Coordination chemistry of a calix[4]arene-based NHC ligand : dinuclear complexes and comparison to IiPr2Me2

The preparation and coordination chemistry of 5,17-bis(3-methyl-1-imidazol-2-ylidene)-25,26,27,28-tetrapropoxycalix[4]arene (1) is described. Starting from the bis(imidazolium) pro-ligand 1·2HI, the free carbene 1 was readily generated in solution through deprotonation using K[OtBu] and its reactivity with rhodium(I) dimers [Rh(COD)Cl]2 (COD = 1,5-cyclooctadiene) and [Rh(CO)2Cl]2 investigated. Dinuclear complexes were isolated in both cases, where the calix[4]arene-based NHC ligand adopts a bridging μ2-coordination mode, and in one case characterised in the solid-state by X-ray diffraction. Using instead an isolated and well-defined (mononuclear) silver transfer agent, generated by reaction of 1·2HI with Ag2O in the presence of a halide extractor, reactions with [Rh(COD)Cl]2 and [Rh(CO)2Cl]2 produced cationic dinuclear complexes bearing μ2-1 and μ2-Cl bridging ligands. The structural formulation of the novel dinuclear adducts of 1 was aided through spectroscopic congruence with model complexes, containing monodentate 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene (IiPr2Me2)

Potassium binding adjacent to cationic transition metal fragments: unusual heterobimetallic adducts of a calix[4]arene-based thione ligand

The synthesis of cationic rhodium and iridium complexes of a bis(imidazol-2-thione) functionalised calix[4]arene ligand and their surprising capacity for potassium binding is described. In both cases uptake of the alkali metal into the calix[4]arene cavity occurs despite adverse electrostatic interactions associated with close proximity to the transition metal fragment (Rh+∙∙∙K+ = 3.715(1) Å, Ir+∙∙∙K+ = 3.690(1) Å). The formation and constituent bonding of these unusual heterobimetallic adducts has been interrogated through extensive solution and solid-state characterisation, examination of the host-guest chemistry of the ligand and its upper-rim unfunctionalised calix[4]arene analogue, and computationally using DFT-based energy decomposition analysis (EDA)

Impact of glacial activity on the weathering of Hf isotopes – Observations from Southwest Greenland

Data for the modern oceans and their authigenic precipitates suggest incongruent release of hafnium (Hf) isotopes by chemical weathering of the continents. The fact that weathering during recent glacial periods is associated with more congruent release of Hf isotopes has led to the hypothesis that the incongruency may be controlled by retention of unradiogenic Hf by zircons, and that glacial grinding enhances release of Hf from zircons. Here we study the relationship between glacial weathering processes and Hf isotope compositions released to rivers fed by land-terminating glaciers of the Greenland Ice Sheet, as well as neighbouring non-glacial streams. The weathered source rocks in the studied area mostly consist of gneisses, but also include amphibolites of the same age (1.9 Ga). Hafnium and neodymium isotope compositions in catchment sediments and in the riverine suspended load are consistent with a predominantly gneissic source containing variable trace amounts of zircon and different abundances of hornblende, garnet and titanite. Glacially sourced rivers and non-glacial streams fed by precipitation and lakes show very unradiogenic Nd isotopic compositions, in a narrow range (ɛNd = −42.8 to −37.9). Hafnium isotopes, on the other hand, are much more radiogenic and variable, with ɛHf between −18.3 and −0.9 in glacial rivers, and even more radiogenic values of +15.8 to +46.3 in non-glacial streams. Although relatively unradiogenic Hf is released by glacial weathering, glacial rivers actually fall close to the seawater array in Hf-Nd isotope space and are not distinctly unradiogenic. Based on their abundance in rocks and sediments and their isotope compositions, different minerals contribute to the radiogenic Hf in solution with a decreasing relevance from garnet to titanite, hornblende and apatite. Neodymium isotopes preclude a much stronger representation of titanite, hornblende and apatite in solution, such as might result from differences in dissolution rates, than estimated from mineral abundance. The strong contrast in Hf isotope compositions between glacial rivers and non-glacial streams results mostly from different contributions from garnet and zircon, where zircon weathering is more efficient in the subglacial environment. A key difference between glacial and non-glacial waters is the water-rock interaction time. While glacial rivers receive continuous contributions from long residence time waters of distributed subglacial drainage systems, non-glacial streams are characterized by fast superficial drainage above the permafrost horizon. Therefore, the increased congruency in Hf isotope weathering in glacial systems could simply reflect the hydrological conditions at the base of the ice-sheet and glaciers, with zircon weathering contributions increasing with water-rock interaction time

Immunization strategies producing a humoral IgG immune response against devil facial tumor disease in the majority of Tasmanian devils destined for wild release

Devil facial tumor disease (DFTD) is renowned for its successful evasion of the host immune system. Down regulation of the major histocompatabilty complex class I molecule (MHC-I) on the DFTD cells is a primary mechanism of immune escape. Immunization trials on captive Tasmanian devils have previously demonstrated that an immune response against DFTD can be induced, and that immune-mediated tumor regression can occur. However, these trials were limited by their small sample sizes. Here, we describe the results of two DFTD immunization trials on cohorts of devils prior to their wild release as part of the Tasmanian Government's Wild Devil Recovery project. 95% of the devils developed anti-DFTD antibody responses. Given the relatively large sample sizes of the trials (N = 19 and N = 33), these responses are likely to reflect those of the general devil population. DFTD cells manipulated to express MHC-I were used as the antigenic basis of the immunizations in both trials. Although the adjuvant composition and number of immunizations differed between trials, similar anti-DFTD antibody levels were obtained. The first trial comprised DFTD cells and the adjuvant combination of ISCOMATRIX™, polyIC, and CpG with up to four immunizations given at monthly intervals. This compared to the second trial whereby two immunizations comprising DFTD cells and the adjuvant combination ISCOMATRIX™, polyICLC (Hiltonol®) and imiquimod were given a month apart, providing a shorter and, therefore, more practical protocol. Both trials incorporated a booster immunization given up to 5 months after the primary course. A key finding was that devils in the second trial responded more quickly and maintained their antibody levels for longer compared to devils in the first trial. The different adjuvant combination incorporating the RNAase resistant polyICLC and imiquimod used in the second trial is likely to be responsible. The seroconversion in the majority of devils in these anti-DFTD immunization trials was remarkable, especially as DFTD is hallmarked by its immune evasion mechanisms. Microsatellite analyzes of MHC revealed that some MHC-I microsatellites correlated to stronger immune responses. These trials signify the first step in the long-term objective of releasing devils with immunity to DFTD into the wild.Ruth Pye, Amanda Patchett, Elspeth McLennan, Russell Thomson, Scott Carver ... A. Bruce Lyons ... et al

Sr-Nd-Hf Isotopic Analysis of <10 mg Dust Samples: Implications for Ice Core Dust Source Fingerprinting

Combined Sr-Nd-Hf isotopic data of two reference materials (AGV-1/BCR2) and 50, 10, and 5 mg aliquots of carbonate-free fine grain (<10 lm) separates of three loess samples (Central Europe/NUS, China/BEI, USA/JUD) are presented. Good agreement between measured and reference Sr-Nd-Hf isotopic compositions (ICs) demonstrate that robust isotopic ratios can be obtained from 5 to 10 mg size rock samples using the ion exchange/mass spectrometry techniques applied. While 87Sr/86Sr ratios of dust aluminosilicate fractions are affected by even small changes in pretreatments, Nd isotopic ratios are found to be insensitive to acid leaching, grain-size or weathering effects. However, the Nd isotopic tracer is sometimes inconclusive in dust source fingerprinting (BEI and NUS both close to ENd(0) –10). Hafnium isotopic values (<10 lm fractions) are homogenous for NUS, while highly variable for BEI. This heterogeneity and vertical arrays of Hf isotopic data suggest zircon depletion effects toward the clay fractions (<2 lm). Monte Carlo simulations demonstrate that the Hf IC of the dust <10 lm fraction is influenced by both the abundance of zircons present and maturity of crustal rocks supplying this heavy mineral, while the <2 lm fraction is almost unaffected. Thus, EHf(0) variations in the clay fraction are largely controlled by the Hf IC of clays/ heavy minerals having high Lu/Hf and radiogenic 176Hf/177Hf IC. Future work should be focused on Hf IC of both the <10 and <2 lm fractions of dust from potential source areas to gain more insight into the origin of last glacial dust in Greenland ice cores

Coordination chemistry of N-heterocyclic carbene and thione functionalised calix[4]arene ligands.

This thesis is a summary of the work carried out exploring the properties and applications of calix[4]arene ligands. Particular attention is given to the flexibility and encapsulation capabilities of these species. Initially synthetic methodology for the incorporation of bisimidazolinium and imidaolium groups was targeted. The synthesis of imidazolinium functionalised species proved problematic, however pro-ligand 2a-2HI was readily prepared via a six-step synthetic procedure. The coordination chemistry of 2a-2HI with [Rh(COD)Cl]2 and [Rh(CO)2Cl]2, via generation of the free carbene (2a) or transmetallation from an isolated silver complex (6a) was explored. Both routes resulted in the formation of bimetallic species. The isolation of these complexes highlights the flexibility of the calix[4]arene scaffold. The role of the calix[4]arene was probed though comparison to complexes of the monodentate IiPr2Me2 ligand. Based on these results, the imidazole-2-thione (NHCS) ligand 3 was derived from 2a and elemental sulfur. Monodentate rhodium and iridium complexes of 3 were readily prepared and found to bind potassium cations within the calix[4]arene cavity. This unusual host-guest chemistry was probed by 1H NMR spectroscopy and in the solid state through comparison to other calix[4]arene hosts

A vision for incorporating human mobility in the study of human-wildlife interactions

As human activities increasingly shape land- and seascapes, understanding human–wildlife interactions is imperative for preserving biodiversity. Habitats are impacted not only by static modifications, such as roads, buildings and other infrastructure, but also by the dynamic movement of people and their vehicles occurring over shorter time scales. Although there is increasing realization that both components of human activity substantially affect wildlife, capturing more dynamic processes in ecological studies has proved challenging. Here we propose a conceptual framework for developing a ‘dynamic human footprint’ that explicitly incorporates human mobility, providing a key link between anthropogenic stressors and ecological impacts across spatiotemporal scales. Specifically, the dynamic human footprint integrates a range of metrics to fully acknowledge the time-varying nature of human activities and to enable scale-appropriate assessments of their impacts on wildlife behaviour, demography and distributions. We review existing terrestrial and marine human-mobility data products and provide a roadmap for how these could be integrated and extended to enable more comprehensive analyses of human impacts on biodiversity in the Anthropocene