Synthesis and characterisation of Fe₆ and Fe₁₂ clusters using bicine

Reaction of bicine {BicH3, N,N-bis(2-hydroxyethyl)glycine} with an Fe(III) oxo-centered pivalate triangle in MeCN in the presence of Et<sub>2</sub>NH yields [Et<sub>2</sub>NH<sub>2</sub>]<sub>2</sub>[Fe<sub>6</sub>O<sub>2</sub>(OH)<sub>2</sub>(Bic)<sub>2</sub>(O<sub>2</sub>CCMe<sub>3</sub>)<sub>8</sub>], which possesses an S = 5 ground state. Changing the base to NaOMe produces [Fe<sub>12</sub>O<sub>4</sub>(Bic)<sub>4</sub>(HBic)<sub>4</sub>(O<sub>2</sub>CCMe<sub>3</sub>)<sub>8</sub>], which contains two Fe6 units bridged by the carboxylate arms from the bicine ligands. The complex displays strong antiferromagnetic coupling leading to an S = 0 ground state

A Proton Magnetic Resonance Study of the Association of Lysozyme with Monosaccharide Inhibitors

It has been shown that the acetamido methyl protons of N-acetyl-d-glucosamine undergo a chemical shift to higher fields in their proton magnetic resonance spectrum when the inhibitor is bound to lysozyme. The observed chemical shift in the presence of the enzyme is different for the agr- and ß-anomeric forms of 2-acetamido-2-deoxy-d-glucopyranose indicating either a difference in the affinity of the anomeric forms for lysozyme or different magnetic environments for the methyl protons in their enzyme-bound state. That the agr- and ß-anomeric forms of GlcAc bind to lysozyme in a competitive fashion was indicated by observing the proton magnetic resonance spectra in the presence of 2-acetamido-d3-2-deoxy-agr-d-glucopyranose. The methyl glycosides, methyl-agr-GlcAc and methyl-ß-GlcAc, were also shown to bind competitively with both anomers of GlcAc. Quantitative analysis of the chemical shift data observed for the association of GlcAc with lysozyme was complicated by the mutarotation of GlcAc between its agr- and ß-anomeric forms. However, in the case of the methyl glucosides, where the conformation of each anomer is frozen, it was possible to analyze the chemical shift data in a straightforward manner, and the dissociation constant as well as the chemical shift of the acetamido methyl protons of the enzyme-inhibitor complex was determined for both anomers. The results indicate that the two anomers of methyl-GlcAc bind to lysozyme with slightly different affinities but that the acetamido methyl groups of both anomers experience identical magnetic environments in the enzyme-inhibitor complex

Intention and motor representation in purposive action

Are there distinct roles for intention and motor representation in explaining the purposiveness of action? Standard accounts of action assign a role to intention but are silent on motor representation. The temptation is to suppose that nothing need be said here because motor representation is either only an enabling condition for purposive action or else merely a variety of intention. This paper provides reasons for resisting that temptation. Some motor representations, like intentions, coordinate actions in virtue of representing outcomes; but, unlike intentions, motor representations cannot feature as premises or conclusions in practical reasoning. This implies that motor representation has a distinctive role in explaining the purposiveness of action. It also gives rise to a problem: were the roles of intention and motor representation entirely independent, this would impair effective action. It is therefore necessary to explain how intentions interlock with motor representations. The solution, we argue, is to recognise that the contents of intentions can be partially determined by the contents of motor representations. Understanding this content-determining relation enables better understanding how intentions relate to actions

Tunable dipolar magnetism in high-spin molecular clusters

We report on the Fe17 high-spin molecular cluster and show that this system is an exemplification of nanostructured dipolar magnetism. Each Fe17 molecule, with spin S=35/2 and axial anisotropy as small as D=-0.02K, is the magnetic unit that can be chemically arranged in different packing crystals whilst preserving both spin ground-state and anisotropy. For every configuration, molecular spins are correlated only by dipolar interactions. The ensuing interplay between dipolar energy and anisotropy gives rise to macroscopic behaviors ranging from superparamagnetism to long-range magnetic order at temperatures below 1K.Comment: Replaced with version accepted for publication in Physical Review Letter

Groundwater seepage landscapes from distant and local sources in experiments and on Mars

© 2014 Author(s). Valleys with theater-shaped heads can form due to the seepage of groundwater and as a result of knickpoint (waterfall) erosion generated by overland flow. This ambiguity in the mechanism of formation hampers the interpretation of such valleys on Mars, particularly since there is limited knowledge of material properties. Moreover, the hydrological implications of a groundwater or surface water origin are important for our understanding of the evolution of surface features on Mars, and a quantification of valley morphologies at the landscape scale may provide diagnostic insights on the formative hydrological conditions. However, flow patterns and the resulting landscapes produced by different sources of groundwater are poorly understood. We aim to improve the understanding of the formation of entire valley landscapes through seepage processes from different groundwater sources that will provide a framework of landscape metrics for the interpretation of such systems. We study groundwater seepage from a distant source of groundwater and from infiltration of local precipitation in a series of sandbox experiments and combine our results with previous experiments and observations of the Martian surface. Key results are that groundwater flow piracy acts on valleys fed by a distant groundwater source and results in a sparsely dissected landscape of many small and a few large valleys. In contrast, valleys fed by a local groundwater source, i.e., nearby infiltration, result in a densely dissected landscape. In addition, valleys fed by a distant groundwater source grow towards that source, while valleys with a local source grow in a broad range of directions and have a strong tendency to bifurcate, particularly on flatter surfaces. We consider these results with respect to two Martian cases: Louros Valles shows properties of seepage by a local source of groundwater and Nirgal Vallis shows evidence of a distant source, which we interpret as groundwater flow from Tharsis

The H.E.S.S. II GRB Program

Gamma-ray bursts (GRBs) are some of the most energetic and exotic events in the Universe, however their behaviour at the highest energies (>10 GeV) is largely unknown. Although the Fermi-LAT space telescope has detected several GRBs in this energy range, it is limited by the relatively small collection area of the instrument. The H.E.S.S. experiment has now entered its second phase by adding a fifth telescope of 600 m$^{2}$ mirror area to the centre of the array. This new telescope increases the energy range of the array, allowing it to probe the sub-100 GeV range while maintaining the large collection area of ground based gamma-ray observatories, essential to probing short-term variability at these energies. We will present a description of the GRB observation scheme used by the H.E.S.S. experiment, summarising the behaviour and performance of the rapid GRB repointing system, the conditions under which potential GRB repointings are made and the data analysis scheme used for these observations.Comment: In Proceedings of the 34th International Cosmic Ray Conference (ICRC2015), The Hague, The Netherland

The evolutionary state of short-period magnetic white dwarf binaries

We present phase-resolved spectroscopy of two new short-period low accretion rate magnetic binaries, SDSS J125044.42+154957.3 (Porb= 86 min) and SDSS J151415.65+074446.5 (Porb= 89 min). Both systems were previously identified as magnetic white dwarfs from the Zeeman splitting of the Balmer absorption lines in their optical spectra. Their spectral energy distributions exhibit a large near-infrared excess, which we interpret as a combination of cyclotron emission and possibly a late-type companion star. No absorption features from the companion are seen in our optical spectra. We derive the orbital periods from a narrow, variable Hα emission line which we show to originate on the companion star. The high radial velocity amplitude measured in both systems suggests a high orbital inclination, but we find no evidence for eclipses in our data. The two new systems resemble the polar EF Eri in its prolonged low state and also SDSS J121209.31+013627.7, a known magnetic white dwarf plus possible brown dwarf binary, which was also recovered by our method