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PubMed2004

Discoloration and mineralization of Orange II using different heterogeneous catalysts containing Fe: a comparative study.

Four heterogeneous catalysts containing Fe including a bentonite-clay-based Fe nanocomposite (Fe-B), hematite (alpha-Fe2O3), amorphous FeOOH, and calcined FeOOH (denoted as FeOOH-M) were employed for the photo-Fenton discoloration and mineralization of 0.2 mM Orange II in the presence of 10 mM H2O2 and 8 W UVC at two different initial solution pH values (3.0 and 6.6). It was found that, at an initial solution pH of 3.0, their photocatalytic activities follow the order Fe-B > FeOOH, FeOOH-M > alpha-Fe2O3. When the Fe-B nanocomposite, FeOOH, and FeOOH-M were used as heterogeneous catalysts, both heterogeneous and homogeneous photo-Fenton reactions were responsible for the discoloration and mineralization of 0.2 mM Orange II because homogeneous photo-Fenton reaction occurred due to the presence of Fe ions leached from the catalysts. At an initial solution pH of 6.6, their photocatalytic activities still follow the order Fe-B > FeOOH, FeOOH-M >> alpha-Fe2O3. However, only heterogeneous photo-Fenton reaction accounted for the discoloration and mineralization of 0.2 mM Orange II because Fe leaching from the catalysts was significantly depressed. In the case of alpha-Fe2O3 as a catalyst, whether at an initial solution pH of 3.0 or 6.6, only heterogeneous photo-Fenton reaction happened for the discoloration and mineralization of 0.2 mM Orange II because Fe leaching from the catalyst is negligible. The apparent discoloration kinetics of Orange II with the four catalysts at two different initial solution pH values was also investigated.

Aluminum Silicates↗
PubMed2006

O2 and CO binding to tetraaza-tripodal-capped iron(II) porphyrins.

A series of tris(2-aminoethylamine) (tren) capped iron(II) porphyrins has been synthesized and characterized and their affinities for dioxygen and carbon monoxide measured. The X-ray structure of the basic scaffold with nickel inserted in the porphyrin is also reported. All the ligands differ by the nature of the group(s) attached to the secondary amine functions of the cap. These various substitutions were introduced to probe if a hydrogen bond with these secondary amine groups acting as the donor could rationalize the high affinity of these myoglobin models. This work clearly indicates that the cage structure of the tren predominates over all the other appended groups with the exception of p-nitrophenol.

Aza Compounds↗
PubMed2003

Structural phase transition at the percolation threshold in epitaxial (La0.7Ca0.3MnO3)1-x:(MgO)x nanocomposite films.

'Colossal magnetoresistance' in perovskite manganites such as La0.7Ca0.3MnO3 (LCMO), is caused by the interplay of ferro-paramagnetic, metal-insulator and structural phase transitions. Moreover, different electronic phases can coexist on a very fine scale resulting in percolative electron transport. Here we report on (LCMO)1-x:(MgO)x (0 < x < or = 0.8) epitaxial nano-composite films in which the structure and magnetotransport properties of the manganite nanoclusters can be tuned by the tensile stress originating from the MgO second phase. With increasing x, the lattice of LCMO was found to expand, yielding a bulk tensile strain. The largest colossal magnetoresistance of 10(5)% was observed at the percolation threshold in the conductivity at xc 0.3, which is coupled to a structural phase transition from orthorhombic (0 < x < or 0.1) to rhombohedral R3c structure (0.33 < or = x < or = 0.8). An increase of the Curie temperature for the Rc phase was observed. These results may provide a general method for controlling the magnetotransport properties of manganite-based composite films by appropriate choice of the second phase.

Calcium Compounds↗
PubMed2003

The natural antioxidant otobaphenol delays the permeability transition of mitochondria and induces their aggregation.

The lignan otobaphenol, (8R,8'R,7R)-4'-hydroxy-5'-methoxy-3,4-methylenedioxy-2',7,8,8'-neolignan, extracted from Virola Aff. Pavonis leaves, completely inhibits at a concentration of 2.5 micro M the Fe(3+)-ascorbate-induced lipoperoxidation of rat liver mitochondria that was determined by oxygen consumption and accumulation of thiobarbituric acid-reactive species. At 25 micro M, it delays the mitochondrial permeability transition induced by tert-butyl hydroperoxide or Ca(2+), substantially inhibits the state 3 respiration, does not affect the state 4 respiration and the ADP/O ratio (with succinate), diminishes the rate of Ca(2+) uptake by mitochondria, and delays the ruthenium red-insensitive uncoupler-induced release of the loaded Ca(2+). Dose-dependent delaying of the calcium-induced swelling of mitochondria in the presence of otobaphenol nonlinearly correlates with its 1,1-diphenyl-2-picrylhydrazyl free radical scavenging activity. At 75 micro M and higher, this lignan causes mitochondrial aggregation and is able to aggregate itself, without mitochondria. The formed aggregates of otobaphenol do not cause an aggregation of subsequently added mitochondria. Thus, otobaphenol seems to be a promising target to prevent the oxidative stress death of cells.

Animals↗
PubMed1982

Isolation of indigenous enteroviruses from chemically treated and dewatered sludge samples.

Samples of wastewater sludge were examined for infectious enteroviruses before and after they had been chemically conditioned and dewatered. The least virus was recovered from the cake produced by filter pressing of sludge, which had a greatly increased solids content (39 to 45% [wt/vol]) relative to the untreated sludge (4.2 to 6.2% [wt/vol]) and in one plant was at pH 11 due to the lime conditioner used. Conditioning with a cationic polyelectrolyte before dewatering by centrifugation produced a watery sludge (2.7 to 5.3% [wt/vol]) from which high titers of infectious virus were recovered which were often greater than those isolated from the untreated sludge (0.6 to 1.4% [wt/vol]). This was thought to be due to saturation of virus and sludge floc adsorption sites by the polyelectrolyte, resulting in the liberation of virions from the sludge solids.

Calcium↗
PubMed2006

Characterization of dissimilatory Fe(III) versus NO3- reduction in the hyperthermophilic archaeon Pyrobaculum aerophilum.

The hyperthermophilic archaeon Pyrobaculum aerophilum used 20 mM Fe(III) citrate, 100 mM poorly crystalline Fe(III) oxide, and 10 mM KNO3 as terminal electron acceptors. The two forms of iron were reduced at different rates but with equal growth yields. The insoluble iron was reduced when segregated spatially by dialysis tubing, indicating that direct contact with the iron was not necessary for growth. When partitioned, there was no detectable Fe(III) or Fe(II) outside of the tubing after growth, suggesting that an electron shuttle, not a chelator, may be used as an extracellular mediator of iron reduction. The addition of 25 and 50% (vol vol(-1)) cell-free spent insoluble iron media to fresh media led to growth without a lag phase. Liquid chromatography analysis of spent media showed that cultures grown in iron, especially insoluble iron, produced soluble extracellular compounds that were absent or less abundant in spent nitrate medium. NADH-dependent ferric reductase activity increased approximately 100-fold, while nitrate reductase activity decreased 10-fold in whole-cell extracts from iron-grown cells relative to those from nitrate-grown cells, suggesting that dissimilatory iron reduction was regulated. A novel 2,6-anthrahydroquinone disulfonate oxidase activity was more than 580-fold higher in iron-grown cells than in nitrate-grown cells. The activity was primarily (>95%) associated with the membrane cellular fraction, but its physiological function is unknown. Nitrate-grown cultures produced two membrane-bound, c-type cytochromes that are predicted to be monoheme and part of nitrite reductase and a bc1 complex using genome analyses. Only one cytochrome was present in cells grown on Fe(III) citrate whose relative abundance was unchanged.

Cytochromes c↗
PubMed1990

[Stable adhesion to dentin. Combination of EDTA 3-2 (NH4/Fe) pretreatment and 2% 4-META/MMA-TBB resin].

An excellent durability of adhesion was obtained in the adhesion of 2% 4-META/MMA-TBB resin to dentin pretreated with EDTA 3-2 (NH4/Fe). Such high bond strength as 15 MPa did not change for up to one year even when they were immersed in water at 37 degrees C. The resin reinforced dentin, a hybrid, was identified between dentin and the cured resin by TEM. The collagen and hydroxyapatite were encapsulated with the copolymer and the crystals were not removed by the demineralization with either HCl or electronic staining. Tensile fracture between the hybrid and dentin like the adhered samples to 10-3 treated dentin did not occur and the cohesive failure in the resin was observed here after the storage in water for a year. EDTA 3-2 (NH4/Fe) could not completely demineralize the hydroxyapatite especially at the deeper portion and the width of the demineralized dentin became thinner than 1 micron. The encapsulated crystals with the resin could improve the resistance of collagen against deterioration in water and such good bonding durability could be obtained.

Acrylic Resins↗
PubMed1985

Iron(III)-adriamycin and Iron(III)-daunorubicin complexes: physicochemical characteristics, interaction with DNA, and antitumor activity.

Fe(III) complexes of two anthracyclines, adriamycin and daunorubicin, have been studied. Using potentiometric and spectroscopic measurements, we have shown that adriamycin and daunorubicin form two well-defined species with Fe(III), which can be formulated as respectively Fe(HAd)3 and Fe(HDr)3. In these formulas, HAd and HDr stand for adriamycin and daunorubicin in which the 1,4-dihydroxy-anthraquinone moiety is half-deprotonated. Both complexes are six-membered chelates. The stability constant is beta = (2.5 +/- 0.5) X 10(28) for both complexes. Interaction with DNA has been studied showing that, despite strong coordination to Fe(III), anthracyclines are able to intercalate between DNA bases pairs, releasing the metal. These complexes display antitumor activity against P 388 leukemia that compares with that of the free drug. Fe(HAd)3, unlike adriamycin, does not catalyze the flow of electrons from NADH to molecular oxygen through NADH dehydrogenase. Moreover, it is shown that the triferric adriamycin compound so called "quelamycin" is in fact a mixture of Fe(HAd)3 and polymeric ferric hydroxide.

Circular Dichroism↗
PubMed1989

Haemoglobin and myoglobin as inhibitors of hydroxyl radical generation in a model system of "iron redox" cycle.

Methionine was oxidized to ethylene by an "Iron Redox" system containing H2O2, Fe-EDTA and ascorbate, generating hydroxyl radicals or another species of similar reactivity. Oxy or met forms of haemoglobin and myoglobin were found to inhibit methionine oxidation. Methionine oxidation was elevated in the "Iron Redox" system by increasing ascorbic acid concentration. However, in the presence of metmyoglobin or methaemoglobin, the increases in ascorbic acid did not lower the haemproteins' inhibitory effects but rather increased them. The pro-oxidative or anti-oxidative activities of haemproteins in biological oxidative reactions seem to be dependent on compartmentalization and on the presence and concentrations of reducing compounds and H2O2.

Animals↗
PubMed2001

The effect of change in pH on the solubility of iron bis-glycinate chelate and other iron compounds.

The effect of a pH change from 2 to 6 was tested on the solubility of ferrous sulfate, ferrous fumarate, iron bis-glycine chelate (Ferrochel) and sodium-iron ethylenediaminetetraacetic acid (NaFeEDTA). It was found that at pH 2 ferrous sulfate, Ferrochel and NaFeEDTA were completely soluble and only 75% of iron from ferrous fumarate was soluble. When pH was raised to 6, iron from amino acid chelate and NaFeEDTA remained completely soluble while solubility from ferrous sulfate and ferrous fumarate decreased 64 and 74%, respectively compared to the amount of iron initially soluble at pH 2. These results suggest that iron solubility from iron bis-glycine chelate and NaFeEDTA is not affected by pH changes within the ranges tested, probably because iron remained associated to the respective compounds.

Edetic Acid↗
PubMed1993

Application of chemical cytochrome P-450 model systems to studies on drug metabolism. VI. N,N-coupling reaction of N-methylaniline catalyzed by polypeptide-bound porphyrinatoiron(III) and cytochrome P-450.

Polypeptide-bound porphyrinatoiron(III) effectively catalyzed the N,N-coupling reaction of N-methylaniline in the presence of NaBH4/O2/tetramethyl-ammonium hydroxide or cumenehydroperoxide, whereas the corresponding non-bound monomer porphyrinatoiron(III) had little catalytic activity. Rat liver microsomes also catalyzed the N,N-coupling which was inhibited by cytochrome P-450 specific inhibitors, SKF-525A and metyrapone. The polypeptide-bound porphinatoiron(III) appears to be an excellent cytochrome P-450 model for drug metabolism studies.

Aniline Compounds↗
PubMed1975

Complexes between synthetic polymer ligands and ferri-delta and ferro-protoporphyrin IX.

The complexes of synthetic polymer ligands, i.e. poly-L-lysine, poly-4-vinyl-pyridine, poly-N-vinyl-2-methylimidazole and the higher branched polyethyleneimine, with ferri- or ferro-protoporphyrin IX were studied from the standpoint of polymer ligand effects by comparison with those of their monomeric model ligand complexes and poly-gamma-benzyl-L-glutamate containing an imidazole nucleus at the chain end. The coordination numbers and formation constants were determined optically and their structures were also estimated. The coordination number of a poly-L-lysine complex was two, but those of other polymer ligand complexes were one. One of the polymer effects, which was indicated by the large formation constants of the polymer complexes, was caused by the increment of the local ligand concentration around the polymer chain. Another was caused by the conformational effect of an alpha-helical structure in the poly-L-lysine complexes. The interaction of a poly-L-lysine-heme complex with molecular oxygen was also studied. An observed pseudo-allosteric phenomenon may be due to the specific structure of a poly-L-lysine complex which is different from those of other polymer ligand complexes.

Allosteric Site↗
PubMed1995

Effects of intra- and intermolecular crosslinking on the free radical reactions of bovine hemoglobins.

Chemical modifications of human or bovine hemoglobins are designed to produce proteins that can act as oxygen-carrying blood substitutes. Concerns about the redox reactivity of cell-free hemoglobin and its contribution to tissue-damaging oxygen free radicals has not been fully established. We determined that bovine hemoglobins intra- or intermolecularly crosslinked differ in their ability to generate or interact with reactive oxygen species. These differences do not correlate with their oxygen affinities. We compared HbBv-FMDA, produced by the reaction of bovine hemoglobin with fumaryl-monodiaspirin and Poly HbBv, a glutaraldehyde polymerized bovine hemoglobin, with unmodified bovine hemoglobin (HbBv). Superoxide radicals are produced during the spontaneous oxidation of hemoglobin. Relative to the other two proteins. Poly HbBv was found to be more susceptible to autoxidation. Spectral changes indicative of protein modification and ferrylhemoglobin formation during the enzymatic peroxidation of these hemoglobins differ qualitatively and occur at an increasing order, poly HbBv > HbBv > HbBv-FMDA. The proteins also differ in the rate of hemoglobin catalyzed NADPH oxidation and aniline hydroxylation, reactions mediated by reactive oxygen species. Taken together, our results and those reported previously on modified human hemoglobins, suggest that redox and oxygen-carrying functions of hemoglobin can be experimentally manipulated as independently selectable parameters that may ultimately aid in the design of a safer reperfusion agent.

Aniline Compounds↗
PubMed2006

Preparation of anion exchanger by amination of acrylic acid grafted polypropylene nonwoven fiber and its ion-exchange property.

To develop the polymeric adsorbent that possess anionic exchangeable function, PP-g-AA-Am fibers were prepared by photoinduced grafting of acrylic acid (AA) onto polypropylene (PP) nonwoven fibers and subsequent conversion of carboxyl group in grafted AA to an amine (Am) group by reaction with diethylene triamine (DETA). The amination of grafted AA increased with increase in the degree of grafting, the reaction time and temperature of the chemical modification process. Catalytic effect of metal chlorides such as AlCl(3) and FeCl(3) on the amination of grafted AA was significant but not essential to lead the amination. FT-IR and solid (13)C NMR data indicate that amine group was introduced into PP-g-AA fiber through amide linkage between grafted AA and DETA. The anion exchange capacity of PP-g-AA-Am fiber increased with increase in the degree of amination, but reached maximum value at about 60% amination of 150% grafted AA. PP-g-AA-Am fiber showed much higher maximum capacity for PO(4)-P and a similar capacity for NO(3)-N compared to commercial anion resins. Furthermore, the PP-g-AA-Am fiber also has adsorption ability for cations because of unaminated residual carboxyl group.

Absorption↗
PubMed1996

Smear layer instability caused by hemostatic agents.

The effect of hemostatic agents, other than a 15.5% Fe2(SO4)3 solution, on prepared tooth structure is unknown. The purpose of this study was to (1) compare the effect of six commonly used hemostatic solutions and two nondental astringents on the dentinal smear layer and (2) determine whether different responses caused by product and/or time could be established. Standardized dentinal smear layers were exposed to eight astringent solutions for 30, 120, and 300 seconds (n = 6). A total of 144 SEM photographs at x2400 magnification were ranked according to predetermined criteria for five categories of smear layer removal and etching of underlying tooth structure. There were significant differences (p < 0.001) caused by the solution, exposure time, and their interaction. Greatest smear layer removal was observed with 21.3% AlCl3-6 hydrate, 8% racemic epinephrine HCl, and 15.5% Fe2(SO4)3 solutions at longer exposures. These caused significantly more removal than did almost pH neutral tetrahydrozoline or oxymetazoline (p < 0.05).

Acid Etching, Dental↗