Synthesis, stereocontrol and structural studies of highly luminescent chiral tris-amidepyridyl-triazacyclononane lanthanide complexes

The configuration of the remote amide chiral moiety determines the helicity of the metal complex in Ln(III) complexes of nonadentate N6O3 ligands based on triazacyclononane. Solution NMR studies revealed the presence of a dominant isomer whose proportion varies from 9 : 1 to 4 : 1 from Ce to Yb and X-ray crystallographic studies at 120 K of the Yb and two enantiomeric Eu complexes confirmed the configuration as S-Δ-λ in the major isomer. Global minimisation methods allowed magnetic susceptibility and electronic relaxation times of the lanthanide ions to be estimated by analysis of variable field longitudinal relaxation rate (R1) data sets. A set of four europium complexes, containing different para-substituted pyridinyl-aryl groups, exist as one major isomer (15 : 1), and absorb light strongly via an ICT transition in the range 320 to 355 nm (ε = 55 to 65 000 M−1 cm−1). The two examples absorbing light at 332 nm, possess overall emission quantum yields of 35 and 37% in aerated water, making these systems as bright as any Eu complex in solution

Dark Matter in the Coming Decade: Complementary Paths to Discovery and Beyond

In this report we summarize the many dark matter searches currently being pursued through four complementary approaches: direct detection, indirect detection, collider experiments, and astrophysical probes. The essential features of broad classes of experiments are described, each with their own strengths and weaknesses. The complementarity of the different dark matter searches is discussed qualitatively and illustrated quantitatively in two simple theoretical frameworks. Our primary conclusion is that the diversity of possible dark matter candidates requires a balanced program drawing from all four approaches.Comment: Report prepared for the Community Summer Study (Snowmass) 2013, on behalf of Cosmic Frontier Working Groups 1-4 (CF1: WIMP Dark Matter Direct Detection, CF2: WIMP Dark Matter Indirect Detection, CF3: Non-WIMP Dark Matter, and CF4: Dark Matter Complementarity); published versio

Effects of Chronic Sleep Restriction during Early Adolescence on the Adult Pattern of Connectivity of Mouse Secondary Motor Cortex

Cortical circuits mature in stages, from early synaptogenesis and synaptic pruning to late synaptic refinement, resulting in the adult anatomical connection matrix. Because the mature matrix is largely fixed, genetic or environmental factors interfering with its establishment can have irreversible effects. Sleep disruption is rarely considered among those factors, and previous studies have focused on very young animals and the acute effects of sleep deprivation on neuronal morphology and cortical plasticity. Adolescence is a sensitive time for brain remodeling, yet whether chronic sleep restriction (CSR) during adolescence has long-term effects on brain connectivity remains unclear. We used viral-mediated axonal labeling and serial two-photon tomography to measure brain-wide projections from secondary motor cortex (MOs), a high-order area with diffuse projections. For each MOs target, we calculated the projection fraction, a combined measure of passing fibers and axonal terminals normalized for the size of each target. We found no homogeneous differences in MOs projection fraction between mice subjected to 5 days of CSR during early adolescence (P25–P30, ≥50% decrease in daily sleep, n=14) and siblings that slept undisturbed (n=14). Machine learning algorithms, however, classified animals at significantly above chance levels, indicating that differences between the two groups exist, but are subtle and heterogeneous. Thus, sleep disruption in early adolescence may affect adult brain connectivity. However, because our method relies on a global measure of projection density and was not previously used to measure connectivity changes due to behavioral manipulations, definitive conclusions on the long-term structural effects of early CSR require additional experiments

High-energy Particle Acceleration and Production of Ultra-high-energy Cosmic Rays in the Giant Lobes of Centaurus A

‘The definitive version is available at www3.interscience.wiley.com '. Copyright Royal Astronomical Society. DOI: 10.1111/j.1365-2966.2008.14265.xThe nearby radio galaxy Centaurus A is poorly studied at high frequencies with conventional radio telescopes because of its very large angular size, but is one of a very few extragalactic objects to be detected and resolved by the Wilkinson Microwave Anisotropy Probe (WMAP).We have used the five-year WMAP data for Cen A to constrain the high-frequency radio spectra of the 10-degree giant lobes and to search for spectral changes as a function of position along the lobes. We show that the high-frequency radio spectra of the northern and southern giant lobes are significantly different: the spectrum of the southern lobe steepens monotonically (and is steeper further from the active nucleus) whereas the spectrum of the northern lobe remains consistent with a power law. The inferred differences in the northern and southern giant lobes may be the result of real differences in their high-energy particle acceleration histories, perhaps due to the influence of the northern middle lobe, an intermediate-scale feature which has no detectable southern counterpart. In light of these results, we discuss the prospects for Gamma-ray Large Area Space Telescope (GLAST) detections of inverse-Compton emission from the giant lobes and the lobes’ possible role in the production of the ultra-high energy cosmic rays (UHECR) detected by the Pierre Auger Observatory. We show that the possibility of a GLAST detection depends sensitively on the physical conditions in the giant lobes, with the northern lobe more likely to be detected, and that any emission observed by GLAST is likely to be restricted to the soft end of the GLAST energy band. On the other hand we argue that the estimated conditions in the giant lobes imply that UHECRs can be accelerated there, with a potentially detectable -ray signature at GeV-TeV energies.Peer reviewe

The Deepwater Horizon Oil Spill Coast Guard Cohort study

A cohort study among Coast Guard personnel involved in the Deepwater Horizon (DWH) oil spill response and non-responders was established to investigate potential acute and longterm health effects from oil spill response work exposures. Results showed positive associations between crude oil exposure and various acute physical symptoms among responders, as well as longer term health effects

Critical analysis of the limitations of Bleaney's theory of magnetic anisotropy in paramagnetic lanthanide coordination complexes

The origins of the breakdown of Bleaney's theory of magnetic anisotropy are described, based on an analysis of eleven different complexes of the second half of the 4f elements that form isostructural series. An examination of the chemical shift and relaxation rate behaviour of resonances located at least four bonds away from the paramagnetic centre was undertaken, and correlated to theoretical predictions. The key limitations relate to comparability of ligand field splitting with spin–orbit coupling, variation in the position of the principal magnetic axis between Ln complexes and the importance of multipolar terms in describing lanthanide ligand field interactions