The prediction of chemical reactivity from first principles: Collision and reaction dynamics

Aquest treball fa una revisió de mesures experimentals i càlculs teòrics sobre la dinàmica de col·lisions i reaccions moleculars. Els experiments se centren en col·lisions, a energies intermèdies, que involucren sistemes del tipus ió-àtom i iómolècula, per les quals es mesuren seccions eficaces totals, estat a estat, així com aquelles que discerneixen les diferents contribucions del moment angular d'espín. Els resultats obtinguts s'interpreten satisfactòriament en termes d'acoblaments no adiabàtics entre els diferents estats electrònics dels sistemes col·lisionants. Els càlculs teòrics utilitzen la metodologia quasiclàssica, així com metodologies mecanoquàntiques recentment desenvolupades, tant aproximades com exactes. S'han obtingut resultats totalment convergits per sistemes tipus, mentre que s'han analitzat, de manera detallada i extensiva, les característiques dinàmiques de sistemes triatòmic, tetraatòmic i pentaatòmic.

X-ray photoelectron spectroscopy of oxygen adsorbates on Al(111): Theory experiment

We present the result of polar angle resolved x¿ray photoemission spectroscopy on Al(111)/O and cluster calculations of the O(1s) binding energy (BE) for various model situations. In the experimental data two O(1s) peaks are observed, separated by 1.3 eV. The angular behavior (depth¿resolution) could indicate that the lower BE peak is associated with an O atom under the surface, and the higher BE peak with an O atom above the surface. Equally, it could indicate oxygen islands on the surface where the perimeter atoms have a higher O(1s) BE than the interior atoms. The cluster calculations show that the former interpretation cannot be correct, since an O ads below the surface has a higher calculated O(1s) BE than one above. Cluster calculations simulating oxygen islands are, however, consistent with the experimental data.

Weakening processes in thrust faults: insights from the Monte Perdido thrust fault (southern Pyrenees, Spain)

The Monte Perdido thrust fault (southern Pyrenees) consists of a 6-m-thick interval of intensely deformed clay-bearing rocks. The fault zone is affected by a pervasive pressure solution seam and numerous shear surfaces. Calcite extensional-shear veins are present along the shear surfaces. The angular relationships between the two structures indicate that shear surfaces developed at a high angle (70°) to the local principal maximum stress axis r1. Two main stages of deformation are present. The first stage corresponds to the development of calcite shear veins by a combination of shear surface reactivation and extensional mode I rupture. The second stage of deformation corresponds to chlorite precipitation along the previously reactivated shear surfaces. The pore fluid factor k computed for the two deformation episodes indicates high fluid pressures during the Monte Perdido thrust activity. During the first stage of deformation, the reactivation of the shear surface was facilitated by a suprahydrostatic fluid pressure with a pore fluid factor kv equal to 0.89. For the second stage, the fluid pressure remained still high (with a k value ranging between 0.77 and 0.84) even with the presence of weak chlorite along the shear surfaces. Furthermore, evidence of hydrostatic fluid pressure during calcite cement precipitation supports that incremental shear surface reactivations are correlated with cyclic fluid pressure fluctuations consis- tent with a fault-valve model.

Intrinsic coordinate system for the tibial plateau

Determination of the sub-chondral bone density, or more precisely the internal density spot, can be used to evaluate the capability of a knee to sustain normal kinematics. To use this technique as a mean of knee kinematics control, the position of the internal density spot must be determined in a reproducible way. This paper presents a definition of an intrinsic polar coordinate system, allowing to measure the position of the internal density spot of the tibial plateau. Tests of reproducibility gave good results and justify the use of this coordinate system for comparison of the internal density spot position between left and right paired knees.

Evaluation of muscular activity duration in shoulders with rotator cuff tears using inertial sensors and electromyography.

Shoulder disorders, including rotator cuff tears, affect the shoulder function and result in adapted muscle activation. Although these adaptations have been studied in controlled conditions, free-living activities have not been investigated. Based on the kinematics measured with inertial sensors and portable electromyography, the objectives of this study were to quantify the duration of the muscular activation in the upper trapezius (UT), medial deltoid (MD) and biceps brachii (BB) during motion and to investigate the effect of rotator cuff tear in laboratory settings and daily conditions. The duration of movements and muscular activations were analysed separately and together using the relative time of activation (TEMG/mov). Laboratory measurements showed the parameter's reliability through movement repetitions (ICC > 0.74) and differences in painful shoulders compared with healthy ones (p < 0.05): longer activation for UT; longer activation for MD during abduction and tendency to shorter activation in other movements; shorter activation for BB. In daily conditions, TEMG/mov for UT was longer, whereas it was shorter for MD and BB (p < 0.05). Moreover, significant correlations were observed between these parameters and clinical scores. This study thus provides new insights into the rotator cuff tear effect on duration of muscular activation in daily activity.

Strategic Adaptation in Function of Chronicity of Schizophrenic Symptoms During A Fluency Task: An fMRI Study

Background: Language processing abnormalities and executive difficulties are hallmark features of schizophrenia. The objective of this study is to assess the blood oxygenation level-dependent (BOLD) response at two different stages of the illness (i.e. comparison between adolescents and adults with schizophrenic symptoms) during a fluency task.Methods: BOLD responses during a covert verbal fluency task were compared between 11 psychotic adolescents with schizophrenic symptoms (mean age 16,9 years) and 14 adults with schizophrenia (mean age 33,4 years). fMRI data were analyzed with standard routine of spm5.Results: First, expected activation's network was found for both groups, separately. Secondly, adolescents showed greater activation in left rolandic opercule (BA 48), left angular (BA 39) and right hippocampus compared to adults. Thirdly, adults demonstrated greater activation in presupplementary motor area (BA 6) and in precentral area (BA 4) compared to adolescents.Conclusions: The adolescents seemed to recruit a verbal network (Broca and Wernicke) and memory abilities to perform a fluency task. In contrast, adults seemed to recruit more executive function abilities to perform a similar task. Despite the evolution of schizophrenia, which is known to have a deleterious influence on the prefrontal cortex development, adult patients seemed to be able to recruit such areas to perform a verbal fluency / executive function task.

On the Upper Ordovician unconformity in the Pyrenees: New evidence from the La Cerdanya area

In recent years, contradictory reports about whether or not an unconformity exists at the base of the Upper Ordovician succession of the Pyrenees have been made. In the Cerdanya area (Central Pyrenees), good outcrop evidence for this unconformity is displayed at the base of the Rabassa conglomerates. In this area, the Upper Ordovician rocks overlie a tilted Cambro-Ordovician sequence, displaying an angular unconformity and indicating a break in the stratigraphic series. Moreover, the existence of such an unconformity is supported by the distribution of Variscan minor structures, suggesting that the Cambro-Ordovician and the Upper Ordovician strata initially had different orientations before the main Variscan folding.

Generalização de um índice de intensidade de infecção em experimentos de avaliação de doenças em plantas

Em experimentos de avaliação de doenças em plantas é comum a classificação de indivíduos de cada parcela experimental, segundo classes de uma escala quantitativa discreta, mediante avaliação visual da severidade de doença. O objetivo deste trabalho foi apresentar a generalização de uma medida que associa uma resposta quantitativa denominada índice de intensidade de infecção, o qual é expresso por I=sen²ômega, a cada distribuição de freqüências obtida nas parcelas, e cuja transformação angular ômega=arcsen I0,5 pode ser submetida à análise da variação. Desde que o cálculo de ômega não envolve os valores ou notas da escala, ele pode ser aplicado também a uma escala qualitativa ordinal.

Statistical assessment of dataset shift and model portability in multi-angle in-track image acquisitions

In this study we propose an evaluation of the angular effects altering the spectral response of the land-cover over multi-angle remote sensing image acquisitions. The shift in the statistical distribution of the pixels observed in an in-track sequence of WorldView-2 images is analyzed by means of a kernel-based measure of distance between probability distributions. Afterwards, the portability of supervised classifiers across the sequence is investigated by looking at the evolution of the classification accuracy with respect to the changing observation angle. In this context, the efficiency of various physically and statistically based preprocessing methods in obtaining angle-invariant data spaces is compared and possible synergies are discussed.

Neurophysiological changes during shortening osteotomies of the spine.

BACKGROUND CONTEXT: Kyphotic deformities with sagittal imbalance of the spine can be treated with spinal osteotomies. Those procedures are known to have a high incidence of neurological complications, in particular at the thoracic level. Motor evoked potentials (MEPs) have been widely used in helping to avoid major neurological deficits postoperatively. Previous reports have shown that a significant proportion of such cases present with important transcranial MEP (Tc-MEP) changes during surgery with some of them being predictive of postoperative deficits. PURPOSE: Our aim was to study Tc-MEP changes in a consecutive series of patients and correlate them with clinical parameters and radiological changes. STUDY DESIGN/SETTING: Retrospective case notes study from a prospective patient register. PATIENT SAMPLE: Eighteen patients undergoing posterior shortening osteotomies (nine at thoracic and nine at lumbar levels) for kyphosis of congenital, degenerative, inflammatory, or post-traumatic origin were included. OUTCOME MEASURES: Loss of at least 80% of Tc-MEP signal expressed as the area under the curve percentual change, of at least one muscle. METHODS: We studied the relation between outcome measure (80% Tc-MEP loss in at least one muscle group) and amount of posterior vertebral body shortening as well as angular correction measured on computed tomography scans, occurrence of postoperative deficits, intraoperative blood pressure at the time of the osteotomy, and hemoglobin (Hb) change. RESULTS: All patients showed significant Tc-MEP changes. In particular, greater than 80% MEP loss in at least one muscle group was observed in five of nine patients in the thoracic group and four of nine patients in the lumbar group. No surgical maneuver was undertaken as a result of this loss in an effort to improve motor responses other than verifying the stability of the construct and the extent of the decompression. Four patients developed postoperative deficits of radicular origin, three of them recovering fully at 3 months. No relation was found between intraoperative blood pressure, Hb changes, and Tc-MEP changes. Severity of Tc-MEP loss did not correlate with postoperative deficits. Shortening of more than 10 mm was linked to more severe Tc-MEP changes in the thoracic group. CONCLUSIONS: Transcranial MEP changes during spinal shortening procedures are common and do not appear to predict severe postoperative deficits. Total loss of Tc-MEP (not witnessed in our series) might require a more drastic approach with possible reversal of the correction and wake-up test.

Cómo elaborar, tutorizar y evaluar un trabajo de fin de máster

Los estudios de nivel superior en el marco de la Unión Europea se componen del Grado y del Postgrado (Másters y doctorados). Los Másters son titulaciones producto de una formación avanzada, multidisciplinar o especializada, dirigida a la consecución de logros académicos en profundidad, de especialidades profesionales o de iniciación a la investigación. Los estudios deMaster exigen la evaluación continua del proceso de aprendizaje que se concreta finalmente en el denominado Trabajo de Fin de Máster, verdadera piedra angular de la formación del estudiante. Ese trabajo final está pensado para evidenciar las competencias adquiridas a lolargo de todo el programa formativo y para demostrar el logro de los objetivos globales del aprendizaje. Es la prueba definitiva de la madurez y de la profesionalidad de una carrera hecha a conciencia...

Cómo elaborar, tutorizar y evaluar un trabajo de fin de máster

Los estudios de nivel superior en el marco de la Unión Europea se componen del Grado y del Postgrado (Másters y doctorados). Los Másters son titulaciones producto de una formación avanzada, multidisciplinar o especializada, dirigida a la consecución de logros académicos en profundidad, de especialidades profesionales o de iniciación a la investigación. Los estudios deMaster exigen la evaluación continua del proceso de aprendizaje que se concreta finalmente en el denominado Trabajo de Fin de Máster, verdadera piedra angular de la formación del estudiante. Ese trabajo final está pensado para evidenciar las competencias adquiridas a lolargo de todo el programa formativo y para demostrar el logro de los objetivos globales del aprendizaje. Es la prueba definitiva de la madurez y de la profesionalidad de una carrera hecha a conciencia...

Cómo elaborar, tutorizar y evaluar un trabajo de fin de máster

Los estudios de nivel superior en el marco de la Unión Europea se componen del Grado y del Postgrado (Másters y doctorados). Los Másters son titulaciones producto de una formación avanzada, multidisciplinar o especializada, dirigida a la consecución de logros académicos en profundidad, de especialidades profesionales o de iniciación a la investigación. Los estudios deMaster exigen la evaluación continua del proceso de aprendizaje que se concreta finalmente en el denominado Trabajo de Fin de Máster, verdadera piedra angular de la formación del estudiante. Ese trabajo final está pensado para evidenciar las competencias adquiridas a lolargo de todo el programa formativo y para demostrar el logro de los objetivos globales del aprendizaje. Es la prueba definitiva de la madurez y de la profesionalidad de una carrera hecha a conciencia...

Métodos indiretos para estimar a massa de forragem em pastos de Cynodon spp

O planejamento e o manejo em sistemas de produção animal em pastagens utilizam como informação essencial valores de massa e taxas de acúmulo de forragem. Este trabalho avaliou dois métodos, régua e prato ascendente, para estimar a massa de matéria seca de forragem em pastagens do gênero Cynodon, cultivares Florakirk, Tifton 85 e Coastcross. Os pastos foram mantidos a 5, 10, 15 e 20 cm de altura por meio de lotação contínua de ovinos em um delineamento experimental de blocos completos ao acaso com 4 repetições. Durante 12 meses foram geradas curvas de calibração do tipo y = a + bx entre altura do pasto (x), medida por meio de cada um dos dois métodos, e a massa de matéria seca de forragem correspondente (y), em kg ha-1. Os valores do intercepto (a) foram os mais influenciados por cultivar e época do ano. Houve variação apenas moderada nos valores do coeficiente angular (b). Essa variação esteve relacionada com modificações da estrutura do dossel forrageiro, particularmente a proporção de material morto. Os métodos não diferiram em precisão, porém o método do prato ascendente mostrou-se mais rápido e ágil. A calibração dos métodos deve ser específica para cada cultivar e realizada freqüentemente para que as equações geradas sejam precisas.

Ambulatory assessment of 3D ground reaction force using plantar pressure distribution.

This study aimed to use the plantar pressure insole for estimating the three-dimensional ground reaction force (GRF) as well as the frictional torque (T(F)) during walking. Eleven subjects, six healthy and five patients with ankle disease participated in the study while wearing pressure insoles during several walking trials on a force-plate. The plantar pressure distribution was analyzed and 10 principal components of 24 regional pressure values with the stance time percentage (STP) were considered for GRF and T(F) estimation. Both linear and non-linear approximators were used for estimating the GRF and T(F) based on two learning strategies using intra-subject and inter-subjects data. The RMS error and the correlation coefficient between the approximators and the actual patterns obtained from force-plate were calculated. Our results showed better performance for non-linear approximation especially when the STP was considered as input. The least errors were observed for vertical force (4%) and anterior-posterior force (7.3%), while the medial-lateral force (11.3%) and frictional torque (14.7%) had higher errors. The result obtained for the patients showed higher error; nevertheless, when the data of the same patient were used for learning, the results were improved and in general slight differences with healthy subjects were observed. In conclusion, this study showed that ambulatory pressure insole with data normalization, an optimal choice of inputs and a well-trained nonlinear mapping function can estimate efficiently the three-dimensional ground reaction force and frictional torque in consecutive gait cycle without requiring a force-plate.