Evaluating Thermal Corrections for Adsorption Processes at the Metal/Gas Interface
International audience; Adsorption and desorption steps are key for active catalysts and rely on a subtle balance between enthalpic and entropic terms. While the enthalpic term is becoming ever more accurate through density functional development, the entropic term remains underrated and its precise determination a great challenge. In this work, we have performed extensive first principles thermodynamic integration (TI) simulations for the 1 adsorption of small (e.g., CO) to larger (e.g., phenol) molecules at metallic surfaces and compared their adsorption free energies to the values obtained by vertical, static statistical mechanics approximations to thermal corrections invoking three diff…
Prism adaptation and neck muscle vibration in healthy individuals: Are two methods better than one?
Studies involving therapeutic combinations reveal an important benefit in the rehabilitation of neglect patients when compared to single therapies. In light of these observations our present work examines, in healthy individuals, sensorimotor and cognitive after-effects of prism adaptation and neck muscle vibration applied individually or simultaneously. We explored sensorimotor after-effects on visuo-manual open-loop pointing, visual and proprioceptive straight-ahead estimations. We assessed cognitive after-effects on the line bisection task. Fifty-four healthy participants were divided into six groups designated according to the exposure procedure used with each: 'Prism' (P) group; 'Vibra…
Modifying auditory perception with prisms? Aftereffects of prism adaptation on a wide auditory spectrum in musicians and nonmusicians
Prism adaptation consists of pointing to visual targets while wearing prisms that shift the visual field laterally. The aftereffects are not restricted to sensorimotor level but extend to spatial cognition. There is a link between spatial representation and auditory frequency, with an association of low frequencies on the left side and high frequencies on the right side of space. The present study aimed first at evaluating the representation of auditory frequencies on a wide range of frequencies in musicians and nonmusicians. We used the ‘auditory interval bisection judgment’ within three auditory intervals. The results showed a pseudoneglect behavior in pretest in musicians and nonmusician…
Ten Facets, One Force Field: The GAL19 Force Field for Water - Noble Metal Interfaces
<div>Understanding the structure of the water/metal interfaces plays an important role in many are as ranging from surface chemistry to environmental processes. Due to their intrinsic complexity, the water/metal interfaces cannot yet be adequately described by quantum mechanical approaches and accurate force-fields are therefore needed. We develop and parametrize GAL19, a novel force-field to describe the interaction of water with two facets (111 and 100) of five metals (Pt, Pd, Au, Ag, Cu). To increase transferability compared to its predecessor GAL17, the water-metal interaction is described as a sum of pair-wise terms. The interaction energy has three contributions: (i) physisorption …
Does force-field adaptation induce after-effects on space representation?
AbstractPrism adaptation is a well-known model to study sensorimotor adaptive processes. It has been shown that following prism exposure, after-effects are not only restricted to the sensorimotor level but extend as well into spatial cognition. The main purpose of the present study was to investigate in healthy individuals whether expansion to spatial cognition is restricted to adaptive processes peculiar to prism adaptation or whether it occurs as well following other forms of adaptive process such as adaptation to a novel dynamic environment during pointing movements. Representational after-effects were assessed by the perceptual line bisection task before and after adaptation to a leftwa…
Visuospatial processing in schizophrenia: Does it share common mechanisms with pseudoneglect?
International audience; ''Schizophrenia patients demonstrate behavioural and cerebral lateralised anomalies, prompting some authors to suggest they exhibit a mild form of right unilateral neglect. To better describe and understand lateralised visuospatial anomalies in schizophrenia, three experiments were run using tasks often utilised to study visuospatial processing in healthy individuals and in neglect patients: the Behavioural Inattention Test (BIT), the manual line bisection task with and without a local cueing paradigm, the landmark task (or line bisection judgement), and the number bisection task. Although the schizophrenia patients did not exhibit the full-blown neglect syndrome, th…
ENANTIOSELECTIVE REDUCTION OF PROCHIRAL KETONES PROMOTED BY AMINO AMIDE RUTHENIUM COMPLEXES: A DFT STUDY
International audience; The origin of enantioselectivity in the reaction of chiral Ru amino amide complexes in the asymmetric transfer hydrogenation of acetophenone was investigated using DFT calculations. For the most stable active catalysts, the full free energy profiles for the reaction were calculated according to the concerted hydrogen transfer mechanism. We succeeded in reproducing the experimentally observed enantioselectivity for the studied Ru amino amide complexes. Our results indicate that the high enantioselectivity can be explained by a stabilizing CH-π interaction existing between the phenyl group of acetophenone and the aromatic substituent of the catalyst, which plays a sign…
Left minineglect or inverse pseudoneglect in children with dyslexia?
International audience; This study compared the visuospatial asymmetries in children with dyslexia and healthy children by using the manual line bisection task, and investigated the processing of spatial context with a 'local' cueing paradigm consisting of geometric symbols placed on the extremities of the lines. The performance between healthy children (leftward bias) and children with dyslexia (rightward bias) was significantly different. Furthermore, the bisection mark was shifted in the direction of the unilaterally cued extremities in all children. As children with dyslexia showed a rightward bias in their spatial representation, which did not interfere with local context processing, w…
Beyond the sensorimotor plasticity: cognitive expansion of prism adaptation in healthy individuals.
Sensorimotor plasticity allows us to maintain an efficient motor behavior in reaction to environmental changes. One of the classical models for the study of sensorimotor plasticity is prism adaptation. It consists of pointing to visual targets while wearing prismatic lenses that shift the visual field laterally. The conditions of the development of the plasticity and the sensorimotor after-effects have been extensively studied for more than a century. However, the interest taken in this phenomenon was considerably increased since the demonstration of neglect rehabilitation following prism adaptation by Rossetti and his colleagues in 1998. Mirror effects, i.e. simulation of neglect in health…
Cross-modal aftereffects of visuo-manual prism adaptation: Transfer to auditory divided attention in healthy subjects.
OBJECTIVE Prism adaptation was shown to modify auditory perception. Using a dichotic listening task, which assesses auditory divided attention, benefits of a rightward prism adaptation were demonstrated in neglect patients (i.e., a syndrome following right hemisphere brain damage) by reducing their left auditory extinction. It is currently unknown whether prism adaptation affects auditory divided attention in healthy subjects. In the present study, we investigated the aftereffects of prism adaptation on dichotic listening. METHOD A sample of 47 young adults performed a dichotic listening task, in which pairs of words were presented with two words sounded simultaneously, one in each ear. Thr…
Prism adaptation power on spatial cognition: Adaptation to different optical deviations in healthy individuals
The main objective of the present study was to determine the minimal optical deviation responsible for cognitive after-effects in healthy individuals and to explore whether there was a relationship between the degree of optical deviation and cognitive after-effects. Therefore different leftward optical deviations (8°, 10° and 15°) were used in three different groups of healthy participants. Sensorimotor after-effects (evaluating the visuo-manual realignment) were assessed using an open-loop pointing task and cognitive after-effects (evaluating changes in spatial representation) were assessed using manual and perceptual (landmark) line bisection tasks. Results revealed that exposure to 8°, 1…
Testing cognition and rehabilitation in unilateral neglect with wedge prism adaptation: multiple interplays between sensorimotor adaptation and spatial cognition
Spatial neglect is a neurological condition characterised by deficits for perceiving, attending, representing, and/or performing actions within their left-sided space, responsible for numerous debilitating effects in everyday life, for poor functional recovery, and for decreased ability to benefit from treatment. Exposure to a right lateral displacement of the visual field (induced by a simple target-pointing task with base-left wedge prisms) is known to directionally bias visuomotor coordination and can be compensated by both sensorimotor adaptation and cognitive processes. Sensorimotor adaptation gives rise to after-effects whose duration is amplified in neglect patients and has been repe…
Pseudoneglect in schizophrenia: A line bisection study with cueing
Numerous authors have reported the existence of lateralised abnormalities towards the right side in patients with schizophrenia.In the present study, a manual line bisection task was used to assess the existence of a visuospatial bias in patients with schizophrenia as compared to healthy subjects and left unilateral neglect patients. In addition, we used a local cueing paradigm (consisting of a number placed on the right, on the left, or at both ends of the line).Healthy subjects showed a leftwards trend in the "no cue" condition (known as pseudoneglect) and neglect patients showed a right bias in all cue conditions. In contrast, patients with schizophrenia placed their manual estimation of…
White Book on Physical and Rehabilitation Medicine in Europe. Introductions, Executive Summary, and Methodology
The White Book (WB) of Physical and Rehabilitation Medicine (PRM) in Europe is produced by the 4 European PRM Bodies (European Academy of Rehabilitation Medicine - EARM, European Society of PRM - ESPRM, European Union of Medical Specialists - PRM Section, European College of PRM-ECPRM served by the European Union of Medical Specialists-PRM Board) and constitutes the reference book for PRM physicians in Europe. It has now reached its third edition; the first was published in 1989 and the second in 2006/2007. The WB has multiple purposes, including providing a unifying framework for European countries, to inform decision-makers on European and national level, to offer educational material for…
Developmental dyslexia and vision
International audience; Developmental dyslexia affects almost 10% of school-aged children and represents a significant public health problem. Its etiology is unknown. The consistent presence of phonological difficulties combined with an inability to manipulate language sounds and the grapheme-phoneme conversion is widely acknowledged. Numerous scientific studies have also documented the presence of eye movement anomalies and deficits of perception of low contrast, low spatial frequency, and high frequency temporal visual information in dyslexics. Anomalies of visual attention with short visual attention spans have also been demonstrated in a large number of cases. Spatial orientation is als…
Cognitive demands impair postural control in developmental dyslexia: A negative effect that can be compensated
Children with developmental dyslexia exhibit delayed reading abilities and various sensori-motor deficits. The way these various symptoms interact remain poorly understood. The objective of this study was twofold. First, we aimed to investigate whether postural control was impaired in dyslexic children when cognitive demands are increased. Second, we checked whether this effect could be reduced significantly by a treatment aiming to recalibrate ocular proprioception. Twelve dyslexic and fifteen treated dyslexic children (>3 months of treatment) were compared with twelve non-dyslexic children in two conditions (mean age: 11.6 ± 2.1, 12.5 ± 1.5 and 10.6 ± 1.7 years respectively). In a first c…
Prism adaptation by mental practice
International audience; The prediction of our actions and their interaction with the external environment is critical for sensorimotor adaptation. For instance, during prism exposure, which deviates laterally our visual field, we progressively correct movement errors by combining sensory feedback with forward model sensory predictions. However, very often we project our actions to the external environment without physically interacting with it (e.g., mental actions). An intriguing question is whether adaptation will occur if we imagine, instead of executing, an arm movement while wearing prisms. Here, we investigated prism adaptation during mental actions. In the first experiment, participa…
Force Field for Water over Pt(111): Development, Assessment, and Comparison
Metal/water interfaces are key in many natural and industrial processes, such as corrosion, atmospheric, or environmental chemistry. Even today, the only practical approach to simulate large interfaces between a metal and water is to perform force-field simulations. In this work, we propose a novel force field, GAL17, to describe the interaction of water and a Pt(111) surface. GAL17 builds on three terms: (i) a standard Lennard-Jones potential for the bonding interaction between the surface and water, (ii) a Gaussian term to improve the surface corrugation, and (iii) two terms describing the angular dependence of the interaction energy. The 12 parameters of this force field are fitted again…
A Force Field for Water Over Pt(111): Development, Assessment And Comparison
International audience
Representational Bias in the Radial Axis in Children With Dyslexia: A Landmarks Alignment Study.
To better identify the distinctive characteristics of space representation in the radial dimension, we have proposed a new paradigm: the landmarks alignment task where two parallel aluminum bars were radially presented. Children had to move a landmark along one bar and place it at the same location as the reference landmark placed by the examiner on the parallel bar. The major interest of this task was its capacity to assess space representation in the radial dimension when considering a spatial landmark that oriented the subject’s attention toward the orthogonal dimension. The most important result showed that in the radial dimension children with dyslexia exhibited a forward bias on the …
Long-term sensorimotor and therapeutical effects of a mild regime of prism adaptation in spatial neglect
International audience; Spatial neglect (SN) is commonly associated with poor functional outcome. Adaptation to a rightward optical deviation of vision has been shown to benefit to SN rehabilitation. The neurophysiological foundations and the optimal modalities of prism adaptation (PA) therapy however remain to be validated. This study is aimed at exploring the long-term sensory-motor, cognitive and functional effects produced by weekly PA sessions over a period of four weeks. A double-blind, monocentric randomized and controlled trial (RCT) was carried out. Twenty patients with left SN secondary to stroke were included, 10 in the “prism” group and 10 in the “control” group. The sensory-mot…
Effets sensori-moteurs et fonctionnels à long terme d’un traitement hebdomadaire par adaptation prismatique dans la négligence : un essai randomisé et contrôlé en double insu
RésuméLa négligence spatiale (NS) constitue un facteur de mauvais pronostic fonctionnel. L’adaptation à une déviation prismatique de la vision vers la droite améliore la NS. Les bases neurophysiologiques et les modalités optimales de l’adaptation prismatique (AP) restent à valider. Cette étude vise à explorer les effets sensori-moteurs, cognitifs et fonctionnels à long terme produits par une séance d’AP hebdomadaire pendant 4 semaines. Un essai monocentrique, en double insu, randomisé et contrôlé a été réalisé. Vingt patients avec NS gauche secondaire à un accident vasculaire cérébral droit ont été inclus (10 dans le groupe « prisme » et 10 dans le groupe « témoin »). Les effets sensori-mot…
Molecular mechanics models for the image charge, a comment on “including image charge effects in the molecular dynamics simulations of molecules on metal surfaces”
We re-investigate the image charge model of Iori and Corni (Iori and Corni, J. Comput. Chem. 2008, 29, 1656). We find that a simple symmetrization of their model allows to obtain quantitatively correct results for the electrostatic interaction of a water molecule with a metallic surface. This symmetrization reduces the magnitude of the electrostatic interaction to less than 10% of the total interaction energy. © 2017 Wiley Periodicals, Inc.
Enhancing Visuomotor Adaptation by Reducing Error Signals: Single-step (Aware) versus Multiple-step (Unaware) Exposure to Wedge Prisms
Abstract Neglect patients exhibit both a lack of awareness for the spatial distortions imposed during visuomanual prism adaptation procedures, and exaggerated postadaptation negative after-effects. To better understand this unexpected adaptive capacity in brain-lesioned patients, we investigated the contribution of awareness for the optical shift to the development of prism adaptation. The lack of awareness found in neglect was simulated in a multiple-step group where healthy subjects remained unaware of the optical deviation because of its progressive stepwise increase from 2° to 10°. We contrasted this method with the classical single-step group in which subjects were aware of the visual …
Space representation in children with dyslexia and children without dyslexia: Contribution of line bisection and circle centering tasks
International audience; Line bisection tasks (different space locations and different line lengths) and circle centering tasks (visuo-proprioceptive and proprioceptive explorations, with left or right starting positions) were used to investigate space representation in children with dyslexia and children without dyslexia. In line bisection, children with dyslexia showed a significant rightward bias for central and right-sided locations and a leftward bias for left-sided location. Furthermore, the spatial context processing was asymmetrically more efficient in the left space. In children without dyslexia, no significant bias was observed in central lines but the spatial context processing wa…
Ten Facets, One Force Field: The GAL19 Force Field for Water–Noble Metal Interfaces
International audience; Understanding the structure of the water/metal interfaces plays an important role in many areas ranging from surface chemistry to environmental processes. The size, required phase-space sampling, and the slow diffusion of molecules at the water/metal interfaces motivate the development of accurate force fields. We develop and parametrize GAL19, a novel force field, to describe the interaction of water with two facets (111 and 100) of five metals (Pt, Pd, Au, Ag, Cu). To increase transferability compared to its predecessor GAL17, the water–metal interaction is described as a sum of pairwise terms. The interaction energy has three contributions: (i) physisorption is de…