Biomedical subjects
Publications and source records attributed to Didier Grandjean.
An in situ cell, which is capable of obtaining time resolved soft X-ray data (200 eV < E < 3000 eV) under hydrothermal conditions has been developed and used to study the self-assembly processes occurring during microporous aluminophosphate crystallization.
New highly mixed phases have been identified in Cu/ZnO systems by EXAFS and XANES at both the Cu and Zn K-edge. The phases were generated by ball-milling Cu(2)O/ZnO mixtures under three different atmospheres of synthetic air (SA), SA + CO(2) and CO(2). The system milled in CO(2) shows disproportionation of Cu(2)O into Cu(0), Cu(1+) (cuprite Cu(2)O-type phase) and Cu(2+) (tenorite CuO-type phase), while most of the Zn(2+) is transformed into a nanocrystalline/amorphous ZnO-type zincite that forms a superficial mixture of oxide and carbonate phases. When synthetic air is added to the CO(2) atmosphere, ball milling results in the oxidation of nearly half the Cu(1+) into Cu(2+) with no Cu metal formed. The copper phase in this material is almost entirely amorphous. In SA, a significant amount of Cu(2+)- and Zn(2+)-based phases appears to react to form a nanocrystalline/amorphous Cu(1-x)Zn(x)O (x approximately 0.3) solid solution. This distorted rock saltlike solid solution, in which Zn and Cu feature different octahedral environments, was never reported before. It is thought to be formed by incorporation of Zn(2+) in the Cu fcc sublattice of the cuprite Cu(2)O matrix and the concomitant oxidation of Cu(1+) into Cu(2+). The formation of such a highly mixed Cu(1-x)Zn(x)O phase indicates strong Cu/Zn interaction in the Cu/ZnO system, which also suggests the presence of highly mixed phases in conventionally prepared activated catalysts.
The effects of the addition of manganese to a series of TiO(2)-supported cobalt Fischer-Tropsch (FT) catalysts prepared by different methods were studied by a combination of X-ray diffraction (XRD), temperature-programmed reduction (TPR), transmission electron microscopy (TEM), and in situ X-ray absorption fine structure (XAFS) spectroscopy at the Co and Mn K-edges. After calcination, the catalysts were generally composed of large Co(3)O(4) clusters in the range 15-35 nm and a MnO(2)-type phase, which existed either dispersed on the TiO(2) surface or covering the Co(3)O(4) particles. Manganese was also found to coexist with the Co(3)O(4) in the form of Co(3-x)Mn(x)O(4) solutions, as revealed by XRD and XAFS. Characterization of the catalysts after H(2) reduction at 350 degrees C by XAFS and TEM showed mostly the formation of very small Co(0) particles (around 2-6 nm), indicating that the cobalt phase tends to redisperse during the reduction process from Co(3)O(4) to Co(0). The presence of manganese was found to hamper the cobalt reducibility, with this effect being more severe when Co(3-x)Mn(x)O(4) solutions were initially present in the catalyst precursors. Moreover, the presence of manganese generally led to the formation of larger cobalt agglomerates ( approximately 8-15 nm) upon reduction, probably as a consequence of the decrease in cobalt reducibility. The XAFS results revealed that all reduced catalysts contained manganese entirely in a Mn(2+) state, and two well-distinguished compounds could be identified: (1) a highly dispersed Ti(2)MnO(4)-type phase located at the TiO(2) surface and (2) a less dispersed MnO phase being in the proximity of the cobalt particles. Furthermore, the MnO was also found to exist partially mixed with a CoO phase in the form of rock-salt Mn(1-x)Co(x)O-type solid solutions. The existence of the later solutions was further confirmed by scanning transmission electron microscopy with electron energy loss spectroscopy (STEM-EELS) for a Mn-rich sample. Finally, the cobalt active site composition in the catalysts after reduction at 300 and 350 degrees C was linked to the catalytic performances obtained under reaction conditions of 220 degrees C, 1 bar, and H(2)/CO = 2. The catalysts with larger Co(0) particles ( approximately >5 nm) and lower Co reduction extents displayed a higher intrinsic hydrogenation activity and a longer catalyst lifetime. Interestingly, the MnO and Mn(1-x)Co(x)O species effectively promoted these larger Co(0) particles by increasing the C(5+) selectivity and decreasing the CH(4) production, while they did not significantly influence the selectivity of the catalysts containing very small Co(0) particles.
A CrAPO-5 molecular sieve has been investigated with X-ray absorption spectroscopy (EXAFS-XANES) as dehydrated material and after loading with water and ammonia to unravel the coordination geometries of Cr3+ in the framework of a microporous crystalline aluminophosphate, more particularly of the AFI-type. A comparison of the XANES data, a preedge analysis with crystal field multiplet calculations and EXAFS data, pointed toward the presence of framework Cr3+ which, on dehydration, takes on a distorted tetrahedral coordination state. Due to the 3d3 configuration of Cr3+, this unusual tetrahedral coordination environment strongly tends to transform into the more stable 6-fold coordination geometry by binding two extraframework water molecules during hydration. In the presence of ammonia, tetrahedral Cr3+ readily transforms into a 5-fold coordination geometry by binding one ammonia molecule. Therefore, depending on the environmental conditions, the Cr3+ ions can occur in a 4-, 5-, or 6-fold coordination. This observation underlines the flexibility of transition metal ions, such as Cr3+, to cope with unusual coordination geometries in inorganic hosts, making them interesting as potential active sites in heterogeneous catalysis.
The vocal expression of human emotions is embedded within language and the study of intonation has to take into account two interacting levels of information--emotional and semantic meaning. In addition to the discussion of this dual coding system, an extension of Brunswik's lens model is proposed. This model includes the influences of conventions, norms, and display rules (pull effects) and psychobiological mechanisms (push effects) on emotional vocalizations produced by the speaker (encoding) and the reciprocal influences of these two aspects on attributions made by the listener (decoding), allowing the dissociation and systematic study of the production and perception of intonation. Three empirical studies are described as examples of possibilities of dissociating these different phenomena at the behavioral and neurological levels in the study of intonation.
The hydrothermal crystallization of CoAPO-5 molecular sieves has been studied using time-resolved in-situ SAXS/WAXS, UV-vis, Raman, and XAS. Data collected during heating to 180 degrees C allowed the observation of different steps occurring during the transformation of the amorphous gel into a crystalline material from a macroscopic and atomic perspective. Raman spectroscopy detected the initial formation of Al-O-P bonds, whereas SAXS showed that these gel particles had a broad size distribution ranging from ca. 7 to 20 nm before crystallization began. WAXS showed that this crystallization was sharp and occurred at around 160 degrees C. Analysis of the crystallization kinetics suggested a one-dimensional growth process. XAS showed that Co(2+) transformed via a two-stage process during heating involving (i) a gradual transformation of octahedral coordination into tetrahedral coordination before the appearance of Bragg peaks corresponding to AFI, suggesting progressive incorporation of Co(2+) into the poorly ordered Al-O-P network up to ca. 150 degrees C, and (ii) a rapid transformation of remaining octahedral Co(2+) at the onset of crystallization. Co(2+) was observed to retard crystallization of AFI but provided valuable information regarding the synthesis process by acting as an internal probe. A three-stage, one-dimensional crystallization mechanism is proposed: (i) an initial reaction between aluminum and phosphate units forming a primary amorphous phase, (ii) progressive condensation of linear Al-O-P chains forming a poorly ordered structure separated by template molecules up to ca. 155 degrees C, and (iii) rapid internal reorganization of the aluminophosphate network leading to crystallization of the AFI crystal structure.
Multiple levels of processing are thought to be involved in the appraisal of emotionally relevant events, with some processes being engaged relatively independently of attention, whereas other processes may depend on attention and current task goals or context. We conducted an event-related fMRI experiment to examine how processing angry voice prosody, an affectively and socially salient signal, is modulated by voluntary attention. To manipulate attention orthogonally to emotional prosody, we used a dichotic listening paradigm in which meaningless utterances, pronounced with either angry or neutral prosody, were presented simultaneously to both ears on each trial. In two successive blocks, participants selectively attended to either the left or right ear and performed a gender-decision on the voice heard on the target side. Our results revealed a functional dissociation between different brain areas. Whereas the right amygdala and bilateral superior temporal sulcus responded to anger prosody irrespective of whether it was heard from a to-be-attended or to-be-ignored voice, the orbitofrontal cortex and the cuneus in medial occipital cortex showed greater activation to the same emotional stimuli when the angry voice was to-be-attended rather than to-be-ignored. Furthermore, regression analyses revealed a strong correlation between orbitofrontal regions and sensitivity on a behavioral inhibition scale measuring proneness to anxiety reactions. Our results underscore the importance of emotion and attention interactions in social cognition by demonstrating that multiple levels of processing are involved in the appraisal of emotionally relevant cues in voices, and by showing a modulation of some emotional responses by both the current task-demands and individual differences.
We report two functional magnetic resonance imaging experiments showing enhanced responses in human middle superior temporal sulcus for angry relative to neutral prosody. This emotional enhancement was voice specific, unrelated to isolated acoustic amplitude or frequency cues in angry prosody, and distinct from any concomitant task-related attentional modulation. Attention and emotion seem to have separate effects on stimulus processing, reflecting a fundamental principle of human brain organization shared by voice and face perception.
We compared electrical brain responses to fearful vs. neutral facial expressions in healthy volunteers while they performed an orthogonal gender decision task. Face stimuli either had a broadband spatial-frequency content, or were filtered to create either low spatial-frequency (LSF) or high spatial-frequency (HSF) faces, always overlapped with their complementary SF content in upside-down orientation to preserve the total stimulus energy. We tested the hypothesis that the coarse LSF content of faces might be responsible for an early modulation of event-related potentials (ERPs) to fearful expressions. Consistent with previous findings, we show that broadband images of fearful faces, relative to neutral faces, elicit a higher global field power of approximately 130 ms poststimulus onset, corresponding to an increased P1 component over lateral occipital electrodes, with neural sources located within the extrastriate visual cortex. Bandpass filtering of faces strongly affected the latency and amplitude of ERPs, with a suppression of the normal N170 response for both LSF and HSF faces, irrespective of expression. Critically, we found that LSF information from fearful faces, unlike HSF information, produced a right-lateralized enhancement of the lateral occipital P1, without any change in the scalp topography, relative to unfiltered (broadband) fearful faces. These results demonstrate that an early P1 response to fear expression depends on a visual pathway preferentially tuned to coarse-magnocellular inputs, and can persist unchanged even when the N170 generators are disrupted by SF filtering.
While artificial neural networks are regularly employed in modeling the perception of facial and vocal emotion expression as well as in automatic expression decoding by artificial agents, this approach is yet to be extended to the modeling of emotion elicitation and differentiation. In part, this may be due to the dominance of discrete and dimensional emotion models, which have not encouraged computational modeling. This situation has changed with the advent of appraisal theories of emotion and a number of attempts to develop rule-based models can be found in the literature. However, most of these models operate at a high level of conceptual abstraction and rarely include the underlying neural architecture. In this contribution, an appraisal-based emotion theory, the Component Process Model (CPM), is described that seems particularly suited to modeling with the help of artificial neural network approaches. This is due to its high degree of specificity in postulating underlying mechanisms including efferent physiological and behavioral manifestations as well as to the possibility of linking the theoretical assumptions to underlying neural architectures and dynamic processes. This paper provides a brief overview of the model, suggests constraints imposed by neural circuits, and provides examples on how the temporal unfolding of emotion can be conceptualized and experimentally tested. In addition, it is shown that the specific characteristics of emotion episodes can be profitably explored with the help of non-linear dynamic systems theory.
We investigated the spatio-temporal dynamic of attentional bias towards fearful faces. Twelve participants performed a covert spatial orienting task while recording visual event-related brain potentials (VEPs). Each trial consisted of a pair of faces (one emotional and one neutral) briefly presented in the upper visual field, followed by a unilateral bar presented at the location of one of the faces. Participants had to judge the orientation of the bar. Comparing VEPs to bars shown at the location of an emotional (valid) versus neutral (invalid) face revealed an early effect of spatial validity: the lateral occipital P1 component (approximately 130 ms post-stimulus) was selectively increased when a bar replaced a fearful face compared to when the same bar replaced a neutral face. This effect was not found with upright happy faces or inverted fearful faces. A similar amplification of P1 has previously been observed in electrophysiological studies of spatial attention using non-emotional cues. In a behavioural control experiment, participants were also better at discriminating the orientation of the bar when it replaced a fearful rather than a neutral face. In addition, VEPs time-locked to the face-pair onset revealed a C1 component (approximately 90 ms) that was greater for fearful than happy faces. Source localization (LORETA) confirmed an extrastriate origin of the P1 response showing a spatial validity effect, and a striate origin of the C1 response showing an emotional valence effect. These data suggest that activity in primary visual cortex might be enhanced by fear cues as early as 90 ms post-stimulus, and that such effects might result in a subsequent facilitation of sensory processing for a stimulus appearing at the same location. These results provide evidence for neural mechanisms allowing rapid, exogenous spatial orienting of attention towards fear stimuli.
Mesoporous alumina membranes ("anodic aluminium oxide", or "AAO") are made by anodic oxidation of aluminium metal. These membranes contain hexagonal arrays of parallel non-intersecting cylindrical pores perpendicular to the membrane surface. By varying the anodisation voltage, the pore diameters are controllable within the range 5-250 nm. We have used AAO membranes as templates for the electrochemical deposition of metals within the pores to produce nanowires. These represent assemblies of one-dimensional quantum wires with prospective applications in electronic, optoelectronic and magnetic devices. Detailed characterisation of the structures of these nanowire assemblies on a variety of length scales is essential to understand their physical properties and evaluate their possible applications. We have used EXAFS, XANES, WAXS, high energy X-ray diffraction and SAXS to study their structure and bonding. In this paper we report the results of our studies of four different nanowire systems supported in AAO membranes. These are the ferromagnetic metals iron and cobalt, the superconducting metal tin, and the semiconductor gallium nitride. Iron nanowires in pores of diameter over the range 12 nm-72 nm are structurally very similar to bcc bulk iron. They have a strong preferred orientation within the alumina pores. Their XANES shows significant differences from that of bulk iron, showing that the electronic structure of the iron nanowires depends systematically on their diameter. Cobalt nanowires are composed of a mixture of hcp and fcc phases, but the ratio of the two phases does not depend in a simple way on the pore diameter or preparation conditions. In bulk cobalt, the fcc beta-phase is normally stable only at high temperatures. Strong preferred orientation of the c-axis in the pores was found. Tin nanowires in alumina membranes with pores diameters between 12 nm and 72 nm have a tetragonal beta-structure at ambient temperature and also at 80 K. Magnetic susceptibility measurements show that they are diamagnetic, and become superconducting at the same temperature as bulk tin (3.7 K). Gallium nitride nanowires have been prepared in alumina membranes with pore diameter 24 nm by a novel method. Gallium nitrate was deposited in the pores from aqueous solution and thermolysed at 1000 degrees C to form Ga2O3, which was reacted with ammonia at 1000 degrees C. The GaN nanowires have the wurtzite structure. Preparation at 1150 degrees C led to the incorporation of aluminium in the GaN. The mesoscopic ordering of the pores in the AAO membranes and their filling by metal nanowires has been studied by SAXS, which shows patterns of Bragg peaks arising from the pore arrays. Additionally, the cobalt nanowires have been the subject of an initial ASAXS study.
Faces are multi-dimensional stimuli bearing important social signals, such as gaze direction and emotion expression. To test whether perception of these two facial attributes recruits distinct cortical areas within the right hemisphere, we used single-pulse transcranial magnetic stimulation (TMS) in healthy volunteers while they performed two different tasks on the same face stimuli. In each task, two successive faces were presented with varying eye-gaze directions and emotional expressions, separated by a short interval of random duration. TMS was applied over either the right somatosensory cortex or the right superior lateral temporal cortex, 100 or 200 ms after presentation of the second face stimulus. Participants performed a speeded matching task on the second face during one of two possible conditions, requiring judgements about either gaze direction or emotion expression (same/different as the first face). Our results reveal a significant task-stimulation site interaction, indicating a selective TMS-related interference following stimulations of somatosensory cortex during the emotional expression task. Conversely, TMS of the superior lateral temporal cortex selectively interfered with the gaze direction task. We also found that the interference effect was specific to the stimulus content in each condition, affecting judgements of gaze shifts (not static eye positions) with TMS over the right superior temporal cortex, and judgements of fearful expressions (not happy expressions) with TMS over the right somatosensory cortex. These results provide for the first time a double dissociation in normal subjects during social face recognition, due to transient disruption of non-overlapping brain regions. The present study supports a critical role of the somatosensory and superior lateral temporal regions in the perception of fear expression and gaze shift in seen faces, respectively.