Rhodium Pyrazolate Complexes as Potential CVD Precursors

Reaction of 3,5-(CF3)(2)PzLi with [Rh(mu-Cl)(eta(2)-C2H4)(2)](2) or [Rh(mu-Cl)(PMe3)(2)](2) in Et2O gave the dinuclear complexes [Rh(eta(2)-C2H4)(2)(mu-3,5-(CF3)(2)-Pz)](2) (1) and [Rh-2(mu-Cl)(mu-3,5-(CF3)(2)-Pz) (PMe3)(4)] (2) respectively (3,5-(CF3)(2)Pz = bis-trifluoromethyl pyrazolate). Reaction of PMe3 with [Rh(COD)(mu-3,5-(CF3)(2)-Pz)](2) in toluene gave [Rh(3,5-(CF3)(2)-Pz)(PMe3)(3)] (3). Reaction of 1 and 3 in toluene (1 : 4) gave moderate yields of the dinuclear complex [Rh(PMe3)(2)(mu-3,5-(CF3)(2)-Pz)](2) (4). Reaction of 3,5-(CF3)(2)PzLi with [Rh(PMe3)(4)]Cl in Et2O gave the ionic complex [Rh(PMe3)(4)][3,5-(CF3)(2)-Pz] (5). Two of the complexes, 1 and 3, were studied for use as CVD precursors. Polycrystalline thin films of rhodium (fcc-Rh) and metastable-amorphous films of rhodium phosphide (Rh2P) were grown from 1 and 3 respectively at 170 and 130 degrees C, 0.3 mmHg in a hot wall reactor using Ar as the carrier gas (5 cc min(-1)). Thin films of amorphous rhodium and rhodium phosphide (Rh2P) were grown from 1 and 3 at 170 and 130 degrees C respectively at 0.3 mmHg in a hot wall reactor using H-2 as the carrier gas (7 cc min(-1)).Welch Foundation F-816Petroleum Research Fund 47014-ACSNSF 0741973Chemistr

Evaluation of long-term counselling at a community health service for women who are on a low income

Aims. Given the lack of research evaluating long-term counselling, coupled with the lack of women-only counselling services, the present study evaluated the long-term counselling service offered by a women-only community health centre. Method. The research ascertained: 1) the characteristics of 155 service users pre-counselling, 2) the views and experiences of 75 service users post-counselling and 3) pre-post-counselling clinical change in 98 service users via the Clinical Outcomes in Routine Evaluation - Outcome Measure (CORE-OM). Results. Unemployment, low income and reports of abuse were related to poorer mental health as measured by the CORE-OM. Content analysis of open-ended questions revealed that women felt supported, comfortable and gained insight through the counselling relationship. They also reported positive changes in their lives, relationships, health behaviours, and psychological wellbeing. Post-counselling improvements were found in CORE-OM scores. Conclusions. Long-term counselling in a women-only environment for socially disempowered women may be beneficial. A research-informed approach to counselling and therapy evaluation, which acknowledges the social context of psychological distress, should be taken across institutions

A sanctuary of tranquillity in a ruptured world: evaluating long-term counselling at a women’s community health centre

The longitudinal study described in this article evaluated long-term counselling provided at a women’s health centre in the UK for service users on low incomes. The article focuses on the qualitative aspect of the study in which 59 women were interviewed individually before and/or after their counselling. The interviews explored how women make sense of long-term counselling in the context of their gendered experiences and complex needs. The data were analysed using thematic analysis informed by a feminist orientation and attachment theory. Four main themes emerged:‘violence and loss in the context of female oppression’, ‘a sanctuary for women’, ‘non-medicalised long-term counselling in a safe setting’, and ‘benefits of the long view’. Participants attributed various benefits to receiving long-term counselling in a women-only environment. These included gaining employment; reduced suicidal ideation, anxiety and depression; improved physical health, improved confidence and being able to make positive changes in their relationships. The women interviewed post-counselling valued long term-counselling in this context, in contrast to short-term therapy in a medicalised environment. Wider implications with regards to clinical practice and research are discussed

Ratcheting Heat Flux against a Thermal Bias

Merely rocking the temperature in one heat bath can direct a steady heat flux from cold to hot against a non-zero thermal bias in stylized nonlinear lattice junctions that are sandwiched between two heat baths. Likewise, for an average zero-temperature difference between the two contacts a net, ratchet-like heat flux emerges. Computer simulations show that this very heat flux can be controlled and reversed by suitably tailoring the frequency ($\lesssim$ 100 MHz) of the alternating temperature field.Comment: 5 pages, 6 figure

Modelling the effects of climate on long-term patterns of dissolved organic carbon concentrations in the surface waters of a boreal catchment

International audienceDissolved organic carbon concentrations ([DOC]) in surface waters are increasing in many regions of Europe and North America. These increases are likely driven by a combination of changing climate, recovery from acidification and change in severity of winter storms in coastal areas. INCA-C, a process-based model of climate effects on surface water [DOC], was used to explore the mechanisms by which changing climate controls seasonal to inter-annual patterns of [DOC] in the lake and outflow stream of a small Finnish catchment between 1990 and 2003. Both production in the catchment and mineralization in the lake controlled [DOC] in the lake. Concentrations in the catchment outflow were controlled by rates of DOC production in the surrounding organic soils. The INCA-C simulation results were compared to those obtained using artificial neural networks (ANN). In general, "black box" ANN models provide better fits to observed data but process-based models can identify the mechanism responsible for the observed pattern. A statistically significant increase was observed in both INCA-C modelled and measured annual average [DOC] in the lake. This suggests that some of the observed increase in surface water [DOC] is caused by climate-related processes operating in the lake and catchment. However, a full understanding of surface water [DOC] dynamics can only come from catchment-scale process-based models linking the effects of changing climate and deposition on aquatic and terrestrial environments

Pervasive contingency and entrenchment in a billion years of Hsp90 evolution [preprint]

Interactions among mutations within a protein have the potential to make molecular evolution contingent and irreversible, but the extent to which epistasis actually shaped historical evolutionary trajectories is unclear. We addressed this question by identifying all amino acid substitutions that occurred during the billion-year evolutionary history of the heat shock protein 90 (Hsp90) ATPase domain beginning from a deep eukaryotic ancestor to modern Saccharomyces cerevisiae and then precisely measuring their fitness effects when introduced into both extant and reconstructed ancestral Hsp90 proteins. We find a pervasive influence of epistasis: of 98 derived states that evolved during history, most were deleterious at times before they happened, and the vast majority also became subsequently entrenched, with the ancestral state becoming deleterious after its substitution. This epistasis was primarily caused by specific interactions among sites rather than a general permissive or restrictive effect on the protein\u27s tolerance to mutation. Our results show that epistasis continually opens and closes windows of mutational opportunity over evolutionary timescales, producing histories and biological states that reflect the transient internal constraints imposed by a protein\u27s fleeting sequence states

Remarks On Sequential Hypothesis Testing

1 online resource (PDF, 9 pages