Challenges for the development of a biotic ligand model predicting copper toxicity in estuaries and seas

This is the author's accepted manuscript. The final published article is available from the link below. Copyright @ 2011 SETAC.An effort is ongoing to develop a biotic ligand model (BLM) that predicts copper (Cu) toxicity in estuarine and marine environments. At present, the BLM accounts for the effects of water chemistry on Cu speciation, but it does not consider the influence of water chemistry on the physiology of the organisms. We discuss how chemistry affects Cu toxicity not only by controlling its speciation, but also by affecting the osmoregulatory physiology of the organism, which varies according to salinity. In an attempt to understand the mechanisms of Cu toxicity and predict its impacts, we explore the hypothesis that the common factor linking the main toxic effects of Cu is the enzyme carbonic anhydrase (CA), because it is a Cu target with multiple functions and salinity-dependent expression and activity. According to this hypothesis, the site of action of Cu in marine fish may be not only the gill, but also the intestine, because in this tissue CA plays an important role in ion transport and water adsorption. Therefore, the BLM of Cu toxicity to marine fish should also consider the intestine as a biotic ligand. Finally, we underline the need to incorporate the osmotic gradient into the BLM calculations to account for the influence of physiology on Cu toxicity.Brunel Universit

Building on Cram's legacy: stimulated gating in hemicarcerands.

CONSPECTUS: Donald Cram's pioneering Nobel Prize-winning work on host-guest molecules led eventually to his creation of the field of container molecules. Cram defined two types of container molecules: carcerands and hemicarcerands. Host-guest complexes of carcerands, called carceplexes, are formed during their synthesis; once a carceplex is formed, the trapped guest cannot exit without breaking covalent bonds. Cram defined a quantity called constrictive binding, arising from the mechanical force that prevents guest escape. The constrictive binding in carceplexes is high. In contrast, hemicarcerands have low constrictive binding and are able to release the incarcerated guests at elevated temperatures without breaking covalent bonds. We have designed molecules that can switch from carcerand to hemicarcerand through a change in structure that we call gating. The original discovery of gating in container molecules involved our computational studies of a Cram hemicarceplex that was observed to release a guest upon heating. We found that the side portals of this hemicarceplex have multiple thermally accessible conformations. An eight-membered ring that is part of a portal changes from a "chair" to a "boat" structure, leading to the enlargement of the side portal and the release of the guest. This type of gating is analogous to phenomena often observed with peptide loops in enzymes. We refer to this phenomenon as thermally controlled gating. We have also designed and synthesized redox and photochemically controlled gated hemicarceplexes. Gates are built onto host molecules so that the opening or closing of such gates is stimulated by reducing or oxidizing conditions, or by ultraviolet irradiation. In both cases, the appropriate stimuli can produce a carceplex (closed gates) or hemicarceplex (open gates). A hemicarceplex with closed gates behaves like a carceplex, due to its very high constrictive binding energy. When the gates are opened, constrictive binding is dramatically lowered, and guest entrance and exit become facile. This stimulated switching between open and closed states controls access of the guest to the binding site. The experimental and computational investigations of gated hemicarcerands and several potential applications of gated hemicarceplexes are described in this Account

Protein-mediated dethreading of a biotin-functionalised pseudorotaxane

In this article, we describe the synthesis of new biotin-functionalised naphthalene derivatives 3 and 4 and their complexation behaviour with avidin and neutravidin using a range of analytical techniques. We have shown using 2-(4prime or minute-hydroxyazobenzene)benzoic acid displacement and ITC experiments{,} that compounds 3 and 4 have the propensity to form reasonably high-affinity bioconjugates with avidin and neutravidin. We have also demonstrated using 1H NMR{,} UV-vis and fluorescence spectroscopy that the naphthalene moiety of 3 and 4 facilitates the formation of pseudorotaxane-like structures with 1 in water. We have then investigated the ability of avidin and neutravidin to modulate the complexation between 1 and 3 or 4. UV-vis and fluorescence spectroscopy has shown that in both cases the addition of the protein disrupts complexation between the naphthalene moieties of 3 and 4 with 1

Anion receptor chemistry: highlights from 2011 and 2012

This review covers advances in anion complexation in the years 2011 and 2012. The review covers both organic and inorganic systems and also highlights the applications to which anion receptors can be applied such as self-assembly and molecular architecture, sensing, catalysis and anion transport

Stability of salts and complexes of humic acids

Základem práce je studium vlivu přítomnosti kovů inkorporovaných do struktury huminových látek při tepelné zátěži za přítomnosti vzdušného kyslíku. Pro tyto účely byla použita lignitická huminová kyselina, u které byl nejprve retitračně-vodivostní metodou stanoven počet vazných míst, tj. karboxylových skupin. Smícháním s roztoky sodných a měďnatých iontů byly získány koncové produkty s různými stupni nasycení zjištěných vazných míst. Pro zhodnocení termooxidační stability byla provedena termogravimetrická analýza a diferenční kompenzační kalorimetrie. Výsledky přinášejí nový pohled na reaktivitu huminové kyseliny s kovovými ionty v kapalné fázi, poukazují na možný vznik „porézní“ struktury sodných humátů a jejich schopnost retence vody.The ground of this work lies in the study of influence of metal ions incorporated onto the structure of humic substances during thermal stress in the presence of air oxygen. For these purposes, lignitic humic acid was used. The amount of binding sites, i.e. carboxylic groups, was determined by retitration-conductometric method. Mixing the humic acid with solutions of sodium and cupric ions gave the final products with different saturation degrees of detected binding sites. For the evaluation of thermooxidative stability, thermogravimetric analysis and differential scanning calorimetry were performed. The results bring new view upon the reactivity of humic acid with metal ions in the liquid state, indicate possible formation of “porous” structure of sodium humates and their water-retention ability.

Leaching Properties of Estuarine Harbor Sediment Before and After Electrodialytic Remediation

Electrodialytic remediation (EDR) can be used to extract heavy metals from a variety of different media. In this work, contaminated harbor sediments from two locations in the United States and one in Norway were subjected to EDR, and were compared with batch extractions conducted with the sediment. pH-dependent leaching tests were used to evaluate changes in leaching properties of treated and control sediments. Significant fractions of total concentrations were removed during treatment (35–95% with an average of 75% for all sediments and elements investigated). The release of elements in pH-dependent leaching tests, however, demonstrated equal or greater leaching from treated sediments in the neutral pH range. Dissolved organic carbon appears to be a significant contributor to post-treatment increases in leaching, and dissolution of significant iron and aluminum sorption sites is hypothesized to also play a role. This research highlights the importance of understanding contaminant speciation and availability, as total metals concentrations, in this particular case, do not relate to estimates of the environmental availability of metals (total concentrations were typically two to three orders of magnitude greater than concentrations released during pH-dependent leaching)

Interactions between cadmium and lead with acidic soils: Experimental evidence of similar adsorption patterns for a wide range of metal concentrations and the implications of metal migration

The importance of high- and low-affinity surface sites for cadmium and lead adsorption in typical European and Asian soils was investigated. Adsorption experiments on surface and deep horizons of acidic brown (Vosges, France) and red loess soils (Hunan, China) were performed at 25 ◦C as a function of the pH (3.5–8) and a large range of metal concentrations in solution (10−9–10−4 mol l−1). We studied the adsorption kinetics using a Cd2+-selective electrode and desorption experiments as a function of the solid/solution ratio and pH. At a constant solution pH, all samples exhibited similar maximal adsorption capacities (4.0 ± 0.5 µmol/g Cd and 20 ± 2 µmol/g Pb). A constant slope of adsorbed–dissolved concentration dependence was valid over 5 orders of magnitude of metal concentrations. Universal Langmuir and Freundlich equations and the SCM formalism described the adsorption isotherms and the pH-dependent adsorption edge over very broad ranges of metal concentrations, indicating no high- or low-affinity sites for metal binding at the soil surface under these experimental conditions. At pH 5, Cd and Pb did not compete, in accordance with the SCM. The metal adsorption ability exceeded the value for soil protection by two orders of magnitude, but only critical load guarantees soil protection since metal toxicity depends on metal availability