Metal ions and carcinogenesis

Metals are essential for the normal functioning of living organisms. Their uses in biological systems are varied, but are frequently associated with sites of critical protein function, such as zinc finger motifs and electron or oxygen carriers. These functions only require essential metals in minute amounts, hence they are termed trace metals. Other metals are, however, less beneficial, owing to their ability to promote a wide variety of eleterious health effects, including cancer. Metals such as arsenic, for example, an produce a variety of diseases ranging from keratosis of the palms and feet to cancers in multiple target organs. The nature and type of metal-induced pathologies appear to be dependent on the concentration, speciation, and length of exposure. Unfortunately, human contact with metals is an inescapable consequence of human life, with exposures occurring from both occupational and environmental sources. A uniform mechanism of action for all harmful metals is unlikely, if not implausible, given the diverse chemical properties of each metal. In this chapter we will review the mechanisms of carcinogenesis of arsenic, cadmium, chromium, and nickel, the four known carcinogenic metals that are best understood. The key areas of speciation, bioavailability, and mechanisms of action are discussed with particular reference to the role of metals in alteration of gene expression and maintenance of genomic integrity.

Cadmium, copper, mercury, and zinc concentrations in tissues of the King Crab (Pseudocarcinus gigas) from southeast Australian waters

The concentrations of cadmium, copper, mercury, and zinc were determined in muscle (body, claw, and leg), hepatopancreas, and gill tissues of Pseudocarcinus gigas, an exceptionally large, long-lived, and deep-dwelling crab species. The accumulation patterns observed are discussed in terms of both intra- and interspecies variations, with particular attention to the possible consequences of the extreme size and depth range of P. gigas. Metal concentrations did not depend significantly on sex of the crab. Significant differences between tissues were detected for all metals, and the distribution of metal between the tissues was different for each metal. Significant correlations were found between metal concentrations in the various tissues and crab size, and these are discussed and rationalised. The concentrations of mercury and zinc in muscle tissue increased with crab size and were high compared to other crab species. The concentrations of cadmium and copper present in edible tissues were not especially high compared to other crab species, but the concentration of cadmium in the hepatopancreas is of dietary concern.

Heavy metal concentrations in wild and cultured blacklip abalone (haliotis rubra Leach) from southern Australian waters

The concentrations of 12 trace metals were assessed in wild and cultured specimens of blacklip abalone, Haliotis rubra, from each of two sites, Geelong and Port Fairy, in Victoria, Australia. Cadmium, copper, iron and zinc were quantified in the foot muscle of specimens from all four populations but the concentrations of aluminium, arsenic, beryllium, chromium, lead, manganese, nickel and vanadium were below the detection limits of the instrumental techniques employed. When similar sized specimens from each population were compared, the concentrations of each of the quantifiable metals varied according to location. The Geelong wild population had the highest or equal highest concentrations of each metal. Metal concentrations in the wild populations were usually greater than or equal to the concentrations in the corresponding cultured population. The concentrations of the regulated essential elements, copper and zinc, decreased with an increase in abalone length whereas the concentrations of iron, manganese and cadmium were independent of length. Metal concentrations in H. rubra from all sites complied with the Australian Food Code and other standards of food safety.

catena-Poly[[[bis[(-)-O-bornyldithiocarbonato-κ2S,S']nickel(II)]-μ-4,4'-bipyridine-κ2N:N'] chloroform disolvate]

The Ni atom in the linear polymeric title complex, {[Ni(C₁₁H₁₇OS₂)₂(C₁₀H₈N₂)]·2CHC1₃}_n or {Ni[S₂C(-)-OC₁₀H₁₇)]₂(NC₅H₄C₅H₄N)·2CHC1₃}_n, is octahedrally coordinated within a trans-N₂S₄ donor set. There are two crystallographically independent polymers and two independent CHC1₃ molecules in the structure. For each polymer unit, the Ni atom and the axis of the 4,4'-bipyridine ligand are located on a twofold axis.

Micro-porous nickel produced by powder metallurgy

Micro-porous nickel (Ni) with an open cell structure was fabricated by a special powder metallurgical process, which includes the adding of a space-holding material. The average pore size of the micro-porous Ni samples approximated 30 μm and 150 μm, and the porosity ranged from 60 % to 80 %. The porous characteristics of the Ni samples were observed using scanning electron microscopy (SEM) and the mechanical properties were evaluated using compressive tests. For comparison, porous Ni samples with a macro-porous structure prepared by both powder metallurgy
(pore size 800 μm) and the traditional chemical vapour deposition (CVD) method (pore size 1300 μm) were also presented. Results indicated that the porous Ni samples with a micro-porous structure exhibited different deformation behaviour and dramatically increased mechanical properties,
compared to those of the macro-porous Ni samples.

Preparation and characterisation of open-cell microporous nickel

In the present study, nickel foams with an open cell microporous structure were fabricated by the so-called space-holding particle sintering method, which included the adding of a particulate polymeric material (PMMA). The average pore size of the nickel foams approximated 10.5 μm; and the porosity ranged from 70 % to 80 %. The porous characteristics of the nickel foams were observed using scanning electron microscopy and the mechanical properties were evaluated using compressive tests. For comparison, nickel foams with an open-cell macroporous structure (pore size approximately 1.3 mm) were also presented. Results indicated that the nickel foams with a microporous structure possess enhanced mechanical properties than those with a macroporous structure.

Characterisation of nickel(II) extraction by 2-hydroxy-5-nonylacetophenone oxime (LIX 84) in a micellar phase

The properties of the nickel(II)/2-hydroxy-5-nonylacetophenone oxime (HNAPO), an active ingredient in LIX 84, extraction system were characterised in a micellar system. The extinction coefficient, λ_max of HNAPO (316 nm) and the Ni²⁺ complex (387 nm) in a neutral micellar system, poly dispersed octa-ethyleneglycol mono-n-dodecyl ether (G₁₂A₈) were determined as 3100 and 3500 M⁻¹ cm⁻¹, respectively. HNAPO was found to have a neutral micellar phase and bulk aqueous phase pK_a of 11.5 and 12.5, respectively. The extraction equilibrium constant, K_ex, was determined to be 10^−8.0, and the deviation from theory observed at high pH can be accounted for by consideration of the competition for nickel(II) ions by hydroxide ions and HNAPO. A micellar phase of octa-ethyleneglycol mono-n-dodecyl ether (C₁₂E₈) was determined to be an appropriate model of the free oil/water interface from the solubilised location of HNAPO. Utilising the interfacial probe, 4-heptadecyl-7-hydroxy coumarin (HHC) allowed the determination of the electrostatic surface potential of mixed micelles of G₁₂A₈ and sodium dodecyl sulphate (SDS) or dodecyl trimethyl ammonium chloride (DTAC). The electrostatic surface potential was a linear function of the number of additional surfactant monomers within the G₁₂A₈ micelle, for the concentration range studied. For G₁₂A₈/DTAC mixed micelles, the surface potential was given by +1.1 mV per DTAC molecule per micelle, and for G₁₂A₈/SDS mixed micelles the relationship was −1.4 mV per SDS molecule per micelle.

Joining magnesia partially stabilised zirconia with nickel by current enhancement

This study confirms that current enhancement is a reliable and efficient method for joining ceramic and metal. Experiments indicated very high bond strengths. Mathematical modelling explained the mechanism of joining and has established critical functions for design and control.

Anisotropic mechanical properties of nickel foams fabricated by powder metallurgy

In the present study, porous nickel foam samples with pore sizes of 20 μm and 150 μm and porosities of 60 % and 70 % were fabricated by the space-holding sintering method via powder metallurgy. Electron scanning microscopy (SEM) and Image-Pro Plus were used to characterise the morphological features of the porous nickel foam samples. The anisotropic mechanical properties of porous nickel foams were investigated by compressive testing loading in different directions, i.e. the major pore axis and minor pore axis. Results indicated that the nominal stress of the nickel foam samples increases with the decreasing of the porosity. Moreover, the foam sample exhibited significantly higher nominal stress for loading in the direction of the major pore axis than loading in direction of the minor pore axis. It is also noticeable that the nominal stress of the nickel foams increases with the decreasing of the pore size. It seems that the deformation behaviour of the foams with a pore size in the micron-order differs from those with a macro-porous structure.

The zwitterion effect in ionic liquids : towards practical rechargeable lithium-metal batteries

Practical lithium-metal batteries are the ultimate goal of battery researchers. The addition of a zwitterionic compound (see Figure) to an ionic liquid electrolyte doped with a lithium salt results in a 100% enhancement of the current densities achieved in the cycling of a lithium-metal cell. This phenomenon arises due to increased lithium-ion mobility or a reduced solid electrolyte interphase layer resistance.

Composite cell components for elevated temperature all-solid-state Li-ion batteries

Application of Li-ion batteries with liquid electrolytes at elevated temperatures (above 60°C) is limited due to the decomposition of the electrolyte. Stable solid state electrolytes can solve this problem, but the conductivity of these electrolytes are relatively low, the interfacial contacts with the electrodes are poor, and the charge transfer kinetics in the electrodes are limited. Solutions for these problems by using composite electrodes and electrolytes have been investigated and the results are described. A new concept for making all-solid-state Li-ion batteries that can be applied in the temperature range between room temperature and about 150°C will be presented.

Lithium-doped plastic crystal electrolytes exhibiting fast ion conduction for secondary batteries

Rechargeable lithium batteries have long been considered an attractive alternative power source for a wide variety of applications. Safety and stability1 concerns associated with solvent-based electrolytes has necessitated the use of lithium intercalation materials (rather than lithium metal) as anodes, which decreases the energy storage capacity per unit mass. The use of solid lithium ion conductors - based on glasses, ceramics or polymers - as the electrolyte would potentially improve the stability of a lithium metal anode while alleviating the safety concerns. Glasses and ceramics conduct via a fast ion mechanism, in which the lithium ions move within an essentially static framework. In contrast, the motion of ions in polymer systems is similar to that in solvent-based electrolytes - motion is mediated by the dynamics of the host polymer, thereby restricting the conductivity to relatively low values. Moreover, in the polymer systems, the motion of the lithium ions provides only a small fraction of the overall conductivity2, which results in severe concentration gradients during cell operation, causing premature failure3. Here we describe a class of materials, prepared by doping lithium ions into a plastic crystalline matrix, that exhibit fast lithium ion motion due to rotational disorder and the existence of vacancies in the lattice. The combination of possible structural variations of the plastic crystal matrix and conductivities as high as 2 3 1024 S cm21 at 60 8C make these materials very attractive for secondary battery applications.

Potential application of solid electrolyte P11 OH in Ni/MH batteries

N,N-Dimethylpyrrolidoium hydroxide (P11 OH) with polymer poly(tetramethyl ammonium acrylate) (PTMA) was investigated as an electrolyte in Ni/MH cells in this work. The efficiency and the performance of the electrolyte was discussed and elucidated with the performance of the cell. Their electrochemical characteristics had been investigated at different temperatures (25 °C and 50 °C) and different discharge current (15 mA g⁻¹ and 30 mA g⁻¹). The results show that the cell with electrolyte polymer-P11OH is dischargeable at these two temperatures, and a discharge capacity of 142 mAh g⁻¹ at 25 °C has been obtained.