Revista Jurídica Digital UANDES
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Stabilizing Terminal Ni(III)–Hydroxide Complex Using NNN-Pincer Ligands: Synthesis and Characterization
No full textThe reaction of [Ni(COD)2] (COD; cyclooctadiene) in THF with the NNN-pincer ligand bis(imino)pyridyl (L1) reveals a susceptibility to oxidation in an inert atmosphere ([O2] level <0.5 ppm), resulting in a transient Ni:dioxygen adduct. This reactive intermediate abstracts a hydrogen atom from THF and stabilizes an uncommon Ni(III) complex. The complex is crystallographically characterized by a molecular formula of [NiIII(L1··)2–(OH)] (1). Various isotopically labeled experiments (16O/18O) assertively endorse the origin of terminal oxygen based ligand in 1 due to the activation of molecular dioxygen. The presence of proton bound to the terminal oxygen in 1 is well supported by NMR, IR spectroscopy, DFT calculations, and hydrogen atom transfer (HAT) reactions promoted by 1. The observation of shakeup satellite peaks for the primary photoelectron lines of Ni(2p) in the X-ray photoelectron spectroscopy (XPS) unambiguously confirms the paramagnetic signature associated with the distorted square planar nickel ion, which is consistent with the trivalent oxidation state assigned for the nickel ion in 1. The variable temperature magnetic susceptibility data of 1 shows dominant antiferromagnetic interactions exist among the paramagnetic centers, resulting in an overall S = 1/2 ground state. Variable temperature X-band EPR studies performed on 1 show evidence for the S = 1/2 ground state, which is consistent with magnetic data. The unusual g-tensor extracted for the ground state S = 1/2 is analyzed under a strong exchange limit of spin-coupled centers. The electronic structure predicted for 1 is in good agreement with theoretical calculations
Regime Legitimation, not Nation-Building: Media Commemoration of the 1917 Revolution in Russia’s Neo-Authoritarian State
No full textScholars predicted that official Russian commemorations of the centenary of the 1917 revolutions would prioritise ‘reconciliation and accord’ between pro- and anti-communists. Such a frame might help construct a new post-Soviet Russian identity. Yet, in 2017, state-affiliated political and media actors gave accounts that contrasted with their previous narratives and with each other. Domestic state-aligned media were unprecedentedly negative about the revolutions’ events and enduring legacies; whilst Russia’s international broadcaster, RT, emphasised the revolution's positive international legacies. We explain this paradox by arguing that regimes of commemoration are directly related to political systems: in neo-authoritarian regimes such as contemporary Russia, history is not used primarily for nation-building, but to build legitimacy for the ruling regime. Referencing similar practices in other neo-authoritarian regimes, we show how state-affiliated actors selectively co-opt interpretations of historical events that circulate in the global media ecology, to ‘arrest’ the ‘memory of the multitude’. Simultaneously, they reinforce core messages that legitimise the existing government
The preschool autism communication therapy – an evidence-based approach to enhancing early autistic development and empowering families
No full textThe Preschool Autism Communication Therapy (PACT) is the only treatment method for early autism to have shown a long-term effect on autism symptom developmental outcomes into middle childhood; as well as evidence of the mechanism through which these effects are produced. The PACT model is designed on the basis of developmental and transactional principles applied to autism, to form a relatively low intensity naturalistic intervention that can be flexibly applied in home or clinic. It works with parents, caregivers or teachers using video-feedback methods to enhance recognition and responsiveness to child communication and optimize child social communication development. There have to date been five replication studies of the core effect of this intervention on parent-child interaction, and four for the effect on child symptom outcomes. PACT has been subjected to the longest post-intervention follow-up to date in the field, showing a sustaining of its effects on child development. An adaptation has been shown effective in low and medium income country settings, and a related pre-emptive intervention effective with infants at autism risk. Training on the PACT model is available through a mixture of online e-learning, face-to-face training and supervised practice teaching (http://research.bmh.manchester.ac.uk/pact/TrainingPACT/).</p
Simple NMR predictors of catalytic hydrogenation activity for Rh(cod)Cl(NHC) complexes featuring fluorinated NHC ligands.
No full textA series of imidazolium salts precursors for N-heterocyclic carbenes (NHCs) featuring fluoroaryl substituents have been prepared along with their selenides and rhodium complexes. Tests of the catalytic activity of the [Rh(cod)Cl(NHC)] complexes in the transfer hydrogenation of acetophenone with iPrOH shows that the activities of the rhodium complexes bearing fluorinated NHCs are better than their non-fluorinated counterparts. The order of activity being 4-F-C6H4 < 2,4-F2-C6H3 < 2,4,5-F3-C6H2 < 2,6-F2-C6H4 < 2,4,6-F3-C6H2. This order of reactivity is consistent with a number of simple NMR measures of the electronic properties of these systems, including 1JCH of the NHC.HBF4 salts, δ(77Se) of the NHC selenides and 1JRh-C and δ(13Ccarbene) of the [Rh(cod)Cl(NHC)] complexes
Comparing Strategies on Explainability of Machine Learning Models with Belief-Rule-Based Expert Systems:A Case Study on Lending Decisions
No full textThe idea to explain the decisions of artificial intelligence (AI) model started in the 1970s to test and engender user trust in expert systems. However, specular advances in computation power and improvements in optimization algorithms shifted the focus towards the accuracy, while the ability to explain the decision has taken a back seat. In future, the decision-making process would be partially or completely dependent on machine learning (ML) algorithms which require humans to trust these algorithms in order to accept those decisions. Several explainable methods and strategies are proposed in the quest to explain the output of black-box ML models. This research compares the explainable machine learning method with the expert system based on belief-rule-base (BRB). Unlike traditional expert system, BRB has the competency to learn from the data and can include knowledge of domain-expert. It can explain the single decision and chain of events leading to the decision. The black-box ML models use local interpretability methods to explain a specific decision and global interpretability method to understand entire model behaviour. In this research, the explainability of mortgage loan decision was compared. It was found that model-agnostic method Shapley provided consistent explanation compared to LIME (local interpretable model-agonistic explanation) for high-performance models such as deep-neural-network, random forest and XGBoost. The global interpretation method, feature importance has issue of dividing the importance among two correlated features. Compared to BRB, these methods cannot reveal the true decision-making process and chain of events leading to a decision.<br/
Computational Study of the Bulk and Surface Properties of the Minor Actinide Dioxides MAnO2 (MAn = Np, Am, Cm); Water Adsorption on Stoichiometric and Reduced {111}, {110} and {100} Surfaces.
No full textHubbard U corrected generalised gradient approximation density functional theory is used to study bulk and surface properties of the minor actinide dioxides NpO2, AmO2 and CmO2. Comparison of lattice parameters, band gaps and densities of states with experimental data indicates that PBE + U (U = 4.50 eV, J = 0.50 eV) is the best approach of those considered. Stoichiometric and oxygen vacancy defect {111}, {110} and {100} surfaces are investigated, including the molecular and dissociative adsorptions of water. Comparison with previous work from our group on UO2 and PuO2 leads to the conclusion that oxygen defect generation energy is essentially linearly correlated with An(IV)/(III) redox potential across the AnO2 series from U to Cm. The geometries of water adsorption are similar across the series, while adsorption energies generally decrease, with the exception of certain PuO2 surfaces, in agreement with very hygroscopic nature of PuO2. Surface defects promote dissociative water adsorption
Leadership in evidence based dentistry
No full textAcademic leaders are responsible for a generation of evidence. They must understand research and its synthesis. One of their priorities should be to reduce waste in dental research and improve value by conducting less research, better research and research for the right reasons. This requires the ability to adapt to change, to work collaboratively, as well as having the vision and courage to be innovative when meeting the challenges of improving oral health worldwide in an evidence-based way.</p
Characterizing wing tears in common pipistrelles (Pipistrellus pipistrellus):investigating tear distribution, wing strength, and possible causes
No full textBats have large, thin wings that are particularly susceptible to tearing. Anatomical specializations, such as fiber reinforcement, strengthen the wing and increase its resistance to puncture, and an extensive vasculature system across the wing also promotes healing. We investigated whether tear positioning is associated with anatomy in common pipistrelles (Pipistrellus pipistrellus). Wing anatomy was described using histological techniques, imaging, and material testing. Tear information, including type, position, time in rehabilitation, and possible causes, was collected from rehabilitators of injured bats across the United Kingdom. Results suggest that the position of the plagiopatagium (the most proximal wing section to the body), rather than its anatomy, influenced the number, location, and orientation of wing tears. While material testing did not identify the plagiopatagium as being significantly weaker than the chiropatagium (the more distal sections of the wing), the plagiopatagium tended to have the most tears. The position of the tears, close to the body and toward the trailing edge, suggests that they are caused by predator attacks, such as from a cat (Felis catus), rather than collisions. Consistent with this, 38% of P. pipistrellus individuals had confirmed wing tears caused by cats, with an additional 38% identified by rehabilitators as due to suspected cat attacks. The plagiopatagium had the lowest number of blood vessels and highest amounts of elastin fibers, suggesting that healing may take longer in this section. Further investigations into the causes of tears, and their effect on flight capabilities, will help to improve bat rehabilitation
Graphene Oxide Flakes Tune Excitatory Neurotransmission in Vivo by Targeting Hippocampal Synapses
No full textSynapses compute and transmit information to connect neural circuits and are at the basis of brain operations. Alterations in their function contribute to a vast range of neuropsychiatric and neurodegenerative disorders and synapse-based therapeutic intervention, such as selective inhibition of synaptic transmission, may significantly help against serious pathologies. Graphene is a two-dimensional nanomaterial largely exploited in multiple domains of science and technology, including biomedical applications. In hippocampal neurons in culture, small graphene oxide nanosheets (s-GO) selectively depress glutamatergic activity without altering cell viability. Glutamate is the main excitatory neurotransmitter in the central nervous system and growing evidence suggests its involvement in neuropsychiatric disorders. Here we demonstrate that s-GO directly targets the release of presynaptic vesicle. We propose that s-GO flakes reduce the availability of transmitter, via promoting its fast release and subsequent depletion, leading to a decline ofglutamatergic neurotransmission. We injected s-GO in the hippocampus in vivo, and 48 h after surgery ex vivo patch-clamp recordings from brain slices show a significant reduction in glutamatergic synaptic activity in respect to saline injections.</p
Talking loud and clear:Sean Pert shares a community initiative to set up trans and non-binary voice and communication groups involving student SLTs
No full textWhile attending a discussion event at Manchester Pride in 2015, I was astonished to hear that Manchester had no integrated care pathway for trans individuals. Th e city, while famous for its diversity and Gay Village, had no one-stop location for trans people to seek support. Paul Martin, OBE, Chief Executive of theLesbian, Gay, Bisexual and Trans (LGBT) Foundation, a charity in central Manchester, explained that trans people often had to travel to diff erent cities to access gender identity clinics (GICs), and even then, waiting lists were long and services frequently limited. Paul commented that service users had highlighted speech and language therapy as particularly challenging to access, while SLTs often reported feeling that they did not have the skills to work with trans individuals. I introduced myself and asked how I and my students at the University of Manchester might help on a voluntary basis