Fragmentation pathways of [Re₂(μ-OR)₃(CO)₆]– (R = H, Me) and ligand exchange reactions with oxygen donor ligands, investigated by electrospray mass spectrometry

The rhenium hydroxy and methoxy carbonyl complexes [Re₂(μOR)₃(CO)₆]⁻ (R = H or Me) have been studied by negative-ion electrospray mass spectrometry (ESMS). The complexes undergo facile exchange reactions with protic compounds, including alcohols and phenols. With dimethyl malonate, ester hydrolysis occurs giving carboxylate-containing complexes, and with H₂O₂ or ButOOH, oxidation to ReO₄⁻occurs. The feasibility and extent of these reactions can conveniently, rapidly, and unambiguously be determined by electrospray mass spectrometry, and is dependent on the acidity and steric bulk of the protic compound. The results also suggest that the complexes can be used as versatile starting materials for the synthesis of a wide range of analogous [Re₂(μ-OR)₃(CO)₆]⁻ complexes by simple reaction with an excess of the appropriate alcohol. By varying the applied cone voltage the fragmentation pathways have been investigated; the hydroxy complex undergoes dehydration followed by CO loss, whereas for the methoxy complex -hydride elimination (and CO loss) is observed, with confirmation provided by deuterium labelling studies. Under ESMS conditions, the neutral complexes [Re₂(μ-OR)₂(μ-dppf )(CO)₆] [R = H or Me; dppf = 1,1 -bis(diphenylphosphino)ferrocene] undergo substantial solvolysis and hydrolysis to give mainly mononuclear species; simple parent ions (e.g. [M + H]⁺) are not formed in appreciable abundance, probably due to the lack of an efficient ionisation pathway

Stress-induced nuclear accumulation is dispensable for Hog1-dependent gene expression and virulence in a fungal pathogen

The authors thank E. Veal for intellectual input. This work was funded by the UK Biotechnology and Biological Research Council [J.Q. BB/K016393/1; A.J.P.B. BB/K017365/1], the National Centre for the Replacement, Refinement and Reduction of Animals in Research (NC3Rs) [D.M.M. NC/N002482/1] and the Wellcome Trust Strategic Award in Medical Mycology and Fungal Immunology [097377]). D.M.M. and A.J.P.B. are also supported by the MRC Centre for Medical Mycology at the University of Aberdeen (MR/N006364/1).Peer reviewedPublisher PD

Spin Hall Effect in Doped Semiconductor Structures

In this Letter we present a microscopic theory of the extrinsic spin Hall effect based on the diagrammatic perturbation theory. Side-jump (SJ) and skew-scattering (SS) contributions are explicitly taken into account to calculate the spin Hall conductivity, and we show their effects scale as $\sigma_{xy}^{SJ}/\sigma_{xy}^{SS} \sim (\hbar/\tau)/\epsilon_F$, with $\tau$ being the transport relaxation time. Motivated by recent experimental work we apply our theory to n- and p-doped 3D and 2D GaAs structures, obtaining $\sigma_s/\sigma_c \sim 10^{-3}-10^{-4}$ where $\sigma_{s(c)}$ is the spin Hall (charge) conductivity, which is in reasonable agreement with the recent experimental results of Kato \textit{et al}. [Science \textbf{306}, 1910 (2004)] in n-doped 3D GaAs system.Comment: 5 pages, 2 figure

Detoxification in rehabilitation in England: effective continuity of care or unhappy bedfellows?

There is evidence that residential detoxification alone does not provide satisfactory treatment outcomes and that outcomes are significantly enhanced when clients completing residential detoxification attend rehabilitation services (Gossop, Marsden, Stewart, & Rolfe, 1999; Ghodse, Reynolds, Baldacchino, et al., 2002). One way of increasing the likelihood of this continuity of treatment is by providing detoxification and rehabilitation within the same treatment facility to prevent drop-out, while the client awaits a rehabilitation bed or in the transition process. However, there is little research evidence available on the facilities that offer both medical detoxification and residential rehabilitation. The current study compares self-reported treatment provision in 87 residential rehabilitation services in England, 34 of whom (39.1%) reported that they offered detoxification services within their treatment programmes. Although there were no differences in self-reported treatment philosophies, residential rehabilitation services that offered detoxification were typically of shorter duration overall, had significantly more beds and reported offering more group work than residential rehabilitation services that did not offer detoxification. Outcomes were also different, with twice as many clients discharged on disciplinary grounds from residential rehabilitation services without detoxification facilities. The paper questions the UK classification of residential drug treatment services as either detoxification or rehabilitation and suggests the need for greater research focus on the aims, processes and outcomes of this group of treatment providers

Measurement of the SOC State Specific Heat in ^4He

When a heat flux Q is applied downward through a sample of liquid 4He near the lambda transition, the helium self organizes such that the gradient in temperature matches the gravity induced gradient in Tlambda. All the helium in the sample is then at the same reduced temperature tSOC = ((T[sub SOC] - T[sub lambda])/T[sub lambda]) and the helium is said to be in the Self-Organized Critical (SOC) state. We have made preliminary measurements of the 4He SOC state specific heat, C[del]T(T(Q)). Despite having a cell height of 2.54 cm, our results show no difference between C[del]T and the zero-gravity 4He specific heat results of the Lambda Point Experiment (LPE) [J.A. Lipa et al., Phys. Rev. B, 68, 174518 (2003)] over the range 250 to 450 nK below the transition. There is no gravity rounding because the entire sample is at the same reduced temperature tSOC(Q). Closer to Tlambda the SOC specific heat falls slightly below LPE, reaching a maximum at approximately 50 nK below Tlambda, in agreement with theoretical predictions [R. Haussmann, Phys. Rev. B, 60, 12349 (1999)]

Generalized Geometric Cluster Algorithm for Fluid Simulation

We present a detailed description of the generalized geometric cluster algorithm for the efficient simulation of continuum fluids. The connection with well-known cluster algorithms for lattice spin models is discussed, and an explicit full cluster decomposition is derived for a particle configuration in a fluid. We investigate a number of basic properties of the geometric cluster algorithm, including the dependence of the cluster-size distribution on density and temperature. Practical aspects of its implementation and possible extensions are discussed. The capabilities and efficiency of our approach are illustrated by means of two example studies.Comment: Accepted for publication in Phys. Rev. E. Follow-up to cond-mat/041274