Rhizosphere Microbial Densities and Trace Metal Tolerance of the Nickel Hyperaccumulator Alyssum Serpyllifolium Subsp. Lusitanicum

In this study we determine culturable microbial densities (total heterotrophs, ammonifiers, amylolytics and cellulolytics) and bacterial resistance to Co, Cr, and Ni in bulk and rhizosphere soils of three populations of the Ni-hyperaccumulator Alyssum serpyllifolium subsp. lusitanicum and the excluder Dactylis glomerata from ultramafic sites (two populations in Northeast (NE) Portugal (Samil (S), Morais (M)) and one population in Northwest (NW) Spain (Melide (L)). The relationship between bioavailable metal concentrations (H₂O-soluble) and microbial densities were analysed. Significant differences in microbial densities and metal-resistance were observed between the two species and their three populations. The hyperaccumulator showed higher microbial densities (except cellulolytics) and a greater rhizosphere effect, but this was only observed in S and M populations. These populations of A. serpyllifolium also showed selective enrichment of Ni-tolerant bacteria at the rhizosphere where Ni solubility was enhanced (densities of Ni-resistant bacteria were positively correlated with H₂O-soluble Ni). These rhizobacteria could solubilise Ni in the soil and potentially improve phytoextraction strategies.     

Magnetic Excitations in Silver Nanocrescents at Visible and Ultraviolet Frequencies

We study magnetic excitations at optical frequencies in disordered crescent-form split-ring resonators made of silver. The resonators that are less than 100 nm in diameter are fabricated on a 4 in. quartz wafer by using a simple, fast, and inexpensive fabrication technique. The measured transmission and polarization-rotation spectra of the resonators reveal the excitation of circulating electric currents that give rise to magnetic dipole moments in the structures at visible and ultraviolet light frequencies. These frequencies have higher values than the limiting magnetic-resonance frequency predicted by the conventional LC resonance model presumably due to the plasmonic nature of the excitations.     

Spectroscopic aspects of the coordination modes of 2,4-dithiohydantoins: Experimental and theoretical study on copper and nickel complexes of cyclohexanespiro-5-(2,4-dithiohydantoin)

The complexation of cyclohexanespiro-5-(2,4-dithiohydantoin), L, with copper and nickel was studied by means of experimental and theoretical methods. The Cu(I) and Ni(II) complexes were synthesized and characterized using ¹³C CPMAS NMR, IR and FAB-MS. Reduction of Cu(II) ions and the formation of Cu(I) complexes with dithiohydantoin was proved. Various coordination modes were investigated on the basis of calculated (DFT-GIAO) shielding constants of the free ligand and model structures of the complexes. General trends in the changes of spectroscopic parameters (NMR chemical shifts, vibrational modes) upon different types of coordination were outlined. Dimeric structures for the Cu(I) and Ni(II) complexes were proposed in which the ligands were coordinated in N3^S4- and N3^S2-bridging ways, respectively, acting as monoanions. The results demonstrate that the combined experimental (¹³C CPMAS NMR, IR) and theoretical (DFT) approach can be used to characterize the molecular structure of solid complexes for which crystallographic data are not available.     

Structural characterization of the coordination behavior of 4,4′-di-methoxy,2,2′-di-ol-benzophenone modified metal alkoxides

For the first time, the coordination behavior of the 4,4′-di-methoxy,2,2′-di-ol-benzophenone (H₂-OBzP) ligand with a series of early transition metal alkoxides (Group 4, 5, and 6) was determined to adopt either the ‘bridging, chelating bridging’ (μ,μ_c-OBzP) or the ‘bichelating bridging’ (μ_c2-OBzP) arrangement. The main products were found to be dimeric with pseudo-octahedral (O_h) bound metal centers. The μ,μ_c-OBzP mode was noted for the larger cations (Hf, Nb, and Ta) and the solvated smallest (Ti/py) whereas the μ_c2-OBzP coordination was observed for the larger Group 4 metal congeners: [(py)(OPrⁱ)₂Ti(μ,μ_c-OBzP)]₂ (1), ‘{[(OBu^t)₂Ti(μ-OBu^t)]₂(μ_c2-OBzP)}_n’ (2), [(ONep)₂Ti(μ-ONep)]₂(μ_c2-OBzP) (3), [(OBu^t)₂Zr(μ-OBu^t)]₂(μ_c2-OBzP) (4), [(MeIm)₂(ONep)₂Zr(μ,μ_c-OBzP)]₂ (5), [(ONep)₂Zr(μ_c2-OBzP)(μ-ONep)(μ₃-O)Zr(ONep)]₂ (5a), [(OBu^t)₂Hf(μ_c2-OBzP)]₂(6), ‘{[(ONep)₂Hf(μ,μ_c-OBzP)]₂·py}_n’ (7), ‘{[(OEt)₃Nb(μ,μ_c-OBzP)]₂}_n’ (8), [(ONep)₃Nb(μ,μ_c-OBzP)]₂ (9), [(OEt)₃Ta(μ,μ_c-OBzP)]₂ (10), [(ONep)₃Ta(μ,μ_c-OBzP)]₂ (11), and [(OEt)₂(O)W(μ,μ_c-OBzP)]₂ (12), [(ONep)₂W(O)(μ,μ_c-OBzp)]₂ (13), [(py)(O)₂W(μ,μ_c-OBzP)]₂ (13a), and [(Me₂Al(μ,²μ_c-OBzP)Al(py)₂] (14) where Me = CH₃, OEt = OCH₂CH₃, OPrⁱ = OCHMe₂, OBu^t = OCMe₃, ONep = OCH₂CMe₃, py = pyridine, MeIm = 1-methyl imidazole, and ²μ_c-refers to the chelation occurs on the same metal. Compounds 2, 7, and 8 are represented by quotation marks since they could not be crystallographically characterized, however, their structural arrangements were deduced from the FTIR spectroscopic data. The coordination mode of the OBzP ligand for 1-13 appears to be driven by the need to fill the O_h geometry, which is achieved by either binding solvent molecules or additional bridging ligands, dictated by the charge and size of the cations employed. The metal alkyl alkoxide compound 14 employs a unique μ,²μ_c-OBzP mode, yielding a +2/+4 charge separated molecular Al complex.     

Simon Labbé's work on iron and copper homeostasis

Iron and copper have a wealth of functions in biological systems, which makes them essential micronutrients for all living organisms. Defects in iron and copper homeostasis are directly responsible for diseases, and have been linked to impaired development, metabolic syndromes and fungal virulence. Consequently, it is crucial to gain a comprehensive understanding of the molecular bases of iron- and copper-dependent proteins in living systems. Simon Labbé maintains parallel programs on iron and copper homeostasis using the fission yeast Schizosaccharomyces pombe (Schiz. pombe) as a model system. The study of fission yeast transition-metal metabolism has been successful, not only in discerning the genes and pathways functioning in Schiz. pombe, but also the genes and pathways that are active in mammalian systems and for other fungi.     

The influence of metal ions on malic enzyme activity and lipid synthesis in Aspergillus niger

In the presence of copper significant induction of citric acid overflow was observed, while concomitantly lower levels of total lipids were detected in the cells. Its effect was more obvious in a medium with magnesium as sole divalent metal ions, while in a medium with magnesium and manganese the addition of copper had a less pronounced effect. Since the malic enzyme was recognised as a supplier of reducing power in the form of reduced nicotinamide adenine dinucleotide phosphate for lipid biosynthesis, its kinetic parameters with regard to different concentrations of metal ions were investigated. Some inhibition was found with Fe(2+) and Zn(2+), while Cu(2+) ions in a concentration of 0.1 mM completely abolished malic enzyme activity. The same metal ions proportionally reduced the levels of total lipids in Aspergillus niger cells. A strong competitive inhibition of the enzyme by Cu(2+) was observed. It seemed that copper competes with Mg(2+) and Mn(2+) for the same binding site on the protein.     

Synthesis of low molecular weight thiols in response to Cd exposure in Thlaspi caerulescens

In this study, we investigated the accumulation of phytochelatins (PCs) and other low molecular weight (LMW) thiols in response to Cd exposure in two contrasting ecotypes differing in Cd accumulation. Using a root elongation test, we found that the highly accumulating ecotype Ganges was more tolerant to Cd than the low Cd-accumulation ecotype Prayon. l -buthionine-(S,R)-sulphoximine (BSO), a potent inhibitor of the γ -glutamylcysteine synthetase ( γ -ECS) (an enzyme involved in the PC biosynthetic pathway), increased the Cd sensitivity of Prayon, but had no effect on Ganges. Although PC accumulation increased in response to Cd exposure, no significant differences were observed between the two ecotypes. Cd exposure induced a dose-dependent accumulation of both Cys and a still unidentified LMW thiol in roots of both ecotypes. Root accumulation of Cys and this thiol was higher in Ganges than in Prayon; the ecotypic differences were more pronounced when the plants were treated with BSO. These findings suggest that PCs do not contribute to the Cd hypertolerance displayed by the Ganges ecotype of Thlaspi caerulescens , whereas Cys and other LMW thiols might be involved.     

Within and between population variation for zinc and nickel accumulation in two species of Thlaspi (Brassicaceae)

In this study, the differences in zinc (Zn) and nickel (Ni) hyperaccumulation were investigated between three populations of Thlaspi pindicum together with genetic variation within populations of T. pindicum and Thlaspi alpinum var. sylvium, both serpentine endemics. Three experiments were conducted under standard conditions in hydroponic assay. Each experiment contained three treatments of metal: 100 microm Zn, 100 microm Ni, and combined 100/100 microm Zn/Ni. Genetic variation within populations was determined using maternal families. No genetic variation within populations was found for either Zn or Ni hyperaccumulation for both T. pindicum and T. alpinum var. sylvium, but differences were observed for both Zn and Ni hyperaccumulation between populations of T. pindicum. In combined Zn/Ni treatments, Zn inhibited Ni translocation in both species, which is unexpected considering that these species are serpentine endemics and well known Ni hyperaccumulators. The lack of genetic variation for metal hyperaccumulation is possibly due to inbreeding. Since Zn hyperaccumulation is not manifested in the field, inadvertent uptake of Zn is a plausible hypothesis for its preferential uptake.     

Purification and characterization of pectate lyase from banana (Musa acuminata) fruits

Pectate lyase (PEL) has been purified by hydrophobic, cation exchange and size exclusion column chromatographies from ripe banana fruit. The purified enzyme has specific activity of 680 +/- 50 pkat mg protein(-1). The molecular mass of the enzyme is 43 kDa by SDS-PAGE. The pI of the enzyme is 8 with optimum activity at pH 8.5. Analysis of the reaction products by paper and anion exchange chromatographies reveal that the enzyme releases several oligomers of unsaturated galacturonane from polygalacturonate. The K(m) values of the enzyme for polygalacturonate and citrus pectin (7.2% methylation) are 0.40 +/- 0.04 and 0.77 +/- 0.08 g l(-1), respectively. PEL is sensitive to inhibition by different phenolic compounds, thiols, reducing agents, iodoacetate and N-bromosuccinimide. The enzyme has a requirement for Ca(2+) ions. However, Mg(2+) and Mn(2+) can substitute equally well. Additive effect on the enzyme activity was observed when any two metal ions (out of Mg(2+), Ca(2+) and Mn(2+)) are present together. The banana PEL is a enzyme requiring Mg(2+), in addition to Ca(2+), for exhibiting maximum activity.