3,945 research outputs found

    Room temperature regioselective catalytic hydrodefluorination of fluoroarenes with trans-[Ru(NHC)4H2] through a concerted nucleophilic Ru−H attack pathway

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    The authors acknowledge the EPSRC (grant EP/J009962/1, DTA) for financial supportThe efficient and highly selective room temperature hydrodefluorination (HDF) of fluoroarenes by the trans-[Ru(IMe4)4H2] catalyst, 3 , is reported. Mechanistic studies show 3 acts directly in catalysis without any ligand dissociation and DFT calculations indicate a concerted nucleophilic attack mechanism. The calculations fully account for the observed selectivities which corroborate earlier predictions regarding the selectivity of HDF.PostprintPeer reviewe

    Unexpected Vulnerability of DPEphos to C-O Activation in the Presence of Nucleophilic Metal Hydrides

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    C−O bond activation of DPEphos occurs upon mild heating in the presence of [Ru(NHC)2(PPh3)2H2] (NHC=N-heterocyclic carbene) to form phosphinophenolate products. When NHC=IEt2Me2, C−O activation is accompanied by C−N activation of an NHC ligand to yield a coordinated N-phosphino-functionalised carbene. DFT calculations define a nucleophilic mechanism in which a hydride ligand attacks the aryl carbon of the DPEphos C−O bond. This is promoted by the strongly donating NHC ligands which render a trans dihydride intermediate featuring highly nucleophilic hydride ligands accessible. C−O bond activation also occurs upon heating cis-[Ru(DPEphos)2H2]. DFT calculations suggest this reaction is promoted by the steric encumbrance associated with two bulky DPEphos ligands. Our observations that facile degradation of the DPEphos ligand via C−O bond activation is possible under relatively mild reaction conditions has potential ramifications for the use of this ligand in high-temperature catalysis.</p

    Learning intrinsic excitability in medium spiny neurons

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    We present an unsupervised, local activation-dependent learning rule for intrinsic plasticity (IP) which affects the composition of ion channel conductances for single neurons in a use-dependent way. We use a single-compartment conductance-based model for medium spiny striatal neurons in order to show the effects of parametrization of individual ion channels on the neuronal activation function. We show that parameter changes within the physiological ranges are sufficient to create an ensemble of neurons with significantly different activation functions. We emphasize that the effects of intrinsic neuronal variability on spiking behavior require a distributed mode of synaptic input and can be eliminated by strongly correlated input. We show how variability and adaptivity in ion channel conductances can be utilized to store patterns without an additional contribution by synaptic plasticity (SP). The adaptation of the spike response may result in either "positive" or "negative" pattern learning. However, read-out of stored information depends on a distributed pattern of synaptic activity to let intrinsic variability determine spike response. We briefly discuss the implications of this conditional memory on learning and addiction.Comment: 20 pages, 8 figure

    Empirical evidence for discrete neurocognitive subgroups in bipolar disorder: clinical implications

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    Background. Recent data suggest trait-like neurocognitive impairments in bipolar disorder (BPD), with deficits about 1 S.D. below average, less severe than deficits noted in schizophrenia. The frequency of significant impairment in BPD is approximately 60%, with 40% of patients characterized as cognitively spared. This contrasts with a more homogeneous presentation in schizophrenia. It is not understood why some BPD patients develop deficits while others do not. Method. A total of 136 patients with BPD completed the MATRICS Consensus Cognitive Battery and data were entered into hierarchical cluster analyses to: (1) determine the optimal number of clusters (subgroups) that fit the sample; and (2) assign subjects to a specific cluster based on individual profiles. We then compared subgroups on several clinical factors and real-world community functioning. Results. Three distinct neurocognitive subgroups were found: (1) an intact group with performance comparable with healthy controls on all domains but with superior social cognition; (2) a selective impairment group with moderate deficits on processing speed, attention, verbal learning and social cognition and normal functioning in other domains; and (3) a global impairment group with severe deficits across all cognitive domains comparable with deficits in schizophrenia. Conclusions. These results suggest the presence of multiple cognitive subgroups in BPD with unique profiles and begin to address the relationships between these subgroups, several clinical factors and functional outcome. Next steps will include using these data to help guide future efforts to target these disabling symptoms with treatment

    Feeling our way: academia, emotions and a politics of care

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    This paper aims to better understand the role of emotions in academia, and their part in producing, and challenging, an increasingly normalized neoliberal academy. It unfolds from two narratives that foreground emotions in and across academic spaces and practices, to critically explore how knowledges and positions are constructed and circulated. It then moves to consider these issues through the lens of care as a political stance towards being and becoming academics in neoliberal times. Our aim is to contribute to the burgeoning literature on emotional geographies, explicitly bringing this work into conversation with resurgent debates surrounding an ethic of care, as part of a politic of critiquing individualism and managerialism in (and beyond) the academy. We consider the ways in which neoliberal university structures circulate particular affects, prompting emotions such as desire and anxiety, and the internalisation of competition and audit as embodied scholars. Our narratives exemplify how attendant emotions and affect can reverberate and be further reproduced through university cultures, and diffuse across personal and professional lives. We argue that emotions in academia matter, mutually co-producing everyday social relations and practices at and across all levels. We are interested in their political implications, and how neoliberal norms can be shifted through practices of caring-with

    Fabrication of CaO-NaO-SiO2/TiO2 Scaffolds for Surgical Applications

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    A series of titanium (Ti) based glasses were formulated (0.62 SiO2-0.14 Na2O-0.24 CaO, with 0.05 mol% TiO2 substitutions for SiO2) to develop glass/ceramic scaffolds for bone augmentation. Glasses were initially characterised using X-ray diffraction (XRD) and particle size analysis, where the starting materials were amorphous with 4.5 μm particles. Hot stage microscopy and high temperature XRD were used to determine the sintering temperature (̃700 °C) and any crystalline phases present in this region (Na2Ca3Si6O16, combeite and quartz). Hardness testing revealed that the Ti-free control (ScC- 2.4 GPa) had a significantly lower hardness than the Ti-containing materials (Sc1 and Sc2 ̃6.6 GPa). Optical microscopy determined pore sizes ranging from 544 to 955 lm. X-ray microtomography calculated porosity from 87 to 93 % and surface area measurements ranging from 2.5 to 3.3 SA/mm3. Cytotoxicity testing (using mesenchymal stem cells) revealed that all materials encouraged cell proliferation, particularly the higher Ti-containing scaffolds over 24-72 h. © Springer Science+Business Media, LLC 2012
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