Visualisation of chemical processes during corrosion of zinc using magnetic resonance imaging

Compositional and structural changes within an electrolyte solution above an electrochemically active metal surface have been visualised using magnetic resonance imaging (MRI) for the first time. In these proof-of-concept experiments, zinc metal was galvanically corroded in a saturated lithium chloride solution. Magnetic resonance relaxation maps were taken during the corrosion process and spatial variations in both T₁ and T₂ relaxation times were observed to change with time. These changes were attributed to changes in the speciation of zinc ions in the electrolyte.

Surface modification for enhanced corrosion resistance using fluid bed reactor chemical vapour deposition (FBR-CVD)

The use of materials with otherwise desirable mechanical properties is often problematic in practice as a result of corrosion. Susceptibility may arise for a number of reasons, including an electrochemically heterogeneous surface or destabilisation of a passive film. These shortcomings have historically been overcome through the use of various coatings or claddings. However, a more robust surface layer with enhanced corrosion resistance could possibly be produced via local surface alloying using a fluidised bed. A fluidised bed treatment allows a surface to be alloyed, producing a distinct surface layer up to tens of microns thick. Surface alloying additions can be selected on the basis of whether they are known or suspected to enhance the corrosion resistance of a particular material, whilst at a minimum, surface alloying likely provides a more electrochemically homogeneous surface. Electrochemical evaluations using potentiodynamic polarisations in NaCl electrolytes have shown chromised plain carbon and stainless steel surfaces have decreased rates of corrosion, decreased passive current densities, and ennobled pitting potentials relative to untreated specimens.

Corrosion impact on drinking water distribution systems : a review and future research direction

At present water treatment and distribution is of high priority to ensure that communities have access to safe and affordable drinking water. Current information states that in the United States a total annual cost of $36 billion (US) is spent replacing aging infrastructure, lost water from unaccounted-for leaks, corrosion inhibitors, internal mortar linings, external coatings, and cathodic protection as a result of corrosion. In order to reduce the cost incurred as a result of corrosion in the water distribution industry, it is essential that better corrosion management and preventative strategies are implemented. However through investigation of research previously undertaken by others, it was found that there was a lack of study of corrosion within distribution systems in the tropics taking into account the related seasonal temperature variations. To assist in the development of management strategies to improve the outcomes of drinking water distribution systems, the authors propose to implement a pilot study involving the installation of a corrosion reactor based on standard corrosion assessment technologies in a water distribution system located in the tropics.

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.

Phenylalanine-544 plays a key role in substrate and inhibitor binding by providing a hydrophobic packing point at the active site of insulin-regulated aminopeptidase

Inhibitors of insulin-regulated aminopeptidase (IRAP) improve memory and are being developed as a novel treatment for memory loss. In this study, the binding of a class of these inhibitors to human IRAP was investigated using molecular docking and site-directed mutagenesis. Four benzopyran-based IRAP inhibitors with different affinities were docked into a homology model of the catalytic site of IRAP. Two 4-pyridinyl derivatives orient with the benzopyran oxygen interacting with the Zn2+ ion and a direct parallel ring-stack interaction between the benzopyran rings and Phe544. In contrast, the two 4-quinolinyl derivatives orient in a different manner, interacting with the Zn2+ ion via the quinoline nitrogen, and Phe544 contributes an edge-face hydrophobic stacking point with the benzopyran moiety. Mutagenic replacement of Phe544 with alanine, isoleucine, or valine resulted in either complete loss of catalytic activity or altered hydrolysis velocity that was substrate-dependent. Phe544 is also important for inhibitor binding, because these mutations altered the Ki in some cases, and docking of the inhibitors into the corresponding Phe544 mutant models revealed how the interaction might be disturbed. These findings demonstrate a key role of Phe544 in the binding of the benzopyran IRAP inhibitors and for optimal positioning of enzyme substrates during catalysis.

Insulin-regulated aminopeptidase : analysis of peptide substrate and inhibitor binding to the catalytic domain

Peptide inhibitors of insulin-regulated aminopeptidase (IRAP) accelerate spatial learning and facilitate memory retention and retrieval by binding competitively to the catalytic site of the enzyme and inhibiting its catalytic activity. IRAP belongs to the M1 family of Zn2+-dependent aminopeptidases characterized by a catalytic domain that contains two conserved motifs, the HEXXH(X)18E Zn2+-binding motif and the GXMEN exopeptidase motif. To elucidate the role of GXMEN in binding peptide substrates and competitive inhibitors, site-directed mutagenesis was performed on the motif. Non-conserved mutations of residues G428, A429 and N432 resulted in mutant enzymes with altered catalytic activity, as well as divergent changes in kinetic properties towards the synthetic substrate leucine β-naphthalamide. The affinities of the IRAP inhibitors angiotensin IV, Nle1-angiotensin IV, and LVV-hemorphin-7 were selectively decreased. Substrate degradation studies using the in vitro substrates vasopressin and Leu-enkephalin showed that replacement of G428 by either D, E or Q selectively abolished the catalysis of Leu-enkephalin, while [A429G]IRAP and [N432A]IRAP mutants were incapable of cleaving both substrates. These mutational studies indicate that G428, A429 and N432 are important for binding of both peptide substrates and inhibitors, and confirm previous results demonstrating that peptide IRAP inhibitors competitively bind to its catalytic site.