Comaprative binding study of aluminum and chromium to human transferrin

The characteristics of aluminum and chromium binding to apotransferrin (apo-tf) have been investigated and compared. Both metal ions were taken up by human transferrin forming complexes with the maximum absorbances at 405 nm for chromium-transferrin (cr-tf) and 240 nm for aluminum-transferrin (Al-tf). In the presence of citric acid, chromium binding to transferrin is five times more than aluminum. The binding of aluminum or chromium to apo-transferrin was reduced by 18 and 22% in the presence of 200 ng/mL of iron. The binding of both metals to apo-tf appears to be pH dependent. In acidic pHs, less chromium and more aluminum binding occurred.     

Fabrication of nickel and chromium nanoparticles using the protein cage of apoferritin

The iron storage protein, apoferritin, has a cavity in which iron is oxidized and stored as a hydrated oxide core. The size of the core is about 7 nm in diameter and is regulated by the cavity size. The cavity can be utilized as a nanoreactor to grow inorganic crystals. We incubated apoferritin in nickel or chromium salt solutions to fabricate hydroxide nanoparticles in the cavity. By using a solution containing dissolved carbon dioxide and by precisely controlling the pH, we succeeded in fabricating nickel and chromium cores. During the hydroxylation process of nickel ions a large portion of the apoferritin precipitated through bulk precipitation of nickel hydroxide. Bulk precipitation was suppressed by adding ammonium ions. However, even in the presence of ammonium ions the core did not form using a degassed solution. We concluded that carbonate ions were indispensable for core formation and that the ammonium ions prevented precipitation in the bulk solution. The optimized condition for nickel core formation was 0.3 mg/mL horse spleen apoferritin and 5 mM ammonium nickel sulfate in water containing dissolved carbon dioxide. The pH was maintained at 8.65 using two buffer solutions: 150 mM HEPES (pH 7.5) and 195 mM CAPSO (pH 9.5) with 20 mM ammonium at 23 degrees C. The pH had not changed after 48 h. After 24 h of incubation, all apoferritins remained in the supernatant and all of them had cores. Recombinant L-ferritin showed less precipitation even above a pH of 8.65. A chromium core was formed under the following conditions: 0.1 mg/mL apoferritin, 1 mM ammonium chromium sulfate, 100 mM HEPES (pH 7.5) with a solution containing dissolved carbon dioxide. About 80% of the supernatant apoferritin (0.07 mg/mL) formed a core. In nickel and chromium core formation, carbonate ions would play an important role in accelerating the hydroxylation in the apoferritin cavity compared to the bulk solution outside.     

Introduction

Biosorption of aluminum by sulfate-reducing bacteria isolated from uranium mine tailings was examined. A top agar method with Alizarin Red S was used for initial screening of the isolates for aluminum tolerance and biosorption. Five strains of aluminumion-fixing sulfate-reducing bacteria and a strain designated UFZ B 406 isolated from another source were used in the experiments. The mechanism of aluminum biosorption was found to be a passive one. Freezing and thawing of the cells resulted in higher sorption of aluminum, whereas heat treatment or the uncoupler carbonyl-cyanide-m- chlorophenylhydrazone (CCCP) had no effect. The pH value had significant influence on the aluminum ion adsorption, the most absorbance being at pH 3 and 5, and the lowest at pH 7. Addition of magnesium and the presence of iron sulfide precipitates decreased aluminum sorption. The relationship between biomass and Al3+ ions accumulated was linear. Polyphosphate granules as possible site of aluminum accumulation were not found to be present. Fluorescence microscopy showed deposition of aluminum ions exclusively on the surface of the cell. Use of the isolates in bioremediation processes for removing aluminum from water is considered.     

Iron Requirements and Aluminum Sensitivity of an Hydroxamic Acid-Requiring Strain of Bacillus megaterium

Bacillus megaterium strain ATCC 19213 secretes a ferric-chelating secondary hydroxamic acid, whereas a mutant (strain SK11) derived from it cannot produce a hydroxamate. Strain SK11 could be cultivated in a sucrose-mineral salts medium (treated with Chelex 100 to reduce trace metals) in the absence of added hydroxamate, if the inoculum was high. The lowest iron supplements necessary for maximal growth of both strains were equivalent (0.01 to 0.04 mug of iron per ml). Addition of either aluminum (0.5 mug/ml) or chromium (0.1 mug/ml) to the medium prevented full growth of strain SK11 at the minimal iron concentration, although elevated iron (1 mug/ml) reversed this inhibition. The iron-free secondary hydroxamate, Desferal, also abolished aluminum and chromium inhibition of strain SK11, producing maximal population densities at the low iron concentration. Growth of the hydroxamate-producing strain 19213 was not altered significantly by the aluminum or chromium levels which inhibited strain SK11. However, strain 19213 responded to these metals by increasing its secretion of a secondary hydroxamate. It was concluded that aluminum and chromium interfered with iron incorporation, either directly or by formation of nonutilizable aggregates with iron. The secondary hydroxamates may have overcome this interference by solubilization of iron for delivery to a single uptake process, or the ferric-hydroxamate chelate may enter the cell by an alternate route.     

In vitro study on the interactive effects of heavy metals on catalase activity of Sarotherodon mossambicus (Peters)

The in vitro effects of individual heavy metal ions as well as their combinations on catalase activity were investigated. Copper was found to be the strongest inhibitor of catalase activity followed by mercury, iron, chromium and cadmium. Copper toxicity on catalase activity was reduced in the presence of all the other metal ions. However, the addition of cadmium, chromium, iron, manganese, lead to mercury and cadmium, iron, manganese, nickel, lead, zinc to chromium increased their inhibitory effects on catalase activity.     

A dual functional turn off florescence sensor using metal–organic framework for sensitive detection of aluminum(III) in aqueous solution

Aluminum, classified as one of the toxic heavy metals, has a recommended daily consumption limit of 3–10 mg, as specified by the World Health Organization (WHO). Herein, the selective and sensitive aluminum(III) fluorescence sensor based on TMU-16 metal–organic frameworks (MOFs) in aqueous medium, is reported. A sensing pathway was found via the cation exchange between aluminum(III) and zinc(II) ions, and caused selectivity and sensitivity detection of aluminum(III) with a 5–100 ppm linear range and 1.99 ppm limit of detection (LOD). This sensor offers the advantage of accurately determining the concentration range of aluminum(III) ions. At low concentrations, only fluorescence quenching was observed, while at higher concentrations, fluorescence emission not only undergoes quenching but also exhibits a blue shift in wavelength. Notably, the sensor demonstrates no interference from cation solutions of mercury(II), zinc(II), nickel(II), lead(II), cobalt(II), cadmium(II), silver(I), chromium(III), and iron(III). Another significant feature of this sensor is its selectivity toward copper(II) and aluminum(III) ions, due to quenching fluorescence in the presence of copper(II) ion. The results presented the sensor's selectivity toward copper(II) at low concentrations and aluminum(III) at high concentrations.     

Molecular exchange of metal ions and tissular calcium overload

In vitro and in vivo, mouse tissues assayed for ⁴⁵Ca²⁺ uptake have shown that ATP increases the Ca²⁺ take-up in the presence of lactates of iron and aluminum, but this effect is absent with the citrates. The in vitro metal ion exchange with ATP has been demonstrated by electrophoresis and by chromatography. It is considered the cause of the increased capacity of ATP to modify the cellular effects of lactates. The in vitro modifications of Ca²⁺ uptake by lactates when in the presence of ATP are much more important than those of citrate. In general, aluminum compounds show a higher Ca²⁺ uptake and, coincidentally, they have shown a higher carcinogenic capacity than iron ATP.     

Chelation of chromium(VI) by combining deferasirox and deferiprone in rats

The present research is aimed to characterize the potential efficiency of two chelators after chromium(VI) administration for 60 days following two doses of 15 and 30 mg/kg chromium(VI) per body weight daily to male rats. However, the hypothesis that the two chelators might be more efficient as combined therapy than as single therapy in removing chromium(VI) from rat organs was considered. In this way, two known chelators deferasirox and deferiprone were chosen and given orally as a single or combined therapy for a period of 1 week. Chromium(VI) and iron concentrations in tissues were determined by flame atomic absorption spectroscopy. The combined chelation therapy results show that deferasirox and deferiprone are able to remove chromium(VI) ions from various tissues while iron concentration returned to normal levels and symptoms also decreased.     

Metal concentrations in water,sediment and sharptooth catfish Clarias gariepinus from three peri-urban rivers in the upper Manyame catchment,Zimbabwe

Concentrations of zinc, cadmium, chromium, nickel, lead, copper and iron were measured in flowing water, riverbed sediments and tissues of sharptooth catfish Clarias gariepinus from three rivers in the upper Manyame catchment over seven months in 2008–2009. The Manyame and Mukuvisi rivers are severely polluted by industrial and domestic effluent, whilst the Gwebi River is not influenced by urban effluent. Key water quality parameters, including dissolved oxygen and conductivity, clearly showed a pollution gradient in the Mukuvisi and Manyame rivers, but water quality in the Gwebi River was good. Levels of zinc, iron, copper, nickel and lead in fish tissues from the three rivers sampled were unusually high, with zinc and iron concentrations being the highest in all the tissues. This was also positively correlated with the concentrations of these metals in water and sediments. Notable differences existed between the water (zinc and copper) and sediments (iron and zinc) of each river. The relatively high metal concentrations in the Gwebi River, as well as conductivity and dissolved ions, were explained by the geological influence of the Great Dyke in its subcatchment. Metals are bound in the sediment but these can be rapidly mobilised into water if environmental changes occur, therefore efforts to monitor and prevent further water quality deterioration are required. The results of this study may have significant negative implications for aquatic organisms and for human health through fish consumption and therefore risk assessment investigations are imperative.     

Biosorption of scandium and yttrium from solutions

Summary The usage of biosorbents allows separation of scandium and yttrium from each other and from Fe, Al, Ti, Si, and Ca in hydrometallurgical processing of ores and wastes. It was shown that sorption of scandium and yttrium increased with the increase in pH of solution. Initial rate of scandium sorption depended on the biomass type; however 85–98% of scandium was sorbed within 10–30 min with most biomass types tested. The presence of aluminum, iron (III), and titanium in the solution inhibited sorption of scandium and particularly yttrium. After four cycles of sorption, 98.8% of scandium and 87% of yttrium was extracted from red mud leach solution by the biomass of Saccharomyces cerevisiae and Aspergillus terreus, respectively. Selectivity of the process of scandium and yttrium recovery could be achieved during sorption and also desorption, when solubilization of sorbed associated elements was inhibited by high pH values.     

Expression of a nonpolymorphic MHC class I-like molecule, CD1D, by human intestinal epithelial cells.

The human CD1 locus encodes three nonpolymorphic MHC class I-like cell surface glycoproteins, CD1a-c, which are expressed primarily by immature thymocytes. A mAb and antipeptide antiserum were utilized to determine the tissue distribution of a fourth CD1 molecule, CD1d. Within the lymphoid lineage, CD1d was expressed on B cells but not on thymocytes. Immunoperoxidase staining of fresh frozen intestinal tissues demonstrated that the majority of intestinal epithelial cells, with the exception of cells at the base of some crypts, expressed CD1d. The CD1d staining was observed in the cytoplasm and along the basolateral membranes of the epithelial cells. The intestinal epithelial cell expression of CD1d was confirmed by immunoblotting with a CD1d antipeptide antiserum. Further immunoperoxidase studies indicated that CD1d, unlike murine CD1, was also expressed by nonlymphoid tissues outside of the gastrointestinal tract. The expression of CD1d outside the lymphoid and myeloid lineages clearly distinguishes this molecule from CD1a-c and suggests that it may serve a distinct function. The prominent expression of CD1d by intestinal epithelial cells suggests that this molecule may be an important ligand for T lymphocytes within the gut-associated lymphoid tissue.     

Iron promotes the survival and neurite extension of serum-starved PC12 cells in the presence of NGF by enhancing cell attachment

Delayed death of serum-starved PC12 cells on a poly-L-lysine (PLL) matrix was observed, even in the presence of NGF. NGF blocked the apoptotic death of attached but not detached cells, which suggests that delayed death may be related to cell detachment from the PLL matrix. Iron selectively blocked this anoikis-like death by increasing cell attachment. Interestingly, the addition of > 10 microM FeCl2 to the culture medium generated gelatinous iron precipitates, and the removal of the precipitates abolished the iron effect. Attachment experiments using poly-HEMA supported the role of iron precipitates on cell-to-matrix adhesion. The expression of integrin beta1, neither N-cadherin nor alpha/beta-catenin, was also significantly increased by iron. In addition to its effect on cell viability, iron promoted the outgrowth of neurites. Our results collectively indicate that iron functions as a necessary co-element for NGF by enhancing cell attachment, survival, and neurite extension.     

Release of Metal Ions from Orthodontic Appliances: An In Vitro Study

In this paper, we report the results of an in vitro experiment on the release of metal ions from orthodontic appliances composed of alloys containing iron, chromium, nickel, silicon, and molybdenum into artificial saliva. The concentrations of magnesium, aluminum, silicon, phosphorus, sulfur, potassium, calcium, titanium, vanadium, manganese, iron, cobalt, copper, zinc, nickel, and chromium were significantly higher in artificial saliva in which metal brackets, bands, and wires used in orthodontics were incubated. In relation to the maximum acceptable concentrations of metal ions in drinking water and to recommended daily doses, two elements of concern were nickel (573 vs. 15 μg/l in the controls) and chromium (101 vs. 8 μg/l in the controls). Three ion release coefficients were defined: α, a dimensionless multiplication factor; β, the difference in concentrations (in micrograms per liter); and γ, the ion release coefficient (in percent). The elevated levels of metals in saliva are thought to occur by corrosion of the chemical elements in the alloys or welding materials. The concentrations of some groups of dissolved elements appear to be interrelated.     

Iron Oxidation and Precipitation of Ferric Hydroxysulfates by Resting Thiobacillus ferrooxidans Cells

The oxidation of ferrous ions, in acid solution, by resting suspensions of Thiobacillus ferrooxidans produced sediments consisting of crystalline jarosites, amorphous ferric hydroxysulfates, or both. These products differed conspicuously in chemical composition and infrared spectra from precipitates formed by abiotic oxidation under similar conditions. The amorphous sediments, produced by bacterial oxidation, exhibited a distinctive fibroporous microstructure when examined by scanning electron microscopy. Infrared spectra indicated outer-sphere coordination of Fe(III) by sulfate ions, as well as inner-sphere coordination by water molecules and bridging hydroxo groups. In the presence of excess sulfate and appropriate monovalent cations, jarosites, instead of amorphous ferric hydroxysulfates, precipitated from bacterially oxidized iron solutions. It is proposed that the jarositic precipitates result from the conversion of outer-sphere (T_d) sulfate, present in a soluble polymeric Fe(III) complex, to inner-sphere (C_3v) bridging sulfate. The amorphous precipitates result from the further polymerization of hydroxo-linked iron octahedra and charge stabilized aggregation of the resulting iron complexes in solution. This view was supported by observations that bacterially oxidized iron solutions gave rise to either amorphous or jarositic sediments in response to ionic environments imposed after oxidation had been completed and the bacteria had been removed by filtration.     

The role of iron in enhancing anaerobic toluene degradation in sulfate-reducing enrichment cultures

Ferrous iron enhanced the toluene degradation rate of sulfidogenic enrichment cultures inoculated with contaminated subsurface soil from an aviation fuel storage facility near the Patuxent River (Md.). Ferrous iron had an analogous effect on the degradation rate of benzoic acid, a transient metabolite of anaerobic toluene degradation in these cultures, when benzoic acid was used as a sole carbon and energy source. Two hypotheses were proposed to explain iron's effect: (a) Iron may have prevented sulfide toxicity via precipitation of sulfide as FeS, and (b) iron might have been a limiting nutrient required for degradation (i.e., amendments of iron could have compensated for iron removed from solution by precipitation as FeS). To test these hypotheses, substrate degradation rates were compared in the presence of FeSO₄ (a sulfate source that both precipitates sulfide species and precludes iron limitation) versus ZnSO₄ (a sulfate source that precipitates sulfide species but does not preclude iron limitation) versus MgSO₄ (a sulfate source that neither precipitates sulfide nor precludes iron limitation). For both toluene and benzoic acid, FeSO₄ and ZnSO₄ were comparable in their enhancement of substrate degradation rates and were superior to MgSO₄ in that respect. Thus, iron appears to ameliorate sulfide toxicity, not nutritional iron limitation, in these cultures. The observation that ethylenediaminetetraacetic acid, a chelating agent capable of retaining iron in solution in the presence of sulfide, did not stimulate the cultures is consistent with this conclusion. The implications of these results for bioremediation of fuel-contaminated aquifers that contain sulfate-reducing bacteria are discussed. Correspondence to: H.R. Beller.     

Comparative in situ study of the intestinal absorption of aluminum, manganese, nickel, and lead in rats

This comparative study of the intestinal absorption of four toxic metals (aluminum, manganese, nickel, and lead) carried out in rats using the in situ intestinal perfusion technique was able to measure the partition of each metal between the intestine (intestinal retention), the blood circulation, and target tissues after 1 h. The perfused metal solutions were at concentrations likely to occur during oral intoxication. It was found that aluminum (48 and 64 mM), even as a citrate complex, crossed the brush border with difficulty (0.4% of the perfused amount); about 60% of this was retained in the intestine and the remainder was found in target tissues (about 36%). Conversely, lead (4.8–48 μM) penetrated the intestine more easily (about 35% of the perfused amount), was slightly retained (about 12% of the input), and was soon found in the tissues (about 58% of the input) and to a lesser degree in circulation (about 29%). Within the same concentration range, nickel and manganese showed certain similarities, such as a reduced crossing of the brush border proportional to the increase in the concentration perfused (0.17–9.5 mM). There was similar intestinal retention and absorption (about 80% and 20% of the input, respectively). Manganese crossed the brush border more easily and was diffused more rapidly into tissues. Finally, the addition of equimolar amounts of iron (4.7 mM) produced opposite effects on the absorption of the two elements, inhibiting manganese and showing a trend to increase in nickel absorption. This could be the result of competition between Fe²⁺ and Mn²⁺ for the same transcellular transporters and the slight predominance of paracellular mechanism in the event of “Fe²⁺-Ni²⁺” association.     

Tracing the toxic ions of an endodontic tricalcium silicate-based sealer in local tissues and body organs

BackgroundThis study aimed to track the toxic ions released by MTA Fillapex, BioRoot RCS, and an experimental tricalcium silicate-based sealer (CEO) into local and distant tissues as well as to investigate their potential adverse effects. In addition, the chemical constituents of the sealers were also evaluated. The main components of the dry powders, pastes, and mixed sealers were characterized.Material and methodsDry powder and sealer discs were each set for 72 h and their main components were characterized by energy dispersive X-ray spectroscopy. Polyethylene tubes filled with sealers were used to measure silicon and calcium ions. Polyethylene tubes filled with sealers or empty tubes were implanted into the dorsal connective tissue of Wistar rats. On days 7, 15, 30, and 45, the animals were euthanized and their brains, livers, kidneys, and subcutaneous tissues were removed and processed to determine the concentrations of chromium, cobalt, copper, lead, iron, magnesium and nickel using an inductively coupled plasma optical emission spectrometer.ResultsThe main compounds in all sealers were carbon, oxygen, silicon, and calcium. MTA Fillapex release more Si while highest levels of Si were found in presence of BioRoot. The release of Si and Ca ions promoted by MTA Fillapex raise by time. No traces of cobalt, chromium, or magnesium were detected in any tissue. Irrespective of the sealer, no traces of copper and lead were found in the subcutaneous tissue; however, they were observed in the organs. The highest concentration of iron was identified in the liver. All sealers exhibited similar nickel traces in the brain, kidney, and liver except for MTA Fillapex, which demonstrated levels higher than CEO in the subcutaneous tissue on day 7. Tracing nickel ions over time revealed that lowest concentrations were found in subcutaneous tissue.ConclusionTaken together, our data demonstrate that CEOs have chemical compositions similar to those of other commercial sealers. Furthermore, none of them exhibited a threat to systemic health. Moreover, the minimal amounts of iron and nickel detected were not related to the sealers.     

Ultrastructure and energy-dispersive x-ray microanalysis of cartilage after rapid freezing, low temperature freeze drying, and embedding in Spurr's resin

In order to undertake meaningful high-resolution x-ray microanalysis of tissues, methods should be used that minimize the introduction of artefacts produced by loss or translocation of ions. The most ideal method is rapid freezing but the subsequent sectioning of frozen tissues is technically difficult. An alternative method is to freeze dry the tissues at a low temperature, and then embed them in resin. This facilitates the rapid production of reproducible thin sections. With freeze-dried, embedded hypertrophic cartilage, the morphology was similar to that seen using aqueous fixatives even when no additional electron density is introduced by the use of osmium vapor. Energy-dispersive analysis of specific areas show that little or no loss or migration of ions occurs from structures such as mitochondria. Mitochondrial granules consisting of calcium and phosphorus precipitates were not observed except where the cells were damaged as a result of the freezing process. This may suggest that these granules only appear when tissue is damaged because of inadequate preservation.     

Transition metal abnormalities in progressive dementias

Abnormal distributions of transition metals inside the brain are potential diagnostic markers for several central nervous system diseases, including Alzheimer’s disease (AD), Parkinson’s disease, dementia with Lewy bodies (DLB), bipolar disorders and depression. To further explore this possibility, the total concentrations of iron, zinc, copper, manganese, aluminum, chromium and cadmium were measured in post-mortem hippocampus and amygdala tissues taken from AD, DLB and Control patients. A statistically significant near fifty percent reduction in the total copper levels of AD patients was observed in both the hippocampus and amygdala. The statistical power of the hippocampus and amygdala copper analysis was found to be 86 and 74% respectively. No statistically significant deviations in the total metal concentrations were found for zinc, manganese, chromium or aluminum. Iron was found to be increased by 38% in AD amygdala tissues, but was unchanged in AD hippocampus tissues. Accounting for differences in tissue water content, as a function of both tissue type and disease state, revealed more consistencies with previous literature. To aid in the design of future experiments, the effect sizes for all tissue types and metals studied are also presented.