Erratum to: Determination of metal ion content of beverages and estimation of target hazard quotients: a comparative study

This is a correction to the following paper: Hague T, Petroczi A, Andrews PR, Barker J, Naughton DP: Determination of metal ion content of beverages and estimation of target hazard quotients: a comparative study. Chem Central J 2008, 2:13.     

The role of outer-sphere surface acidity in alkene epoxidation catalyzed by calixarene-Ti(IV) complexes

Cooperativity between Br?nsted acidic defect sites on oxide surfaces and Lewis acid catalyst sites consisting of grafted calixarene-Ti(IV) complexes is investigated for controlling epoxidation catalysis. Materials are synthesized that, regardless of the surface or calixarene substituent, demonstrate nearly identical UV-visible ligand-to-metal charge-transfer bands and Ti K-edge X-ray absorption near edge spectral features consistent with site-isolated, coordinatively unsaturated Ti(IV) atoms. Despite similar Ti frontier orbital energies demonstrated by these spectra, replacing a homogeneous triphenylsilanol ligand with a silanol on a SiO2 surface increases cyclohexene epoxidation rates with tert-butyl hydroperoxide 20-fold per Ti site. Supporting calixarene-Ti active sites on fully hydroxylated Al2O3 or TiO2, which possess lower average surface hydroxyl pKa than that of SiO2, reduces catalytic rates 50-fold relative to SiO2. These effects are consistent with SiO2 surfaces balancing two competing factors that control epoxidation rates-equilibrated hydroperoxide binding at Ti, disfavored by stronger surface Br?nsted acidity, and rate-limiting oxygen transfer from this intermediate to alkenes, favored by strongly H-bonding intermediates. These observations also imply that Ti-OSi rather than Ti-OCalix bonds are broken upon hydroperoxide binding to Ti in kinetically relevant steps, which is verified by the lack of a calixarene upper-rim substituent effect on epoxidation rate. The pronounced sensitivity of observed epoxidation rates to the support oxide, in the absence of changes to the Ti coordination environment, provides experimental evidence for the importance of outer-sphere H-bonding interactions for the exceptional epoxidation reactivity of titanium silicalite and related catalysts.     

Determination of metal ion content of beverages and estimation of target hazard quotients: a comparative study

Background  

Considerable research has been directed towards the roles of metal ions in nutrition with metal ion toxicity attracting particular attention. The aim of this study is to measure the levels of metal ions found in selected beverages (red wine, stout and apple juice) and to determine their potential detrimental effects via calculation of the Target Hazard Quotients (THQ) for 250 mL daily consumption.     

Electrocatalytic and magnetic properties of ultrathin nanostructured iron-melanin films on Au(111)

We have prepared ultrathin, nanostructured melanin films on Au(111) by means of electrochemical self-assembly. These films were characterized by using Auger electron spectroscopy, X-ray absorption near-edge structure spectroscopy, scanning tunneling microscopy, magnetic force microscopy, and electrochemical techniques. Two types of nanostructures are present in the film: melanin nanoparticles and Fe(3)O(4) nanoparticles. The melanin nanoparticles contain Fe bonded to oxygen-containing phenolic groups in an octahedral configuration similar to that found in Fe(2)O(3). The inorganic-organic composite exhibits magnetic properties and catalyzes the electroreduction of hydrogen peroxide in alkaline and neutral electrolyte solutions. The electrocatalytic activity depends on the Fe-bound melanin and appears to be similar to that found for Fe-porphyrins.     

Microfluidic platform for electrophysiological studies on Xenopus laevis oocytes under varying gravity levels

Voltage clamp measurements reveal important insights into the activity of membrane ion channels. While conventional voltage clamp systems are available for laboratory studies, these instruments are generally unsuitable for more rugged operating environments. In this study, we present a non-invasive microfluidic voltage clamp system developed for the use under varying gravity levels. The core component is a multilayer microfluidic device that provides an immobilisation site for Xenopus laevis oocytes on an intermediate layer, and fluid and electrical connections from either side of the cell. The configuration that we term the asymmetrical transoocyte voltage clamp (ATOVC) also permits electrical access to the cytosol of the oocyte without physical introduction of electrodes by permeabilisation of a large region of the oocyte membrane so that a defined membrane patch can be voltage clamped. The constant low level air pressure applied to the oocyte ensures stable immobilisation, which is essential for keeping the leak resistance constant even under varying gravitational forces. The ease of oocyte mounting and immobilisation combined with the robustness and complete enclosure of the fluidics system allow the use of the ATOVC under extreme environmental conditions, without the need for intervention by a human operator. Results for oocytes over-expressing the epithelial sodium channel (ENaC) obtained under laboratory conditions as well as under conditions of micro- and hypergravity demonstrate the high reproducibility and stability of the ATOVC system under distinct mechanical scenarios.