Coordination effects on the binding of late 3d single metal species to cyanographene.

Anchoring single metal atoms on suitable substrates is a convenient route towards materials with unique electronic and magnetic properties exploitable in a wide range of applications including sensors, data storage, and single atom catalysis (SAC). Among a large portfolio of available substrates, carbon-based materials derived from graphene and its derivatives have received growing concern due to their high affinity to metals combined with biocompatibility, low toxicity, and accessibility. Cyanographene (GCN) as highly functionalized graphene containing homogeneously distributed nitrile groups perpendicular to the surface offers exceptionally favourable arrangement for anchoring metal atoms enabling efficient charge exchange between the metal and the substrate. However, the binding characteristics of metal species can be significantly affected by the coordination effects. Here we employed density functional theory (DFT) calculations to analyse the role of coordination in the binding of late 3d cations (Fe2+, Fe3+, Co2+, Ni2+, Cu2+, Cu+, and Zn2+) to GCN in aqueous solutions. The inspection of several plausible coordination types revealed the most favourable arrangements. Among the studied species, copper cations were found to be the most tightly bonded to GCN, which was also confirmed by the X-ray photoelectron spectroscopy (XPS), atomic absorption spectroscopy (AAS), and isothermal titration calorimetry (ITC) measurements. In general, the inclusion of coordination effects significantly reduced the binding affinities predicted by implicit solvation models. Clearly, to build-up reliable models of SAC architectures in the environments enabling the formation of a coordination sphere, such effects need to be properly taken into account.

Hydrologic Alterations from Climate Change Inform Assessment of Ecological Risk to Pacific Salmon in Bristol Bay, Alaska.

We developed an integrated hydrologic model of the upper Nushagak and Kvichak watersheds in the Bristol Bay region of southwestern Alaska, a region under substantial development pressure from large-scale copper mining. We incorporated climate change scenarios into this model to evaluate how hydrologic regimes and stream temperatures might change in a future climate, and to summarize indicators of hydrologic alteration that are relevant to salmon habitat ecology and life history. Model simulations project substantial changes in mean winter flow, peak flow dates, and water temperature by 2100. In particular, we find that annual hydrographs will no longer be dominated by a single spring thaw event, but will instead be characterized by numerous high flow events throughout the winter. Stream temperatures increase in all future scenarios, although these temperature increases are moderated relative to air temperatures by cool baseflow inputs during the summer months. Projected changes to flow and stream temperature could influence salmon through alterations in the suitability of spawning gravels, changes in the duration of incubation, increased growth during juvenile stages, and increased exposure to chronic and acute temperature stress. These climate-modulated changes represent a shifting baseline in salmon habitat quality and quantity in the future, and an important consideration to adequately assess the types and magnitude of risks associated with proposed large-scale mining in the region.