Bromostibine complexes of iron(II): hypervalency and reactivity

The halostibine complexes [CpFe(CO)2(SbMe2Br)][CF3SO3] and [CpFe(CO)2(SbMe2Br)][BF4] both contain significant interactions between the anion and the formally neutral Sb(III) ligand, which simultaneously displays Lewis acidic and Lewis basic properties. The unexpected secondary product [CpFe(CO)(Me2BrSb-?-Br-SbBrMe2)] is formed in the presence of excess ligand, the strongly associated Br– anion bridging the two Sb donors to form a four-membered FeSb2Br ring.<br/

Magnetothermodynamics: Measuring equations of state in a relaxed magnetohydrodynamic plasma

We report the first measurements of equations of state of a fully relaxed magnetohydrodynamic (MHD) laboratory plasma. Parcels of magnetized plasma, called Taylor states, are formed in a coaxial magnetized plasma gun, and are allowed to relax and drift into a closed flux conserving volume. Density, ion temperature, and magnetic field are measured as a function of time as the Taylor states compress and heat. The theoretically predicted MHD and double adiabatic equations of state are compared to experimental measurements. We find that the MHD equation of state is inconsistent with our data.Comment: 4 pages, 4 figure

Use of Item Response Analysis to Investigate Measurement Properties and Clinical Validity of Data for the Dynamic Gait Index

Background and Purpose. The Dynamic Gait Index (DGI) is a standardized clinical assessment that aids in evaluating a subject’s ability to modify gait in response to changing demands. The purpose of this study was to use Rasch measurement theory to examine whether the DGI rating scale meets suggested psychometric guidelines, whether the hierarchical order of DGI tasks is consistent with a clinically logical testing procedure, and whether the DGI represents a unidimensional construct. Subjects. Subjects were 84 community-dwelling male veterans (age range=64–88 years; mean±SD=75±6.47 years). Methods. Data were retrieved retrospectively from the participants’ clinical records. The Rasch measurement model with the WINSTEPS program was used in this study because it offers distinct advantages over traditional psychometric approaches. Results. Overall, the DGI showed sound item psychometric properties. Each of the original 4 rating scale categories appeared to distinctly identify subjects at different ability levels. The analysis revealed a clear item difficulty hierarchical order that is generally consistent with clinical expectations. In addition, fit statistics and principal components analysis indicated that the 8 items of the DGI appear to represent a single construct. Discussion and Conclusion. The results suggest that the rating scale of the DGI is used appropriately for community-dwelling older subjects with balance problems. The findings support the continued use of this well-constructed scale for clinical and research assessment in a community-dwelling population of older subjects. [Chiu YP, Fritz SL, Light KE, Velozo CA. Use of item response analysis to investigate measurement properties and clinical validity of data for the Dynamic Gait Index. Phys Ther. 2006;86:778–787.

Beyond platitudes: a qualitative study of Australian Aboriginal people's perspectives on biobanking.

BACKGROUND: Biobanks are vital resources for genetics and genomics, and it is broadly recognised that for maximal benefit it is essential that they include samples and data from diverse ancestral groups. The inclusion of First Nations people, in particular, is important to prevent biobanking research from exacerbating existing health inequities, and to ensure that these communities share in the benefits arising from research. AIMS: To explore the perspectives of Australian Aboriginal people whose tissue - or that of their family members - has been stored in the biobank of the National Centre for Indigenous Genomics (NCIG). METHODS: Semi-structured interviews with 42 Aboriginal people from the Titjikala, Galiwinku, Tiwi Islands, Yarrabah, Fitzroy Crossing, Derby, One Arm Point and Mulan communities, as well as a formal discussion with A. Hermes, an Indigenous Community Engagement Coordinator at the NCIG who had conducted the interviews. The interviews and the structured discussion were double coded using a procedure informed by Charmaz's outline of grounded theory analysis and Morse's outline of the cognitive basis of qualitative research. RESULTS: In this article, we report on A. Hermes' interviews with members from the above Aboriginal communities, as well as on her personal views, experiences, and interpretations of the interviews she conducted with other community members. We found that participation in the NCIG biobank raised issues around broken trust, grief and loss, but also - somewhat unexpectedly - was perceived as a source of empowerment, hope and reconnection. CONCLUSIONS: This research reminds us (again) of the need to engage deeply with communities in order to respond appropriately with respect for their cultural values and norms, and to develop culturally relevant policies and processes that enhance the benefits of biobank participation and minimise potential harms

Feasibility of Electromyography-Triggered Neuromuscular Stimulation as an Adjunct to Constraint-Induced Movement Therapy

Background and Purpose. The purpose of this case report is to explore the feasibility of electromyography-triggered neuromuscular stimulation (EMG-stim) as an adjunct to constraint-induced movement therapy (CIMT). Case Description. The patient was a 72-year-old man, 10 years poststroke, who did not meet traditional CIMT criteria. The EMG-stim was applied to the wrist extensors of the patient\u27s weaker arm for one half of the CIMT training hours. Outcomes. The intervention was feasible for this individual. Improvements were observed in motor behavior, quality and amount of use, muscle activity, wrist range of motion, and reaction time of the more-affected extremity. These improvements were paralleled by a change in the size and location of the extensor digitorum communis muscle representation in the primary motor cortex, as measured by transcranial magnetic stimulation mapping. Discussion. These changes suggest that using EMG-stim as an adjunct to CIMT should be further investigated in individuals who have low functional abilities following stroke

[Pd4(μ3-SbMe3)4(SbMe3)4]: A Pd(0) tetrahedron with μ3-bridging trimethylantimony ligands

The palladium(II) chlorostibine complex [PdCl2(SbMe2Cl)2]2 has a dimeric structure in the solid state, stabilized by hyper-coordination at the Lewis amphoteric Sb centers. Reaction with 8 equiv of MeLi forms [Pd4(μ3-SbMe3)4(SbMe3)4], whose structure comprises a tetrahedral Pd(0) core with four terminal SbMe3 ligands and four μ3-SbMe3 ligands, one capping each triangular Pd3 face. Density functional theory calculations, supported by energy decomposition analysis and the natural orbitals for chemical valence scheme, highlight significant donor and acceptor orbital contributions to the bonding between both the terminal and the bridging SbMe3 ligands and the Pd4 core

Scarring Effects on Tunneling in Chaotic Double-Well Potentials

The connection between scarring and tunneling in chaotic double-well potentials is studied in detail through the distribution of level splittings. The mean level splitting is found to have oscillations as a function of energy, as expected if scarring plays a role in determining the size of the splittings, and the spacing between peaks is observed to be periodic of period {$2\pi\hbar$} in action. Moreover, the size of the oscillations is directly correlated with the strength of scarring. These results are interpreted within the theoretical framework of Creagh and Whelan. The semiclassical limit and finite-{$\hbar$} effects are discussed, and connections are made with reaction rates and resonance widths in metastable wells.Comment: 22 pages, including 11 figure