultaneous nitrification and denitrification.

Aluminum Silicates↗
PubMed2001

Mitochondrial perturbations and oxidant stress in lymphocytes from patients undergoing surgery and general anesthesia.

BACKGROUND: Previous studies have shown that a profound suppression of immune function transiently occurs in patients who undergo surgery under general anesthesia. The decline in the absolute counts of peripheral blood lymphocytes constitutes a major factor accounting for this immune defect, and recent evidence indicates that apoptosis plays a crucial role in determining postsurgical lymphocytopenia. HYPOTHESIS: An altered oxidation-reduction status of mitochondria may contribute through apoptosis to the loss of lymphocytes following surgical trauma and general anesthesia. DESIGN: We studied 16 patients with American Society of Anesthesiologists' physical status I or II who underwent elective surgery under general anesthesia. The data were collected prospectively. SETTING: University hospital. MAIN OUTCOME MEASURES: Samples of peripheral blood were drawn on the day before surgery and at 24 and 96 hours after the operation. Following lymphocyte isolation, the mitochondrial transmembrane potential was assessed by flow cytometry using 3,3'-dihexylocarbo-cyanine iodide, and stains with hydroethidine and 2'-7'-dichlorofluorescein diacetate were used to determine the generation of reactive oxygen species. The labeling of lymphocytes with monobromobimane was used to assess the presence of reduced glutathione. RESULTS: At 24 hours after surgery, we detected a significantly elevated frequency of peripheral blood lymphocytes (P =.002), which incorporated low levels of 3,3'-dihexylocarbo-cyanine iodide, compared with the preoperative period. At this same time point, the frequency of lymphocytes with the hydroethidine- and 2'-7'-dichlorofluorescein diacetate-positive phenotype was elevated compared with baseline levels. Conversely, at 24 hours after surgery, the frequency of cells that stained positive for glutathione was strongly decreased compared with preoperative values. Overall measurements returned to the baseline levels at 96 hours after surgery. CONCLUSION: The strict association we observed between the overproduction of reactive oxygen species and the disruption of the mitochondrial transmembrane potential supports the view that alterations in mitochondrial energy metabolism, paralleled by the presence of a pro-oxidant oxidation-reduction status, could be involved in the accelerated apoptotic loss of lymphocytes following surgical trauma and general anesthesia.

Anesthesia, General↗
PubMed2006

Influence of sediment redox conditions on release/solubility of metals and nutrients in a Louisiana Mississippi River deltaic plain freshwater lake.

The influence of sediment redox conditions on solubility of selected metals and nutrients in sediment from a coastal Louisiana freshwater lake (Lake Cataouatche) receiving diverted Mississippi River water was quantified. Sediment redox was cycled step wise in 50 mV increments between oxidized (-200 to +500 mV) and reduced (+500 to -200 mV) conditions. Changes in sediment oxidation/reduction status and pH influenced solubility of both metals and nutrients. When redox potential (Eh) was increased from -200 to +500 mV, sediment pH decreased from 7.1 to 5.7. When the sediment Eh decreased from +500 to -200 mV, pH increased from 5.7 to 7.1. The increase in sediment acidity upon oxidation resulted in the release of the Pb, Ca, Mg, Al, and Zn into solution. The solution concentration of these elements was inversely proportional to Eh (P</=0.05). The concentration of Fe, Mn, and P in sediment suspension was strongly governed by changes in oxidation-reduction status of sediment. The oxidation of reduced sediment resulted in a decrease in amount of Fe and Mn in solution, a result of the conversion of soluble ferrous and manganous form to less soluble ferric and manganic form. Following reduction of oxidized sediment, Fe and Mn became more soluble because the ferric iron and manganic manganese form changed to ferrous and manganous form. Phosphorus behavior as influenced by oxidation/reduction status was closely related to Fe and Mn chemistry with an increase in phosphate following iron reduction. This study demonstrated that sediment redox potential is an important parameter affecting metal and nutrient solubility and mobility in Louisiana coastal freshwater lake sediment. Reduction or aeration status of sediment should be considered in predicting the release of these elements into the aquatic environment.

Environmental Monitoring↗
PubMed2005

Ordering the reductive and cytochrome P450 oxidative steps in demethylsterigmatocystin formation yields general insights into the biosynthesis of aflatoxin and related fungal metabolites.

The biosynthesis of the potent environmental carcinogen aflatoxin B1 involves ca. 15 steps beyond the first polyketide intermediate. Central among these is the rearrangement of the anthraqinone versicolorin A to the xanthone demethylsterigmatocystin. Genetic evidence strongly suggests that two enzymes are required for this process, a cytochrome P450, AflN, and a probable NADPH-dependent oxidoreductase, AflM. Given the overall redox change evident in this skeletal rearrangement, two rounds of oxidation and a reduction necessarily occur. Earlier experiments indicated that reductive deoxygenation of versicolorin A is not the first step. In the present report we consider a mechanistic alternative that AflM-mediated reduction is instead the last of these three reactions prior to formation of the xanthone intermediate. To this end, 9-hydroxydihydrodemethylsterigmatocystin was prepared by total synthesis as was its 9-deoxy analogue, an established aflatoxin precursor. During the final isolation of the "angular" synthetic xanthone targets it was found that acid catalysis promoted their isomerization to thermodynamically favored "linear" xanthones. Whole-cell and ground-cell incubations of the 9-hydroxy- and 9-deoxyxanthones were conducted with a mutant strain of Aspergillus parasiticus blocked at the first step of the pathway and examined for their ability to support aflatoxin production. The 9-deoxyxanthone gave dramatically enhanced levels of the mycotoxin. The 9-hydroxyxanthone, on the other hand, afforded no detectable increase in aflatoxins above controls, indicating that reductive deoxygenation at C-9 of a xanthone precursor does not take place in aflatoxin biosynthesis. Constraints imposed by earlier studies and the experiments in this paper serve to eliminate simple and intuitive conversions of versicolorin A to demethylsterigmatocystin and lead inescapably to a more subtle reaction sequence of oxidation-reduction-oxidation. Previous puzzling observations of extensive A-ring hydrogen exchange in the course of the rearrangement of versicolorin A to demethylsterigmatocystin have now been explained by a new mechanism that is consistent with all extant data. We propose that P450-mediated aryl epoxidation (AflN) initially disrupts the aromatic A-ring of versicolorin A. Oxirane opening enables A-ring proton exchange, as does the subsequent AflM-mediated reductive step. A second cycle of P450 oxidation (AflN), this time a Baeyer-Villiger cleavage, enables decarboxylation and the formation of demethylsterigmatocystin. Mechanistic and stereoelectronic principles that underlie this proposal are described and may prove general as illustrated in biogenetic hypotheses for four other fungal anthraquinone --> xanthone transformations.

Aflatoxin B1↗
PubMedDate not supplied

Clearance rate of intravenously administered lipid emulsion in canine endotoxemia.

The effect of endotoxemia on the initial catabolism of intravenously given lipid emulsion was investigated in dogs. Two types of endotoxemia were prepared. One was produced by peritonitis which was established by ligation of the artery and vein of an isolated intestine (group 1, n = 6). The other was made by an intravenous injection of Escherichia coli lipopolysaccharide in a dose of 1.5 mg/kg of body weight (group 2, n = 6). Group 1 showed evident peritonitis with a positive limulus test 48 hr after the procedure, but no significant changes of blood sugar level and lactate/pyruvate ratio, while group 2 demonstrated profound hypoglycemia, significant elevation of lactate/pyruvate ratio, and low arterial pressure 3 to 5 hr after the injection of lipopolysaccharide. The clearance rate of intravenously administered lipid emulsion (K value) of group 1 before the peritonitis was 0.0105 +/- 0.0017 and after the peritonitis it was 0.0105 +/- 0.0019. The difference was not significant, while the K value of group 2 which was 0.0133 +/- 0.0056 before the injection of lipopolysaccharide decreased significantly to 0.0069 +/- 0.0024 after the injection of lipopolysaccharide. These results suggest that, in case of endotoxemia with normally maintained oxidation-reduction potential, the initial catabolism of intravenously given lipid emulsion is kept in a normal level, while oxidation-reduction potential is impaired, it is inhibited.

Animals↗
PubMed1994

Microbial oxidation and reduction of manganese: consequences in groundwater and applications.

In the natural environment, manganese is found as reduced soluble or adsorbed Mn(II) and insoluble Mn(III) and Mn(IV) oxides. Mn oxidation has been reported in various microorganisms. Several possible pathways, indirect or direct, have been proposed. A wider variety of Mn-reducing microorganisms, from highly aerobic to strictly anaerobic, has been described. The mechanisms of Mn reduction can be either an indirect process resulting from interactions with organic or inorganic compounds, or a direct enzymatic (electron-transfer) reaction. The role of microorganisms in Mn cycle is now well demonstrated by various methods in superficial natural environments, and research has been initiated on subsurface sediments. Observations in vivo (Rhône valley) and under in vitro suggested that bacterial activities are the main processes that promote manganese evolution and migration in shallow aquifers. After the building of hydroelectric dams, the stream of the Rhône was modified, giving rise to mud deposition on the bank. In the mud, bacteria are stimulated by the high organic content and consume oxygen. The redox potential drops. The manganese oxides previously formed under aerobic conditions are reduced and soluble manganese (Mn(II)) migrates into the aquifer. If the subsurface sediments are coarse-grained, the aquifer is well aerated, allowing the re-oxidation of Mn(II) by the oligotrophic attached bacteria in aquifer sediments. If the aquifer is confined, aeration is not sufficient for Mn-reoxidation. Mn(II) remains in a reduced state and migrates to the wells. Furthermore, the presence of organic matter in subsurface sediments results in the reduction of previously formed Mn oxides. Pseudo-amorphous manganese oxides, which were probably recently formed by bacteria, are more readily reduced than old crystalline manganese oxides. Although the concentrations of soluble manganese found in groundwaters are not toxic, it still is a problem since its oxidation results in darkening of water and plugging of pipes in drinking or industrial water systems. Soluble manganese can be removed from water by biological processes involving manganese-oxidizing bacteria, either in situ, or in sand filters after pumping. Various procedures are mentioned.

Bacteria↗
PubMed1997

Identification of lutein and zeaxanthin oxidation products in human and monkey retinas.

PURPOSE: To characterize fully all the major and minor carotenoids and their metabolites in human retina and probe for the presence of the oxidative metabolites of lutein and zeaxanthin. METHODS: Carotenoids of a composite of 58 pairs of human retinas and a monkey retina were elucidated by comparing their high-performance liquid chromatography (HPLC)-ultraviolet/visible absorption spectrophotometry (UV/Vis)-mass spectrometry (MS) profile with those of authentic standards prepared by organic synthesis. RESULTS: In addition to lutein and zeaxanthin, several oxidation products of these compounds were present in the extracts from human retina. A major carotenoid resulting from direct oxidation of lutein was identified as 3-hydroxy-beta, epsilon-caroten-3'-one. Minor carotenoids were identified as: 3'-epilutein, epsilon,epsilon-carotene-3,3'-diol, epsilon,epsilon-carotene-3,3'-dione, 3'-hydroxy-epsilon,epsilon-caroten-3-one, and 2,6-cyclolycopene-1,5-diol. Several of the geometric isomers of lutein and zeaxanthin were also detected at low concentrations. These were as follows: 9-cis-lutein, 9'-cislutein, 13-cis-lutein, 13'-cis-lutein, 9-cis-zeaxanthin, and 13-cis-zeaxanthin. Similar results were also obtained from HPLC analysis of a freshly dissected monkey retina. CONCLUSIONS: Lutein, zeaxanthin, 3'-epilutein, and 3-hydroxy-beta,epsilon-caroten-3'-one in human retina may be interconverted through a series of oxidation-reduction reactions similar to our earlier proposed metabolic transformation of these compounds in humans. The presence of the direct oxidation product of lutein and 3'-epilutein (metabolite of lutein and zeaxanthin) in human retina suggests that lutein and zeaxanthin may act as antioxidants to protect the macula against short-wavelength visible light. The proposed oxidative-reductive pathways for lutein and zeaxanthin in human retina, may therefore play an important role in prevention of age-related macular degeneration and cataracts.

Animals↗