Preparation of organometallic cobalt(III) complexes containing bidentate chiral amine ligands as potential transfer hydrogenation catalysts

Mixed coordination sphere cobalt(III) complexes containing a chiral bidentate amine ligand and an organic carbocyclic ligand have been prepared and characterized. The integration of this mixed ligand environment involving an organometallic and Werner-type ligand along with the earth abundant metal in a high oxidation state has the potential for interesting reactivity. Complexes of the type [Co(CpR)(X-DPEN)(I)](I), where CpR = cyclopentadienyl (Cp, R = H) or pentamethylcyclopentadienyl (Cp*, R = Me) and X = meso-1,2-, 1R,2R-, and 1S,2S-, have been prepared by ligand substitution from [Co(CpR)(I)2(CO)] with 1,2-diphenyletheylenediamine (DPEN). The outer sphere iodide is readily exchangeable with sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (NaBArF) or cesium acetate (CsOAc), and both iodides can be exchanged with silver(I) acetate (AgOAc). The latter reactions with AgOAc results in either [Co(CpR)(X-DPEN)(OH2)](OAc)2 or [Co(CpR)(X-DPEN)(OAc)](OAc) depending on the solvent profile, and partial iodide removal to produce [Co(Cp*)(1S,2S-DPEN)(OAc)](I) in the presence of CsOAc. The complexes are isolated as diamagnetic black, dark purple, or, in the case of acetate complexes, pink solids and characterized by 1H-NMR, 13C-NMR and UV-vis spectroscopy as well as either elemental analysis or mass spectrometry. Four complexes, [Co(Cp)(1R,2R-DPEN)(I)](I) (1), [Co(Cp)(1S,2S-DPEN)(I)](BArF) (2a), [Co(Cp*)(1S,2S-DPEN)(I)](I) (4), and [Co(Cp*)(1S,2S-DPEN)(OAc)](I) (13) have been characterized by single-crystal X-ray diffraction. The preparation, characterization, and initial reactivity of these complexes as potential catalysts for aqueous hydrogen transfer as well as the extension to the substituted chiral amine (R,R)-N-(2-amino-1,2-diphenylethyl)-p-toluenesulfonamide (Ts-DPEN) will be discussed

Preditores socio-demográficos, clínicos e de saúde oral auto-percebida nos idosos

Poster apresentado nas XXIV Jornadas Internacionais de Medicina Dentária do ISCSEM, 4-5 Março 2015, Egas Moniz, Caparica, Portugal

Bond assessment between rebars embedded into a parent material using a single-function bond-slip model

Publisher Copyright: © 2023 The Author(s)The pull-out test is usually used to evaluate the local bond behaviour between a rebar such as a ribbed steel rebar or a Fiber Reinforced Polymer (FRP) and a parent material, like concrete or timber. Although some codes recommend using a piecewise bond-slip model for ribbed or round steel rebars embedded in concrete, there is no globally accepted bond-slip model for FRP composites. Consequently, this piecewise bond-slip model is usually adapted for FRP composites embedded in a parent material (substrate). The present work therefore aims to propose a novel single-function bond-slip model that may be calibrated and used to model the pull-out test and the detachment process of an embedded rebar from a parent material. The model requires the calibration of three parameters that may vary according to the type of rebar and its parent material. Since the governing equation of the detachment between the rebar and the parent material during a pull-out test has no known analytical solution, the Finite Difference Method (FDM) was applied to find the interfacial slips throughout the embedded length. The results were compared and validated with the experimental pull-out tests of ribbed steel rebars embedded into a concrete block as well as with the numerical results obtained from the use of the Finite Element Method (FEM). To cover a broader range of materials and show the versatility of the novel bond-slip model, the results were also compared with other experimental data available in the literature. The results showed a very high precision of the new bond-slip model when applied to several pull-out tests especially when ribbed steel rebars-to-concrete and FRP-to-concrete interfaces or FRP-to-timber interfaces were used.publishersversionpublishe

Warped metrics for location-scale models

This paper argues that a class of Riemannian metrics, called warped metrics, plays a fundamental role in statistical problems involving location-scale models. The paper reports three new results : i) the Rao-Fisher metric of any location-scale model is a warped metric, provided that this model satisfies a natural invariance condition, ii) the analytic expression of the sectional curvature of this metric, iii) the exact analytic solution of the geodesic equation of this metric. The paper applies these new results to several examples of interest, where it shows that warped metrics turn location-scale models into complete Riemannian manifolds of negative sectional curvature. This is a very suitable situation for developing algorithms which solve problems of classification and on-line estimation. Thus, by revealing the connection between warped metrics and location-scale models, the present paper paves the way to the introduction of new efficient statistical algorithms.Comment: preprint of a submission to GSI 2017 conferenc

A sentence-completion task

Funding Information: JC was financed by national funding through FCT—Fundação para a Ciência e a Tecnologia, I.P., on the scope of Norma Transitória DL57/2016/CP1439/CT02 and received also national funding from FCT—Fundação para a Ciência e a Tecnologia, I.P, through the Research Center for Psychological Science of the Faculty of Psychology, University of Lisbon (UIDB/04527/2020 and UIDP/04527/2020). The funders had no role in study design, data collection and analysis, or preparation of the manuscript.It has been proposed that individuals with autism spectrum disorder (ASD) struggle both with response initiation and with response inhibition, both of which are functions of the executive system. Experimental tasks are unlikely pure measures of a single cognitive domain, and in this study we aim at understanding the contributions of response initiation difficulties to possible deficits in inhibitory control in autism. A sample of adults diagnosed with ASD and a control sample participated in this study. To participants it was asked to perform a sentence-completion task with two different condition: Part A—targeting response initiation and Part B—engaging inhibitory processes. Importantly, we have analyzed the B-A latencies that have been proposed for the removal of the response initiation confound effect. Results show that no differences between the groups were found in accuracy measures, either in Part A (ASD: M = 0.78; Controls: M = 0.90) nor Part B (ASD: M = 0.03; Controls: M = 0.02). However, in both conditions autistic participants were significantly slower to respond than the group of participants with typical development (Part A—ASD: M = 2432.5 ms; Controls M = 1078.5 ms; Part B—ASD M = 6758.3 ms; Controls M = 3283.9 ms). Critically, we show that when subtracting the response times of Part A from Part B (B-A latencies) no group differences attributable to inhibitory processes remained (ASD: M = 4325.76; Controls: M = 2205.46). With this study we corroborate the existence of difficulties with response initiation in autism and we question the existence of troubles in inhibition per se.publishersversionpublishe

Preliminary effects of intermittent light stimulation

Funding Information: This study was funded by the Foundation for Science and Technology—FCT (Portuguese Ministry of Science, Technology and Higher Education), under the grant UIDB/05380/2020. The funders had no role in the study design, data collection and analysis, or preparation of the manuscript. The authors have no relevant financial or non‐financial interests to disclose. Publisher Copyright: © 2023 The British Psychological Society.Several authors have contributed extensively to the neurocognitive understanding of timing. In Autism Spectrum Disorder (ASD) on the contrary, internal timing and its functioning is not well understood. In this study, we have adapted a simple finger-tapping motor task, with a timing component, as we aim at understanding whether the processing of time is preserved in this population. We have tested a group of people on the autism spectrum without intellectual disabilities and a control sample recruited from the general population, matched for age, sex, schooling and general cognitive abilities on this task with a learning and testing phase. In the testing phase, we have added two exploratory conditions where participants were exposed to intermittent light stimulation of 4 and 8 Hz. Results show that both in the learning and testing phase, besides troubles in the motor component encountered by the people on the spectrum, their timing component performance was also problematic. This reveals to be especially true for time intervals below the 1 s range, as hypothesized, whereas performance in longer intervals is clearly preserved. It was also observed that the exposure to intermittent light stimulation specifically overcomes the difficulties observed in the autistic group, at the timing components at this millisecond time range. The observed timing difficulties in this group seem to be restricted to the system responsible for the processing of time intervals in the milliseconds range, which helps accommodate disparate findings in the literature.publishersversionepub_ahead_of_prin

A systematic review of normative studies using images of common objects

Common objects comprise living and non-living things people interact with in their daily-lives. Images depicting common objects are extensively used in different fields of research and intervention, such as linguistics, psychology, and education. Nevertheless, their adequate use requires the consideration of several factors (e.g., item-differences, cultural-context and confounding correlated variables), and careful validation procedures. The current study presents a systematic review of the available published norms for images of common objects. A systematic search using PRISMA guidelines indicated that despite their extensive use, the production of norms for such stimuli with adult populations is quite limited (N = 55), particularly for more ecological images, such as photos (N = 14). Among the several dimensions in which the items were assessed, the most commonly referred in our sample were familiarity, visual complexity and name agreement, illustrating some consistency across the reported dimensions while also indicating the limited examination of other potentially relevant dimensions for image processing. The lack of normative studies simultaneously examining affective, perceptive and semantic dimensions was also documented. The number of such normative studies has been increasing in the last years and published in relevant peer-reviewed journals. Moreover, their datasets and norms have been complying with current open science practices. Nevertheless, they are still scarcely cited and replicated in different linguistic and cultural contexts. The current study brings important theoretical contributions by characterizing images of common objects stimuli and their culturally-based norms while highlighting several important features that are likely to be relevant for future stimuli selection and evaluative procedures. The systematic scrutiny of these normative studies is likely to stimulate the production of new, robust and contextually-relevant normative datasets and to provide tools for enhancing the quality of future research and intervention.info:eu-repo/semantics/publishedVersio

Mandioquinha-salsa: manejo cultural.

bitstream/item/107364/1/CNPH-MANDIOQ.-SALSA-MANEJ.-CULT.-98-2.pd