The role of strain on the recrystallization behaviour of hot worked and annealed magnesium alloy Mg-3Al-1Zn

The present work examines the microstructure that evolves during the hot deformation and subsequent annealing of magnesium alloy AZ31. In particular, the role of strain on the progression of dynamic recrystallization (DRX) and post-deformation recrystallization is investigated. It is found that the grain size developed after post-deformation recrystallization is larger when the deformation strain, and hence the degree of DRX, is low (for strains up to 0.4). Also, the kinetics of post-deformation recrystallization are found to be independent of strain for strain values of 0.4 and above. Whilst increasing strain alters the texture of the un-recrystallized microstructure (for the deformation mode examined), the texture does not change significantly during post-deformation recrystallization.

Designing microstructures to enhance the plasticity of wrought magnesium alloys

The data examines the design of magnesium alloys for improved ductility by the edition of rare earth elements. These elements, such as cerium and gadolinium modify the texture of wrought products and also refine the grain size.

Highly selective and sensitive DNA assay based on electrocatalytic oxidation of ferrocene bearing zinc(II)-cyclen complexes with diethylamine

A highly selective and sensitive electrochemical biosensor has been developed that detects DNA hybridization by employing the electrocatalytic activity of ferrocene (Fc) bearing cyclen complexes (cyclen = 1,4,7,10-tetraazacyclododecane, Fc[Zn(cyclen)H2O]2(ClO4)4 (R1), Fc(cyclen)2 (R2), Fc[Zn(cyclen)H2O](ClO4)2 (R3), and Fc(cyclen) (R4)). A sandwich-type approach, which involves hybridization of a target probe hybridized with the preimmobilized thiolated capture probe attached to a gold electrode, is employed to fabricate a DNA duplex layer. Electrochemical signals are generated by voltammetric interrogation of a Fc bearing Zn−cyclen complexes that selectively and quantitatively binds to the duplex layers through strong chelation between the cyclen complexes and particular nucleobases within the DNA sequence. Chelate formation between R1 or R3 and thymine bases leads to the perturbation of base-pair (A−T) stacking in the duplex structure, which greatly diminishes the yield of DNA-mediated charge transport and displays a marked selectivity to the presence of the target DNA sequence. Coupling the redox chemistry of the surface-bound Fc bearing Zn−cyclen complex and dimethylamine provides an electrocatalytic pathway that increases sensitivity of the assay and allows the 100 fM target DNA sequence to be detected. Excellent selectivity against even single-base sequence mismatches is achieved, and the DNA sensor is stable and reusable.

Changes in zinc ligation promote remodeling of the active site in the zinc hydrolase superfamily

The zinc hydrolase superfamily is a group of divergently related proteins that are predominantly enzymes with a zinc-based catalytic mechanism. The common structural scaffold of the superfamily consists of an eight-stranded β-sheet flanked by six α-helices. Previous analyses, while acknowledging the likely divergent origins of leucine aminopeptidase, carboxypeptidase A and the co-catalytic enzymes of the metallopeptidase H clan based on their structural scaffolds, have failed to find any homology between the active sites in leucine aminopeptidase and the metallopeptidase H clan enzymes. Here we show that these two groups of co-catalytic enzymes have overlapping dizinc centers where one of the two zinc atoms is conserved in each group. Carboxypeptidase A and leucine aminopeptidase, on the other hand, no longer share any homologous zinc-binding sites. At least three catalytic zinc-binding sites have existed in the structural scaffold over the period of history defined by available structures. Comparison of enzyme-inhibitor complexes show that major remodeling of the substrate-binding site has occurred in association with each change in zinc ligation in the binding site. These changes involve re-registration and re-orientation of the substrate. Some residues important to the catalytic mechanism are not conserved amongst members. We discuss how molecules acting in trans may have facilitated the mutation of catalytically important residues in the active site in this group.

An electrochemical impedance study of ionic liquid film formation and aqueous corrosion of magnesium alloy ZE41

Ionic liquid surface treatments are proposed as a method of controlling corrosion processes on magnesium alloys. An important magnesium alloy, ZE41 (nominally 4% Zn and 1% rare earth), was treated with the ionic liquid trihexyl(tetradecyl)phosphonium diphenylphosphate (P₆₆₆₁₄DPP). Impedance spectra were acquired at intervals during the treatment, indicating the development of a film and allowing a measure of the film formation process to be obtained over time. Mechanically polished and electro-polished surfaces were prepared; these surfaces, treated and untreated, were subsequently exposed to 0.1 M NaCl aqueous solutions. The corrosion behavior of the prepared surfaces were assessed using impedance spectroscopy and optical microscopy. The results indicated a significant role for the method of surface preparation used and, in both cases, the ionic liquid treatment produced a more corrosion-resistant surface.

On the impact of second phase particles on twinning in magnesium alloys

Deformation twinning is an important deformation mode in magnesium alloys. Despite this, little is known on the extent to which the stress for twinning can be altered by a dispersion of second phase particles. The current paper presents a series of findings on the role of differently shaped particles on both the stress required for twinning and the characteristics of the twins that form. It is shown that plate shaped particles are, as one might expect, an effective strengthener to {10-12} twinning. When precipitate plates form on the basal planes, the relative hardening of basal slip is minor in comparison to that seen for twinning. This provides opportunity for the alloy designer to control the apparent critical resolved shear stresses (CRSS) for the different deformation modes. Possible sources for the hardening of twins are discussed.