A new organic-inorganic hybrid framework containing octahedral hexarhenium cluster and its transformation by ligand exchange

A new organic-inorganic hybrid solid with 3-D framework, [Mn(DMF)₃]₂[Re₆Se₈(CN)₆] (1), has been synthesized and transformed to [H][Mn(salen)]₃[Re₆Se₈(CN)₆] (2) by a ligand exchange. Hexarhenium chalcocyanide clusters are closest packed in cubic symmetry for 1 and rhombohedral symmetry for 2. The manganese complexes in the interstitial sites are three-coordinated to the rhenium cluster in 1 and two-coordinated in 2.     

Synthesis and characterization of metal ion imprinted nano-porous polymer for the selective recognition of copper

Selective recognition of metal ions utilizing metal ion-imprinted polymers (MIIPs) received much importance in diverse fields owing to their high selectivity for the target metal ions. In the present study, a copper ion imprinted polymer was synthesized without an additional complexing ligand or complex with a broad aim to avoid the conventional extra metal ion complexing ligand during the synthesis of MIIP. The complete removal of the copper metal ion from the MIIP was confirmed by AAS and SEM–EDX. SEM image of the MIIP exhibited nano-patterns and it was also found to be entirely different from that of non-imprinted polymer and polymer with copper metal ions. BET surface area analysis revealed more surface area (47.96 m²/g) for the Cu(II)-MIIP than non-imprinted control polymer (41.43 m²/g). TGA result of polymer with copper metal ion indicated more char yield (18.41%) when compared to non-imprinted control polymer (8.3%) and Cu(II)-MIIP (less than 1%). FTIR study confirmed the complexation between Cu(II)-MIIP and Cu(II) metal ion through carbonyl oxygen of acryl amide. The Cu(II)-MIIP exhibited an imprinting efficiency of 2.0 and it was showing 8% interference from a mixture of Zn, Ni and Co ions. A potentiometric ion selective electrode devised with Cu(II)-MIIP showed more potential response for Cu(II) ion than that was fabricated from non-imprinted polymer.     

Overexpression, purification and characterization of the catalytic component of Oplophorus luciferase in the deep-sea shrimp, Oplophorus gracilirostris

The luciferase secreted by the deep-sea shrimp Oplophorus consists of 19 and 35kDa proteins. The 19-kDa protein (19kOLase), the catalytic component of luminescence reaction, was expressed in Escherichia coli using the cold-shock inducted expression system. 19kOLase, expressed as inclusion bodies, was solubilized with 6M urea and purified by urea-nickel chelate affinity chromatography. The yield of 19kOLase was 16 mg from 400 ml of cultured cells. 19kOLase in 6M urea could be refolded rapidly by dilution with 50mM Tris-HCl (pH 7.8)-10mM EDTA, and the refolded protein showed luminescence activity. The luminescence properties of refolded 19kOLase were characterized, in comparison with native Oplophorus luciferase. Luminescence intensity with bisdeoxycoelenterazine as a substrate was stimulated in the presence of organic solvents. The 19kOLase is a thermolabile protein and is 98 % inhibited by 1muM Cu2+. The cysteine residue of 19kOLase is not essential for catalysis of the luminescence reaction.     

Heavy metal sorption by released polysaccharides and whole cultures of two exopolysaccharide-producing cyanobacteria

The metal removal capacity of cultures of two capsulated, exopolysaccharide-producing cyanobacteria, Cyanospira capsulata and Nostoc PCC7936, were tested using copper (II) as the model metal. C. capsulata cultures removed the greatest amount of copper, with a maximum per unit of biomass (q _max) of 115.0±5.1 mg copper g⁻¹ of protein, compared with 85.0±3.2 removed with Nostoc PCC7936 cultures. Water solutions of pure polysaccharides (RPSs) released into the culture medium by C. capsulata and Nostoc PCC7936 achieved q _max values of 20.2±0.8 mg g⁻¹ copper per polysaccharide dry weight with C. capsulata RPS and 11.0±1.5 mg g⁻¹ with Nostoc PCC7936 RPS. Cultures of the two cyanobacteria also removed Zn (II) and Ni (II), in both single-metal systems and in multimetal systems with Cu; in the various single-metal systems more copper was removed than Zn or Ni, while in the multimetal systems a smaller amount of each individual metal was removed but the overall amount of all metal ions sorbed or the amount of copper sorbed in the copper-only system was almost the same with C. capsulata, and slightly higher with Nostoc PCC7936.     

A biogeochemical framework for metal detoxification in sulfidic systems

We develop a comprehensive biogeochemical framework for understanding and quantitatively evaluating metals bio-protection in sulfidic microbial systems. We implement the biogeochemical framework in CCBATCH by expanding its chemical equilibrium and biological sub-models for surface complexation and the formation of soluble and solid products, respectively. We apply the expanded CCBATCH to understand the relative importance of the various key ligands of sulfidic systems in Zn detoxification. Our biogeochemical analysis emphasizes the relative importance of sulfide over other microbial products in Zn detoxification, because the sulfide yield is an order of magnitude higher than that of other microbial products, while its reactivity toward metals also is highest. In particular, metal-titration simulations using the expanded CCBATCH in a batch mode illustrate how sulfide detoxifies Zn, controlling its speciation as long as total sulfide is greater than added Zn. Only in the absence of sulfide does complexation of Zn to biogenic organic ligands play a role in detoxification. Our biogeochemical analysis conveys fundamental insight on the potential of the key ligands of sulfidic systems to effect Zn detoxification. Sulfide stands out for its reactivity and prevalence in sulfidic systems.     

Uncoupling metallonuclease metal ion binding sites via nudge mutagenesis

The hydrolysis of phosphodiester bonds by nucleases is critical to nucleic acid processing. Many nucleases utilize metal ion cofactors, and for a number of these enzymes two active-site metal ions have been detected. Testing proposed mechanistic roles for individual bound metal ions has been hampered by the similarity between the sites and cooperative behavior. In the homodimeric PvuII restriction endonuclease, the metal ion dependence of DNA binding is sigmoidal and consistent with two classes of coupled metal ion binding sites. We reasoned that a conservative active-site mutation would perturb the ligand field sufficiently to observe the titration of individual metal ion binding sites without significantly disturbing enzyme function. Indeed, mutation of a Tyr residue 5.5 A from both metal ions in the enzyme-substrate crystal structure (Y94F) renders the metal ion dependence of DNA binding biphasic: two classes of metal ion binding sites become distinct in the presence of DNA. The perturbation in metal ion coordination is supported by 1H-15N heteronuclear single quantum coherence spectra of enzyme-Ca(II) and enzyme-Ca(II)-DNA complexes. Metal ion binding by free Y94F is basically unperturbed: through multiple experiments with different metal ions, the data are consistent with two alkaline earth metal ion binding sites per subunit of low millimolar affinity, behavior which is very similar to that of the wild type. The results presented here indicate a role for the hydroxyl group of Tyr94 in the coupling of metal ion binding sites in the presence of DNA. Its removal causes the affinities for the two metal ion binding sites to be resolved in the presence of substrate. Such tuning of metal ion affinities will be invaluable to efforts to ascertain the contributions of individual bound metal ions to metallonuclease function.     

Physiological, morphological and metabolic changes in Tetrahymena pyriformis for the in vivo cytotoxicity assessment of metallic pollution: Impact on d-β-hydroxybutyrate dehydrogenase

The individual cytotoxicity of cadmium chloride, iron sulphate and chromium nitrate has been investigated by using the freshwater ciliate Tetrahymena pyriformis. The metabolic enzymes and antioxidant defense biomarkers were assessed. The results obtained reveal that their metal salts have perturbed the physiology and morphology of T. pyriformis. Also, the biomarkers assessed were sensitive to the presence of metal salts and this sensitivity was metal salt and dose dependant. To estimate the impact of their metal salts on mitochondria, we studied their effects in vivo and in vitro on the d-β-hydroxybutyrate dehydrogenase (BDH) (EC 1.1.1.30) inner mitochondrial membrane enzyme. The results showed a high inhibition of BDH in terms of activity, protein expression and kinetic parameters.     

The influence of ferrous sulfate utilization on the sugar yields from dilute-acid pretreatment of softwood for bioethanol production

By employing metal salts in dilute-acid pretreatment the severity can be reduced due to reduced activation energy. This study reports on a dilute-acid steam pretreatment of spruce chips by addition of a small amount of ferrous sulfate to the acid catalyst, i.e., either SO₂, H₂SO₃ or H₂SO₄. The utilization of ferrous sulfate resulted in a slightly increased overall glucose yield (from 74% to 78% of the theoretical value) in pretreatment with SO₂ and H₂SO₃. Impregnation with ferrous sulfate and sulfuric acid did not give any improvement compared with pretreatment based solely on H₂SO₄.     

Effects of vegetation and fertilizer on metal and Sb plant uptake in a calcareous shooting range soil

Shooting range soils frequently contain anomalous concentrations of metals (e.g. Pb, Zn, Mn) and Sb coming from bullets which may be released into the environment. In a pot experiment, we investigated metal and Sb uptake by three plant species (Plantago lanceolata, Lolium perenne and Triticum aestivum) growing on a calcareous shooting range soil (pH 7.8; 500 mg kg⁻¹ Pb, 21 mg kg⁻¹ Sb) and the uptake changes when an acidic fertilizer solution was applied to the soil. Metal and Sb solubility in the soil was determined by extraction with 0.1 M NaNO₃. In addition, we measured pH, electrical conductivity and dissolved organic carbon in drainage samples. The results showed significant increase over time of pH (from 7.8 to 8.3) and decrease of electrical conductivity and dissolved organic carbon (from 230 to ∼130 mg L⁻¹). Fertilizer application increased NaNO₃-extractable Pb and Sb and root:shoot biomass ratio but not plant metal uptake. In T. aestivum spikes accumulated more Zn, Ni and Cu than shoots and grains. Mn and Zb uptake was correlated in L. perenne shoots. P. lanceolata, a Sb-bioindicator, did not accumulate high amounts of Sb (<1 mg kg⁻¹).     

The Influence of Soil Properties on the Mobility of Metals Following a Single Application of Polluted Sewage Sludge to Seventy Agricultural Topsoils: A Laboratory Column Study

The main aim of this study was to examine the influence of soil properties on the leaching of Cd, Cr, Cu, Ni, Pb, and Zn following the application of polluted sewage sludge to contrasting topsoils. Seventy agricultural soil samples from different parts of Spain were amended with a single dose of sewage sludge (equivalent to 50 t dry weight ha^?1) and a column study was performed under controlled conditions. After two, four, and six months of incubation, 283 ml of distilled water (equivalent to a rainfall event of 25 l m^?2) was applied. The leachates were then collected and analyzed for metals. For all of the soils considered, the pH was the most important parameter for the control of mobility metals (except for Cu, determined by the sand and soil organic carbon and only to a lesser extent by the soil pH r² = 0.604, p < 0.001) and was negatively related to all of the studied metals. For Pb and Zn, soil pH was the single soil property explaining their mobility (r² = 0.411, p < 0.001 for Pb; r² = 0.713, p < 0.001 for Zn) while for Cd, Cr and Ni, EC, sand and silt also appeared in the statistical models (r² = 0.753, p < 0.001 for Cd; r² = 0.366, p < 0.001 for Cr; r² = 0.784, p < 0.001 for Ni). In the basic soils, soil texture was the most important soil property controlling the mobility of metals (except for that of Pb, which it only weakly predicted). For the acidic-neutral soils, the soil pH was the most important soil property controlling metal mobility (except for that of Cr, which was mainly determined by the pseudo-total Cr content).