Application of technetium and rhenium carbonyl chemistry to nuclear medicine. Preparation of [NEt4]2[TcCl3(CO)3] from [NBu4][TcO4] and structure of [NEt4][Tc2(μ-Cl)3(CO)6]; structures of the model complexes [NEt4][Re2(μ-OEt)2(μ-OAc)(CO)6] and [ReBr({-CH2S(CH2)2Cl}2)(CO)3]

A detailed investigation of the one-pot synthesis of [NEt4]2[MX3(CO)3] [M=Tc (1a) or Re (1b); X= Cl−, Br−] is presented. The intermediates [NEt4][Tc2-(μ-Cl)3(CO)6] (2a), [NBu4][Tc3(μ3-H)(μ-H)3(CO)9] (3) and [Tc3(μ-H)3(CO)12] (4) have been isolated and characterized. The X-ray structure of (2a) is described. Complex (2a) crystallizes in the monoclinic space group P21/c with a=19.491(6), b=18.323(2) and c=17.497(9)AÅ, and β=97.59(2)°. Quantitative conversion of (2a), (3) and (4) into the aqua-ion [M(OH2)3(CO)3]+ [M=Tc (5a) or Re (5b)] is described. To evaluate an optimal and simple chelating group for the "fac-M(CO)3” moiety, the reaction with the bidentate thioether ligand Cl(CH2)2S(CH2)2S(CH2)2Cl (qyp) has been investigated and the structure of the neutral complex [ReBr(qyp)(CO)3] (6) is described. Complex (6) crystallizes in the monoclinic space group P21/c with a=15.935(6), b=2.788(4) and c= 7.955(10)AÅ, and β=98.57(1)°. To extend the knowledge about substitution chemistry of organometallic complexes in aqueous solution, the acetato ligand [OOCCH3]− has been reacted with (1b), resulting in the formation of the dinuclear, acetato-bridged complex [NEt4][Re2(μ-OH)2(μ-OAc)(CO)6], which converted into [Re2(μ-OEt)2(μ-OAc)(CO)6]− (7) after recrystallization from EtOH. The X-ray structure of (7) has been determined. Complex (7) crystallizes in the monoclinic space group P21/c with a=16.288(3), b=12.4272(10) and c=13.620(3)AÅ, and β=76.63(1)°. For a future application of the small "fac-M(CO)3” moiety, it seems thus advantageous to combine these two ligand groups in one simple chelating functio

Quantifying full phenological event distributions reveals simultaneous advances, temporal stability and delays in spring and autumn migration timing in long-distance migratory birds

Acknowledgements We thank all Fair Isle Bird Observatory staff and volunteers for help with data collection and acknowledge the foresight of George Waterston and Ken Williamson in instigating the observatory and census methodology. We thank all current and previous directors of Fair Isle Bird Observatory Trust for their contributions, particularly Dave Okill and Mike Wood for their stalwart support for the long-term data collection and for the current analyses. Dawn Balmer and Ian Newton provided helpful guidance on manuscript drafts. We thank Ally Phillimore and two anonymous referees for helpful comments. This study would have been impossible without the Fair Isle community's invaluable support and patience over many decades, which is very gratefully acknowledged. WTSM and JMR designed and undertook analyses, wrote the paper and contributed to data collection and compilation, MB contributed to analysis and editing, all other authors oversaw and undertook data collection and compilation and contributed to editing.Peer reviewedPostprin

Possible chiral phase transition in two-dimensional solid 3^3He

We study a spin system with two- and four-spin exchange interactions on the triangular lattice, which is a possible model for the nuclear magnetism of solid $^3$He layers. It is found that a novel spin structure with scalar chiral order appears if the four-spin interaction is dominant. Ground-state properties are studied using the spin-wave approximation. A phase transition concerning the scalar chirality occurs at a finite temperature, even though the dimensionality of the system is two and the interaction has isotropic spin symmetry. Critical properties of this transition are studied with Monte Carlo simulations in the classical limit.Comment: 4 pages, Revtex, 4 figures, to appear in Phys.Rev.Let

Spectral and morphological analysis of the remnant of Supernova 1987A with ALMA & ATCA

We present a comprehensive spectral and morphological analysis of the remnant of Supernova (SN) 1987A with the Australia Telescope Compact Array (ATCA) and the Atacama Large Millimeter/submillimeter Array (ALMA). The non-thermal and thermal components of the radio emission are investigated in images from 94 to 672 GHz ($\lambda$ 3.2 mm to 450 $\mu$m), with the assistance of a high-resolution 44 GHz synchrotron template from the ATCA, and a dust template from ALMA observations at 672 GHz. An analysis of the emission distribution over the equatorial ring in images from 44 to 345 GHz highlights a gradual decrease of the east-to-west asymmetry ratio with frequency. We attribute this to the shorter synchrotron lifetime at high frequencies. Across the transition from radio to far infrared, both the synchrotron/dust-subtracted images and the spectral energy distribution (SED) suggest additional emission beside the main synchrotron component ($S_{\nu}\propto\nu^{-0.73}$) and the thermal component originating from dust grains at $T\sim22$ K. This excess could be due to free-free flux or emission from grains of colder dust. However, a second flat-spectrum synchrotron component appears to better fit the SED, implying that the emission could be attributed to a pulsar wind nebula (PWN). The residual emission is mainly localised west of the SN site, as the spectral analysis yields $-0.4\lesssim\alpha\lesssim-0.1$ across the western regions, with $\alpha\sim0$ around the central region. If there is a PWN in the remnant interior, these data suggest that the pulsar may be offset westward from the SN position.Comment: ApJ accepted. 21 pages, emulateapj. References update

Mechanisms of cerebellar tonsil herniation in patients with Chiari malformations as guide to clinical management

Background The pathogenesis of Chiari malformations is incompletely understood. We tested the hypothesis that different etiologies have different mechanisms of cerebellar tonsil herniation (CTH), as revealed by posterior cranial fossa (PCF) morphology. Methods In 741 patients with Chiari malformation type I (CM-I) and 11 patients with Chiari malformation type II (CM-II), the size of the occipital enchondrium and volume of the PCF (PCFV) were measured on reconstructed 2D-CT and MR images of the skull. Measurements were compared with those in 80 age- and sex-matched healthy control individuals, and the results were correlated with clinical findings. Results Significant reductions of PCF size and volume were present in 388 patients with classical CM-I, 11 patients with CM-II, and five patients with CM-I and craniosynostosis. Occipital bone size and PCFV were normal in 225 patients with CM-I and occipitoatlantoaxial joint instability, 55 patients with CM-I and tethered cord syndrome (TCS), 30 patients with CM-I and intracranial mass lesions, and 28 patients with CM-I and lumboperitoneal shunts. Ten patients had miscellaneous etiologies. The size and area of the foramen magnum were significantly smaller in patients with classical CM-I and CM-I occurring with craniosynostosis and significantly larger in patients with CM-II and CM-I occurring with TCS. Conclusions Important clues concerning the pathogenesis of CTH were provided by morphometric measurements of the PCF. When these assessments were correlated with etiological factors, the following causal mechanisms were suggested: (1) cranial constriction; (2) cranial settling; (3) spinal cord tethering; (4) intracranial hypertension; and (5) intraspinal hypotension

Effects of acute fatigue on the volitional and magnetically-evoked electromechanical delay of the knee flexors in males and females

Neuromuscular performance capabilities, including those measured by evoked responses, may be adversely affected by fatigue; however, the capability of the neuromuscular system to initiate muscle force rapidly under these circumstances is yet to be established. Sex-differences in the acute responses of neuromuscular performance to exercise stress may be linked to evidence that females are much more vulnerable to ACL injury than males. Optimal functioning of the knee flexors is paramount to the dynamic stabilisation of the knee joint, therefore the aim of this investigation was to examine the effects of acute maximal intensity fatiguing exercise on the voluntary and magnetically-evoked electromechanical delay in the knee flexors of males and females. Knee flexor volitional and magnetically-evoked neuromuscular performance was assessed in seven male and nine females prior to and immediately after: (i) an intervention condition comprising a fatigue trial of 30-seconds maximal static exercise of the knee flexors, (ii) a control condition consisting of no exercise. The results showed that the fatigue intervention was associated with a substantive reduction in volitional peak force (PFV) that was greater in males compared to females (15.0%, 10.2%, respectively, p < 0.01) and impairment to volitional electromechanical delay (EMDV) in females exclusively (19.3%, p < 0.05). Similar improvements in magnetically-evoked electromechanical delay in males and females following fatigue (21%, p < 0.001), however, may suggest a vital facilitatory mechanism to overcome the effects of impaired voluntary capabilities, and a faster neuromuscular response that can be deployed during critical times to protect the joint system

Potential effects of oilseed rape expressing oryzacystatin-1 (OC-1) and of purified insecticidal proteins on larvae of the solitary bee Osmia bicornis

Despite their importance as pollinators in crops and wild plants, solitary bees have not previously been included in non-target testing of insect-resistant transgenic crop plants. Larvae of many solitary bees feed almost exclusively on pollen and thus could be highly exposed to transgene products expressed in the pollen. The potential effects of pollen from oilseed rape expressing the cysteine protease inhibitor oryzacystatin-1 (OC-1) were investigated on larvae of the solitary bee Osmia bicornis (= O. rufa). Furthermore, recombinant OC-1 (rOC-1), the Bt toxin Cry1Ab and the snowdrop lectin Galanthus nivalis agglutinin (GNA) were evaluated for effects on the life history parameters of this important pollinator. Pollen provisions from transgenic OC-1 oilseed rape did not affect overall development. Similarly, high doses of rOC-1 and Cry1Ab as well as a low dose of GNA failed to cause any significant effects. However, a high dose of GNA (0.1%) in the larval diet resulted in significantly increased development time and reduced efficiency in conversion of pollen food into larval body weight. Our results suggest that OC-1 and Cry1Ab expressing transgenic crops would pose a negligible risk for O. bicornis larvae, whereas GNA expressing plants could cause detrimental effects, but only if bees were exposed to high levels of the protein. The described bioassay with bee brood is not only suitable for early tier non-target tests of transgenic plants, but also has broader applicability to other crop protection products

Garden and landscape-scale correlates of moths of differing conservation status: significant effects of urbanization and habitat diversity

Moths are abundant and ubiquitous in vegetated terrestrial environments and are pollinators, important herbivores of wild plants, and food for birds, bats and rodents. In recent years, many once abundant and widespread species have shown sharp declines that have been cited by some as indicative of a widespread insect biodiversity crisis. Likely causes of these declines include agricultural intensification, light pollution, climate change, and urbanization; however, the real underlying cause(s) is still open to conjecture. We used data collected from the citizen science Garden Moth Scheme (GMS) to explore the spatial association between the abundance of 195 widespread British species of moth, and garden habitat and landscape features, to see if spatial habitat and landscape associations varied for species of differing conservation status. We found that associations with habitat and landscape composition were species-specific, but that there were consistent trends in species richness and total moth abundance. Gardens with more diverse and extensive microhabitats were associated with higher species richness and moth abundance; gardens near to the coast were associated with higher richness and moth abundance; and gardens in more urbanized locations were associated with lower species richness and moth abundance. The same trends were also found for species classified as increasing, declining and vulnerable under IUCN (World Conservation Union) criteria