In contrast to phosphine oxides and arsine oxides, which are common and exist as stable monomeric species featuring the corresponding pnictoryl functional group (Pn=O/Pn⁺-O^-; Pn = P, As), stibine oxides are generally polymeric, and the properties of the unperturbed stiboryl group (Sb=O/Sb⁺-O^-) remain unexplored. We now report the isolation of the monomeric stibine oxide, Dipp₃SbO (where Dipp = 2,6-diisopropylphenyl). Spectroscopic, crystallographic and computational studies provide insight into the nature of the Sb=O/Sb⁺-O^- bond. Moreover, isolation of Dipp₃SbO allows the chemistry of the stiboryl group to be explored. Here we show that Dipp₃SbO can act as a Brønsted base, a hydrogen-bond acceptor and a transition-metal ligand, in addition engaging in 1,2-addition, O-for-F₂ exchange and O-atom transfer. In all cases, the reactivity of Dipp₃SbO differed from that of the lighter congeners Dipp₃AsO and Dipp₃PO.

Pentaphenylantimony (SbPh₅) has been previously crystallized in either a square pyramidal or trigonal bipyramidal geometry. Investigation of the solution-state structure of SbPh₅ has been hampered by the extreme fluxionality of this compound, but previous vibrational spectroscopic studies concluded that it maintains a square pyramidal geometry in solution. This non-VSEPR-compliant geometry, which is also assumed by BiPh₅ in the solid state, stands in contrast to the trigonal bipyramidal geometries of PPh₅ and AsPh₅. A range of phenomena have been invoked to explain this discrepancy, most notably, the increased importance of relativistic effects as group 15 is descended. We present crystallographic, spectroscopic, and computational data revealing that SbPh₅ in fact assumes the VSEPR-compliant trigonal bipyramidal geometry in solution. In particular, Sb X-ray absorption spectroscopy (XAS) was used to obtain geometry-sensitive spectra that do not suffer from the slow spectroscopic time scale that has prevented NMR studies from elucidating the structure of this fluxional molecule. Sb K-edge and L_III-edge XAS spectra of crystalline solids featuring SbPh₅ in either a square pyramidal (nonsolvate) or trigonal bipyramidal (cyclohexane hemisolvate or THF hemisolvate) form were compared to spectra of SbPh₅ in solution. The solution-state spectra agree with those from solids containing trigonal bipyramidal SbPh₅. The most diagnostic spectroscopic feature was the distribution of intensity in the Sb L_III pre-edge features. These distributions were rationalized using time-dependent density functional theory calculations that take into account spin-orbit coupling. Our use of Sb XAS not only resolves a long-standing physical inorganic question but also demonstrates more widely the utility of XAS in establishing the structures of fluxional main-group compounds. This conclusion was further supported by solid- and solution-state Raman data. Finally, we note that the present high-resolution diffraction data allow τ for nonsolvated SbPh₅ to be revised to 0.216.

PBT2 (5,7-dichloro-2-[(dimethylamino)methyl]-8-hydroxyquinoline) is a small Cu(II)-binding drug that has been investigated in the treatment of neurodegenerative diseases, namely, Alzheimer's disease (AD). PBT2 is thought to be highly effective at crossing the blood-brain barrier and has been proposed to exert anti-Alzheimer's effects through the modulation of metal ion concentrations in the brain, specifically the sequestration of Cu(II) from amyloid plaques. However, despite promising initial results in animal models and in clinical trials where PBT2 was shown to improve cognitive function, larger-scale clinical trials did not find PBT2 to have a significant effect on the amyloid plaque burden compared with controls. We propose that the results of these clinical trials likely point to a more complex mechanism of action for PBT2 other than simple Cu(II) sequestration. To this end, herein we have investigated the solution chemistry of Cu(II) coordination by PBT2 primarily using X-ray absorption spectroscopy (XAS), high-energy-resolution fluorescence-detected XAS, and electron paramagnetic resonance. We propose that a novel bis-PBT2 Cu(II) complex with asymmetric coordination may coexist in solution with a symmetric four-coordinate Cu(II)-bis-PBT2 complex distorted from coplanarity. Additionally, PBT2 is a more flexible ligand than other 8HQs because it can act as both a bidentate and a tridentate ligand as well as coordinate Cu(II) in both 1:1 and 2:1 PBT2/Cu(II) complexes.

Research on urban insect pollinators is changing views on the biological value and ecological importance of cities. The abundance and diversity of native bee species in urban landscapes that are absent in nearby rural lands evidence the biological value and ecological importance of cities and have implications for biodiversity conservation. Lagging behind this revised image of the city are urban conservation programs that historically have invested in education and outreach rather than programs designed to achieve high-priority species conservation results. We synthesized research on urban bee species diversity and abundance to determine how urban conservation could be repositioned to better align with new views on the ecological importance of urban landscapes. Due to insect pollinators' relatively small functional requirements-habitat range, life cycle, and nesting behavior-relative to larger mammals, we argue that pollinators put high-priority and high-impact urban conservation within reach. In a rapidly urbanizing world, transforming how environmental managers view the city can improve citizen engagement and contribute to the development of more sustainable urbanization.

The co-authors of this paper hereby state their intention to work together to launch the Genomic Observatories Network (GOs Network) for which this document will serve as its Founding Charter. We define a Genomic Observatory as an ecosystem and/or site subject to long-term scientific research, including (but not limited to) the sustained study of genomic biodiversity from single-celled microbes to multicellular organisms.An international group of 64 scientists first published the call for a global network of Genomic Observatories in January 2012. The vision for such a network was expanded in a subsequent paper and developed over a series of meetings in Bremen (Germany), Shenzhen (China), Moorea (French Polynesia), Oxford (UK), Pacific Grove (California, USA), Washington (DC, USA), and London (UK). While this community-building process continues, here we express our mutual intent to establish the GOs Network formally, and to describe our shared vision for its future. The views expressed here are ours alone as individual scientists, and do not necessarily represent those of the institutions with which we are affiliated.