959 resultados para dissociation constants


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Background. Many studies have separately reported abnormalities of frontal and temporal lobe structures in schizophrenia, but little is known of structural fronto-temporal associations in this condition. We investigated whether male patients with chronic schizophrenia would show abnormal patterns of correlation between regional brain volumes.

Methods. Structural magnetic resonance images of the brain in 42 patients were compared with 43 matched unaffected controls. We explored the pattern of association between regional brain volumes by correlational analyses, and non-parametrically tested for significance of between-group differences by randomization.

Results. The schizophrenics demonstrated significant volume deficits in several brain regions (left temporal lobe and hippocampus, right dorsolateral prefrontal cortex), and significant volume increases in the ventricular system (third ventricle and left temporal horn of the lateral ventricle). Controls demonstrated large positive correlations (r > 0.4) between prefrontal and temporal lobe regions. By contrast, inter-regional correlations significantly reduced in schizophrenics included those between prefrontal, anterior cingulate and temporal regions, and between posterior cingulate and hippocampus (P < 0.05). The most salient abnormality in patients was a dissociation between prefrontal and superior temporal gyrus volumes (P < 0.01).

Conclusions. These results support the existence of a relative 'fronto-temporal dissociation' in schizophrenia which we suggest may be due to lack of mutually trophic influences during frontal and temporal lobe development.

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Background: This study examined dissociation, shame, guilt and intimate relationship difficulties in those with chronic and complex PTSD. Little is known about how these symptom clusters interplay within the complex PTSD constellation. Dissociation was examined as a principle organizing construct
within complex PTSD. In addition, the impact of shame, guilt and dissociation on relationship difficulties was explored.
Methods: Sixty five treatment-receiving adults attending a Northern Irish service for conflict-related trauma were assessed on measures of dissociation, state and trait shame, behavioral responses to shame, state and trait guilt, complex PTSD symptom severity and relationship difficulties.
Results: Ninety five percent (n=62) of participants scored above cut-off for complex PTSD. Those with clinical levels of dissociation (n=27) were significantly higher on complex PTSD symptom severity, state and trait shame, state guilt, withdrawal in response to shame and relationship preoccupation than subclinical dissociators (n=38). Dissociation and state and trait shame predicted complex PTSD. Fear of relationships was predicted by dissociation, complex PTSD and avoidance in response to shame, while complex PTSD predicted relationship anxiety and relationship depression.
Limitations: The study was limited to a relatively homogeneous sample of individuals with chronic and complex PTSD drawn from a single service.
Conclusions: Complex PTSD has significant consequences for intimate relationships, and dissociation makes an independent contribution to these difficulties. Dissociation also has an organizing effect on
complex PTSD symptoms.

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Following on from a quantitative study, this research used a qualitative methodology to investigate the lived experience of 3 men with chronic posttraumatic stress disorder associated with the conflict in Northern Ireland who reported auditory hallucinations. Data analysis used the Framework method. Results showed that beliefs about voices, dissociation of identity and body, and interpersonal impact were central superordinate themes associated with auditory hallucinations in posttraumatic stress disorder. Central subordinate themes included feeling a lack of controllability over voices, experiencing them as ego-dystonic, and feeling an increased sense of isolation and shame because of their presence. Results provide an in-depth analysis of participants' lived experiences and enhance understanding of previous quantitative findings.

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Following trauma, most people with initial symptoms of stress recover, but it is important to identify those at risk for continuing difficulties so resources are allocated appropriately. There has been limited investigation of predictors of posttraumatic stress disorder following natural disasters. This study assessed psychological difficulties experienced in 101 adult treatment seekers following exposure to a significant earthquake. Peritraumatic dissociation, posttraumatic stress symptoms, anxiety, depression, and emotional support were assessed. Path analysis was used to determine whether the experience of some psychological difficulties predicted the experience of other difficulties. As hypothesized, peritraumatic dissociation was found to predict posttraumatic stress symptoms and anxiety. Posttraumatic stress symptoms then predicted anxiety and depression. Depression and anxiety were highly correlated. Contrary to expectations, emotional support was not significantly related to other psychological variables. These findings justify the provision of psychological support following a natural disaster and suggest the benefit of assessing peritraumatic dissociation and posttraumatic stress symptoms soon after the event to identify people in need of monitoring and intervention.

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Reactivity of supported gold catalysts is a hot topic in catalysis for many years. This communication reports an investigation on the dissociation of molecular hydrogen at the perimeter sites of Au/TiO2 and the spillover of hydrogen atoms from the gold to the support using density functional theory calculations. It is found that the heterolytic dissociation is favoured in comparison with homolytic dissociation of molecular hydrogen at the perimeter sites. However, the surface oxygen of the rutile TiO2(110) surface at these sites can be readily passivated by the formed OH, suggesting that further dissociation of molecular hydrogen may occur at pure gold sites.

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The energetics of the low-temperature adsorption and decomposition of nitrous oxide, N(2)O, on flat and stepped platinum surfaces were calculated using density-functional theory (DFT). The results show that the preferred adsorption site for N(2)O is an atop site, bound upright via the terminal nitrogen. The molecule is only weakly chemisorbed to the platinum surface. The decomposition barriers on flat (I 11) surfaces and stepped (211) surfaces are similar. While the barrier for N(2)O dissociation is relatively small, the surface rapidly becomes poisoned by adsorbed oxygen. These findings are supported by experimental results of pulsed N(2)O decomposition with 5% Pt/SiO(2) and bismuth-modified Pt/C catalysts. At low temperature, decomposition occurs but self-poisoning by O((ads)) prevents further decomposition. At higher temperatures some desorption Of O(2) is observed, allowing continued catalytic activity. The study with bismuth-modified Pt/C catalysts showed that, although the activation barriers calculated for both terraces and steps were similar, the actual rate was different for the two surfaces. Steps were found experimentally to be more active than terraces and this is attributed to differences in the preexponential term. (C) 2004 Elsevier Inc. All rights reserved.

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Resonance-enhanced multiphoton ionization of H2 + exposed to elliptically polarized VUV laser pulses is investigated. Differential cross sections for nuclei and electron are obtained using numerical solutions of the time-dependent Schrödinger equation. In this work in progress, we explore the dependence of the dissociative ionization observables with the polarization of the light.

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BaH (and its isotopomers) is an attractive molecular candidate for laser cooling to ultracold temperatures and a potential precursor for the production of ultracold gases of hydrogen and deuterium. The theoretical challenge is to simulate the laser cooling cycle as reliably as possible and this paper addresses the generation of a highly accurate ab initio $^{2}\Sigma^+$ potential for such studies. The performance of various basis sets within the multi-reference configuration-interaction (MRCI) approximation with the Davidson correction (MRCI+Q)is tested and taken to the Complete Basis Set (CBS) limit. It is shown that the calculated molecular constants using a 46 electron Effective Core-Potential (ECP) and even-tempered augmented polarized core-valence basis sets (aug-pCV$n$Z-PP, n= 4 and 5) but only including three active electrons in the MRCI calculation are in excellent agreement with the available experimental values. The predicted dissociation energy De for the X$^2\Sigma^+$ state (extrapolated to the CBS limit) is 16895.12 cm$^{-1}$ (2.094 eV), which agrees within 0.1$\%$ of a revised experimental value of <16910.6 cm$^{-1}$, while the calculated re is within 0.03 pm of the experimental result.

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Choline supplementation improving memory functions in rodents is assumed to increase the synthesis and release of acetylcholine in the brain. We have found that a combined pre- and postnatal supplementation results in long-lasting facilitation of spatial memory in juvenile rats when training was conducted in presence of a local salient cue. The present work was aimed at analysing the effects of peri- and postnatal choline supplementation on spatial abilities of naive adult rats. Rats given a perinatal choline supplementation were trained in various cued procedures of the Morris navigation task when aged 5 months. The treatment had a specific effect of reducing the escape latency of the rats when the platform was at a fixed position in space and surrounded by a suspended cue. This effect was associated with an increased spatial bias when the cue and platform were removed. In this condition, the control rats showed impaired spatial discrimination following the removal of the target cue, most likely due to an overshadowing of the distant environmental cues. This impairment was not observed in the treated rats. Further training with the suspended cue at unpredictable places in the pool revealed longer escape latencies in the control than in the treated rats suggesting that this procedure induced a selective perturbation of the normal but not of the treated rats. A special probe trial with the cue at an irrelevant position and no escape platform revealed a significant bias of the control rats toward the cue and of the treated rats toward the uncued spatial escape position. This behavioural dissociation suggests that a salient cue associated with the target induces an alternative "non spatial" guidance strategy in normal rats, with the risk of overshadowing of the more distant spatial cues. In this condition, the choline supplementation facilities a spatial reliance on the cue, that is an overall facilitation of learning a set of spatial relations between several visual cues. As a consequence, the improved escape in presence of the cue is associated with a stronger memory of the spatial position following disappearance of the cue. This and previous observations suggest that a specific spatial attention process relies on the buffering of highly salient visual cues.to facilitate integration of their relative position in the environment.

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Les déficits auditifs spatiaux se produisent fréquemment après une lésion hémisphérique ; un précédent case report suggérait que la capacité explicite à reconnaître des positions sonores, comme dans la localisation des sons, peut être atteinte alors que l'utilisation implicite d'indices sonores pour la reconnaissance d'objets sonores dans un environnement bruyant reste préservée. En testant systématiquement des patients avec lésion hémisphérique inaugurale, nous avons montré que (1) l'utilisation explicite et/ou implicite des indices sonores peut être perturbée ; (2) la dissociation entre l'atteinte de l'utilisation explicite des indices sonores versus une préservation de l'utilisation implicite de ces indices est assez fréquente ; et (3) différents types de déficits dans la localisation des sons peuvent être associés avec une utilisation implicite préservée de ces indices sonores. Conceptuellement, la dissociation entre l'utilisation explicite et implicite de ces indices sonores peut illustrer la dichotomie des deux voies du système auditif. Nos résultats parlent en faveur d'une évaluation systématique des fonctions auditives spatiales dans un contexte clinique, surtout quand l'adaptation à un environnement sonore est en jeu. De plus, des études systématiques sont nécessaires afin de mettre en lien les troubles de l'utilisation explicite versus implicite de ces indices sonores avec les difficultés à effectuer les activités de la vie quotidienne, afin d'élaborer des stratégies de réhabilitation appropriées et afin de s'assurer jusqu'à quel point l'utilisation explicite et implicite des indices spatiaux peut être rééduquée à la suite d'un dommage cérébral.

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The assembly and testing of apparatus for the measurement of elastic and photoelastic constants by Brillouin scattering, using a Fabry-Perot interferometer and with argon ion laser excitation is described. Such measurements are performed on NaCI, KBr and LiF using the A = 488.0 nm laser line. The elastic constants obtained here are in very good agreement with the ultrasonic data for all three materials. The discrepancy between ultrasonic and hypersonic sound velocities which was reported by some authors for KBr and LiF is not confirmed, and the elastic constants obtained for LiF are the most accurate to date. Also, the present photoelastic constants are in good agreement with the data obtained by ultrasonic techniques for all three crystals. The results for the KBr and LiF crystals constitute the first set of photoelastic constants obtained for these materials by Brillouin spectroscopy. Our results for LiF are the best available to date.

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A new approach to treating large Z systems by quantum Monte Carlo has been developed. It naturally leads to notion of the 'valence energy'. Possibilities of the new approach has been explored by optimizing the wave function for CuH and Cu and computing dissociation energy and dipole moment of CuH using variational Monte Carlo. The dissociation energy obtained is about 40% smaller than the experimental value; the method is comparable with SCF and simple pseudopotential calculations. The dipole moment differs from the best theoretical estimate by about 50% what is again comparable with other methods (Complete Active Space SCF and pseudopotential methods).

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The interaction of biological molecules with water is an important determinant of structural properties both in molecular assemblies, and in conformation of individual macromolecules. By observing the effects of manipulating the activity of water (which can be accomplished by limiting its concentration or by adding additional solutes, "osmotic stress"), one can learn something about intrinsic physical properties of biological molecules as well as measure an energetic contribution of closely associated water molecules to overall equilibria in biological reactions. Here two such studies are reported. The first of these examines several species of lysolipid which, while present in relatively low concentrations in biomembranes, have been shown to affect many cellular processes involving membrane-protein or membrane-membrane interactions. Monolayer elastic constants were determined by combining X-ray diffraction and the osmotic stress technique. Spontaneous radii of curvature of lysophosphatidylcholines were determined to be positive and in the range +30A to +70A, while lysophosphatidylethanolamines proved to be essentially flat. Neither lysolipid significantly affected the bending modulus of the monolayer in which it was incorporated. The second study examines the role of water in theprocess of polymerization of actin into filaments. Water activity was manipulated by adding osmolytes and the effect on the equilibrium dissociation constant (measured as the criticalmonomer concentration) was determined. As water activity was decreased, the critical concentration was reduced for Ca-actin but not for Mg-actin, suggesting that 10-12 fewer water molecules are associated with Ca-actin in the polymerized state. Thisunexpectedly small amount of water is discussed in the context of the common structural motif of a nucleotide binding cleft.

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L’objectif de cette étude était d’évaluer l’influence des habiletés perceptives sur les capacités de production vocale dans l’amusie congénitale. Treize amusiques et douze contrôles appariés ont réalisé quatre tâches : deux tâches de discrimination perceptive et deux tâches de production vocale. Les stimuli utilisés pour les tâches étaient des enregistrements vocaux provenant des participants, rendant les tâches plus écologiques et enlevant le besoin pour les participants de modifier le timbre des stimuli lorsqu’ils chantent. Les résultats ont démontré que, malgré le fait que les contrôles aient surpassé la performance des amusiques dans toutes les tâches, il y avait beaucoup plus de variabilité dans les performances des amusiques que prévu. La moitié des amusiques avaient des performances égales à celles des contrôles sur les deux tâches perceptives. D’autres amusiques montraient des performances égales ou semblables à celles des contrôles sur au moins une des tâches d’imitation vocale. Ces résultats mènent à croire qu’il serait possible que ces deux types d’habiletés musicales soient dissociables.