114 research outputs found

    Diagnostic Assessment of Autism in Children Using Telehealth in a Global Context: a Systematic Review

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    Reflecting the significant delays in autism assessments globally, studies have explored whether autism assessments conducted via telehealth are feasible and accurate. This systematic review investigated the psychometric properties of autism assessment tools for children administered via telehealth and examined the diagnostic accuracy of telehealth assessment procedures compared to care-as-usual in-person assessments. Relevant databases (MEDLINE, Embase and PsycInfo) were searched for eligible studies (PROSPERO: CRD42022332500). In total, 18 studies were included, collectively assessing 1593 children for autism. Telehealth assessments for autism were largely comparable to in-person assessments, with a diagnostic agreement of 80–88.2%. Individual behavioral observation tools, diagnostic interviews, and clinician-administered screening tools demonstrated acceptable validity. For many children, diagnostic decision-making can be expedited without loss of validity using telehealth

    Machine learning for emergent middleware

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    Highly dynamic and heterogeneous distributed systems are challenging today's middleware technologies. Existing middleware paradigms are unable to deliver on their most central promise, which is offering interoperability. In this paper, we argue for the need to dynamically synthesise distributed system infrastructures according to the current operating environment, thereby generating "Emergent Middleware'' to mediate interactions among heterogeneous networked systems that interact in an ad hoc way. The paper outlines the overall architecture of Enablers underlying Emergent Middleware, and in particular focuses on the key role of learning in supporting such a process, spanning statistical learning to infer the semantics of networked system functions and automata learning to extract the related behaviours of networked systems

    Mechanisms of Homogeneous Stoichiometric, Catalytic and Photocatalytic Dihydrogen Formation Using Thiocomplexes

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    In neutral aqueous solutions (pH 7.5-8.5), with cysteine as a ligand and vanadium (II) or chromium (II) as reductants two electrons are transferred to the solvent and there is formation of dihydrogen. The role of cysteine is essentially catalytic. It is postulated that the reaction proceeds via a dissociative proton oxidative addition rate determining step. Estimated thermodynamics for this and subsequent steps are favorable. Electron transfer to the solvent may be prevented by paths which are competitive to the formation of the hydride. Two systems are described, in which the electrons end up on the thioligand: one involving reductive scission of a carbon-sulfur bond and desulfurization, the other reductive scission of a sulfur-sulfur bond, proceeding by parallel one- and two-electron paths. Dihydrogen formation in acid solutions using metal ions of low valence is relatively slow. The reasons are kinetic rather than thermodynamic, and are related to positive-positive repulsions in the critical hydride formation step. If, however, the conditions allow negative charge accumulation on the metal ion (e.g. via an excess of a negatively charged ligand) the reaction is accele-rated. This is the case in the formation of dihydrogen from chromium (II) in concentrated HC1, with the couple Mo2Cl8 4-/Mo2 (μ-H) (μ-Cl)2Cl6 3-acting catalytically. Catalytic dihydrogen formation also takes place using dithiolenes. The mechanisms investigated include the transfer of the electrons from the free radical of N,N1-dimethyl-4,41-dipyridine (MV.+) to water. © 1988 IUPA

    Stereochemical Nonrigidity and Geometrical Isomerism in Six-Coordinate Trigonal Prismatic Complexes: The Case of Asymmetric Molybdenum and Tungsten Tris(dithiolenes)

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    The isomerization of nine asymmetric tris(dithiolenes) of tungsten and molybdenum, of the general formula (R1R2C2S2)3M is studied with NMR methods. In the complexes investigated, R1 = H, R2 = p-CH3OPh, p-CH3-Ph, or Ph, and M = W or Mo, or R1 = H, R2 = p-ClPh orp-BrPh, and M = W, or R1 = Ph, R2 = p-CH3OPh, and M = W, as shown in formula I. The complexes are proved to be trigonal prismatic in solution and stereochemically nonrigid at room temperature. An equilibrium favoring the trans isomer (formula III) is established, with the concentration of this isomer being three times that of the cis due to entropy reasons. The kinetics and mechanism of the isomerization is investigated and a scheme is proposed involving the rotation of only one ligand around an axis lying on the dithiolenic ring, passing from the metal to the center of the carbon-carbon bond. This mechanism satisfies energy criteria and is allowed by symmetry selection rules, as theoretical EHMO calculations indicate

    Studies of the low-rank Greek coals. 1. Classification

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    Physical and chemical measurements of Greek coals lead to a classification by rank into five categories, ranging from subbituminous C to peat. This classification is further documented by ESR spectroscopy and powder X-ray diffraction. In order to accommodate all the deposits, a new category is introduced between lignite B and peat, designated as lignitized peat, which is clearly and operationally distinguished from peat and higher-rank lignites. © 1989

    A Study on the Interaction of Eu2+(aq) with Pyridinecarboxylic Acids

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    Europous ion forms with isonicotinic, N-methylisonicotinic, nicotinic, and picolinic acids one to one complexes having several features, which are rather unusual for a lanthanide ion. They are formed in strongly acidic aqueous solutions and have absorption maxima around 420 nm. The formation constants are 0.15 1. mol-1 for nicotinic acid, 0.2 1. mol-1 for picolinic acid, 1.9 1. mol-1 for isonicotinic acid, and 0.4 1. mol-1 for N-methylisonicotinic acid, respectively. Evidence is presented that the complexes involve charge transfer from the metal ion to the ligand. The complexes of nicotinic and picolinic acids are stable toward further redox reaction. The complexes of isonicotinic acid and its N-methyl derivative, however, undergo further reduction leading in the first case to isonicotinaldehyde and in the second very likely to the dihydro derivative. In the presence of Eu3+(aq) the kinetics of the redox reaction of isonicotinic acid and its N-methyl derivative are second order in europous ion, first order in the organic acid, first order in hydrogen ion, and inverse first order in Eu3+(aq). A unified mechanism is proposed to explain the results for both of these acids, which is also consistent with the results obtained on complex formation and with the postulate of a charge transfer from europous ion to the ligand. © 1975, American Chemical Society. All rights reserved

    Photocatalytic splitting of water: increase in conversion and energy storage efficiency

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    The yield of the photocatalytic splitting of water using tris-[1-(4-methoxyphenyl)-2-phenyl-1,2-ethylenodithiolenic-S,S′] tungsten as a photocatalyst-catalyst increases by more than threefold on going from 20 to 70°C, and there is no indication that the effect levels off at this temperature. The intensity of light (within the error limits of our experiments) does not have appreciable effect. The nature of the reversible electron acceptor also influences the energy storage efficiency, e.g. 1,1-dibenzyl-4,4′-bipyridiniumdichloride gives an energy storage efficiency approximately 10% higher than methylviologen. The energy storage efficiency also depends on the presence of electron donors; if Ph3N is added, the energy storage efficiency increases by 20%. With ethylenediaminetetraacetic acid (EDTA) the results are even more spectacular; there is a twofold increase, but only initially. At longer times the system is unstable. Overall light energy storage efficiencies can be as high as 7%, and the expectations for further improvement are very good. © 1994
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