Metalloporphyrin anion sensors: the effect of the metal centre on the anion binding properties of amide-functionalised and tetraphenyl metalloporphyrins

This article describes the synthesis and anion binding properties of a series of ‘picket fence’ metalloporphyrin complexes, within which the metal centre is systematically varied. The porphyrin structure contains four amide bonds and is the same for each metal. The anion binding properties of these receptors are further contrasted with those of their tetraphenylporphyrin congeners to elucidate both the effect of the metal centre and the influence of the amide groups on the anion recognition process. Anion binding was demonstrated using UV/visible and 1H NMR spectroscopies, electrochemistry and luminescence. The metal centre was found to be highly influential in the strength and selectivity of binding; for example, the cadmium and mercury complexes exhibited far greater affinities for anions than the zinc complexes in competitive solvents such as DMSO. The amide functionalities were found to enhance the anion binding process.

Survival, reproduction and population growth of the bee pollinator, Osmia rufa (Hymenoptera: Megachilidae), along gradients of heavy metal pollution

1. Bees are one of the most important groups of pollinators in the temperate zone. Although heavy metal pollution is recognised to be a problem affecting large parts of the European Union, we currently lack insights into the effects of heavy metals on wild bee survival and reproduction. 2. We investigated the impact of heavy metal pollution on the wild bee Osmia rufa (Hymenoptera: Megachilidae) by comparing their survival, reproduction and population dynamics along two independent gradients of heavy metal pollution, one in Poland and the other in the United Kingdom. We used trap nests to evaluate the response of fitness and survival parameters of O. rufa. To quantify the levels of pollution, we directly measured the heavy metal concentration in provisions collected by O. rufa. 3. We found that with increasing heavy metal concentration, there was a steady decrease in number of brood cells constructed by females and an increase in the proportion of dead offspring. In the most polluted site, there were typically 3–4 cells per female with 50–60% dead offspring, whereas in unpolluted sites there were 8 to 10 cells per female and only 10–30% dead offspring. Moreover, the bee population growth rate (R0) decreased along the heavy metal pollution gradients. In unpolluted sites, R0 was above 1, whereas in contaminated sites, the values tended to be below 1. 4. Our findings reveal a negative relationship between heavy metal pollution and several fitness parameters of the wild bee O. rufa, and highlight a mechanism whereby the detrimental effects of heavy metal pollution may severely impact wild bee communities.

REVIEW: Fireballs, Flares and Flickering

We review our understanding of the prototype ``Propeller'' system AE Aqr and we examine its flaring behaviour in detail. The flares are thought to arise from collisions between high density regions in the material expelled from the system after interaction with the rapidly rotating magnetosphere of the white dwarf. We show calculations of the time-dependent emergent optical spectra from the resulting hot, expanding ball of gas and derive values for the mass, lengthscale and temperature of the material involved. We see that the fits suggest that the secondary star in this system has reduced metal abundances and that, counter-intuitively, the evolution of the fireballs is best modelled as isothermal.

RuII(α-diimine) or RuIII(α-diimine·–)? Structural, spectroscopic, and theoretical evidence for the stabilization of a prominent metal-to-Ligand charge- transfer excited-state configuration in the ground state

The new compounds [Ru(R-DAB)(acac)2] (R-DAB = 1,4-diorganyl- 1,4-diazabuta-1,3-diene; R = tert-butyl, 4-methoxyphenyl, 2,6-dimethylphenyl; acac– = 2,4-pentanedionate) exhibit intrachelate ring bond lengths 1.297metal-to-ligand chargetransfer (MLCT) excited states of conventional (α-diimine)- ruthenium(II) complexes and in view of other (α-diimine)- metal complexes with ambiguous oxidation-state assignments.