EPR and pulsed ENDOR study of intermediates from reactions of aromatic azides with group 13 metal trichlorides

The reactions of group 13 metal trichlorides with aromatic azides were examined by CW EPR and pulsed ENDOR spectroscopies. Complex EPR spectra were obtained from reactions of aluminium, gallium and indium trichlorides with phenyl azides containing a variety of substituents. Analysis of the spectra showed that 4-methoxy-, 3-methoxy- and 2-methoxyphenyl azides all gave ‘dimer’ radical cations [ArNHC6H4NH2]+• and trimers [ArNHC6H4NHC6H4NH2]+• followed by polymers. 4-Azidobenzonitrile, with its electron-withdrawing substituent, did not react. In general the aromatic azides appeared to react most rapidly with AlCl3 but this reagent tended to generate much polymer. InCl3 was the least reactive group 13 halide. DFT computations of the radical cations provided corroborating evidence and suggested that the unpaired electrons were accommodated in extensive π-delocalised orbitals. A mechanism to account for the reductive conversion of aromatic azides to the corresponding anilines and thence to the dimers and trimers is proposedPublisher PDFPeer reviewe

Like grandparents, like parents: Empirical evidence and psychoanalytic thinking on the transmission of parenting styles

The authors discuss the issue of intergenerational transmission of parenting from an empirical and psychoanalytic perspective. After presenting a framework to explain their conception of parenting, they describe intergenerational transmission of parenting as a key to interpreting and eventually changing parenting behaviors. Then they present (1) the empirical approach aimed at determining if there is actually a stability across generations that contributes to harsh parenting and eventually maltreatment and (2) the psyphoanalytic thinking that seeks to explain the continuity in terms of representations and clinical phenomena. The authors also discuss the relationship between the attachment and the caregiving systems and hypothesize a common base for the two systems in childhood experience. Finally, they propose the psychoanalytic perspective as a fruitful theoretical framework to integrate the evidence for the neurophysiological mediators and moderators of intergenerational transmission. Psychoanalytically informed research can provide clinically relevant insights and hypotheses to be tested

Beyond variability: Subjective timing and the neurophysiology of motor cognition.

Movement simulation helps increasing the chances to reach goals. A cognitive task used to study the neuro-behavioral aspects of movement simulation is mental rotation: people mentally re-orient rotated pictures of hands. However, the involvement of the primary motor cortex (M1) in mental rotation is largely controversial. Such inconsistency could arise from potential methodological flaws in experimental procedures and data analysis. In particular, until now, the timing of M1 activity has been computed in absolute terms: from the onset of mental rotation (onset-locked), neglecting intra- and inter-subject variability. A novel phase-locked approach is introduced to synchronize the same phases of cognitive processing among different subjects and sessions. This approach was validated in the particular case of corticospinal excitability of the motor cortex during mental rotation. We identified the relative time-windows during which the excitability of M1 is effector-specifically modulated by different features of mental rotation. These time windows correspond to the 55%-85% of the subjective timing. In sum, (i) we introduce a new method to study the neurophysiology of motor cognition, and (ii) validating this method, we shed new light on the involvement of M1 in movement simulation

Geometric and analytic views in existence theorems for optimal control. III. Weak solutions

Existence theorems are proved for weak optimal solutions of problems of optimization with distributed and boundary control. Many examples are given. Application is made of recent remarks on closure properties of linear and nonlinear operators. Recent geometric, topological, and analytical views are brought to bear on the underlying seminormality conditions.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/45209/1/10957_2004_Article_BF00934060.pd

To hear or not to hear: Sound Availability Modulates Sensory-Motor Integration

When we walk in place with our eyes closed after a few minutes of walking on a treadmill, we experience an unintentional forward body displacement (drift), called the sensory-motor aftereffect. Initially, this effect was thought to be due to the mismatch experienced during treadmill walking between the visual (absence of optic flow signaling body steadiness) and proprioceptive (muscle spindles firing signaling body displacement) information. Recently, the persistence of this effect has been shown even in the absence of vision, suggesting that other information, such as the sound of steps, could play a role. To test this hypothesis, six cochlear-implanted individuals were recruited and their forward drift was measured before (Control phase) and after (Post Exercise phase) walking on a treadmill while having their cochlear system turned on and turned off. The relevance in testing cochlear-implanted individuals was that when their system is turned off, they perceive total silence, even eliminating the sounds normally obtained from bone conduction. Results showed the absence of the aftereffect when the system was turned off, underlining the fundamental role played by sounds in the control of action and breaking new ground in the use of interactive sound feedback in motor learning and motor development

Closure theorems for orientor fields and weak convergence

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/46195/1/205_2004_Article_BF00250438.pd

A new digital predictive predistorter for behavioral power amplifier linearization

This letter presents a new digital adaptive predistorter (PD) for power amplifier (PA) linearization based on a nonlinear auto-regressive moving average (NARMA) structure. The distinctive characteristic of this PD is its straightforward deduction from the NARMA PA model, without the need of using an indirect learningapproachto identify the PD function.The PD itself presents a NARMA structure, and hence it can be quickly implemented by means of lookup tables. Single and multicarrier modulated signals collected from a three-stage LDMOS class AB PA, with a maximum output power of 48-dBm CW have been used to validate the linearity performance of this new predictive predistorter.Peer Reviewe

Prediction of minimum temperatures in an alpine region by linear and non-linear post-processing of meteorological models

International audienceModel Output Statistics (MOS) refers to a method of post-processing the direct outputs of numerical weather prediction (NWP) models in order to reduce the biases introduced by a coarse horizontal resolution. This technique is especially useful in orographically complex regions, where large differences can be found between the NWP elevation model and the true orography. This study carries out a comparison of linear and non-linear MOS methods, aimed at the prediction of minimum temperatures in a fruit-growing region of the Italian Alps, based on the output of two different NWPs (ECMWF T511?L60 and LAMI-3). Temperature, of course, is a particularly important NWP output; among other roles it drives the local frost forecast, which is of great interest to agriculture. The mechanisms of cold air drainage, a distinctive aspect of mountain environments, are often unsatisfactorily captured by global circulation models. The simplest post-processing technique applied in this work was a correction for the mean bias, assessed at individual model grid points. We also implemented a multivariate linear regression on the output at the grid points surrounding the target area, and two non-linear models based on machine learning techniques: Neural Networks and Random Forest. We compare the performance of all these techniques on four different NWP data sets. Downscaling the temperatures clearly improved the temperature forecasts with respect to the raw NWP output, and also with respect to the basic mean bias correction. Multivariate methods generally yielded better results, but the advantage of using non-linear algorithms was small if not negligible. RF, the best performing method, was implemented on ECMWF prognostic output at 06:00 UTC over the 9 grid points surrounding the target area. Mean absolute errors in the prediction of 2 m temperature at 06:00 UTC were approximately 1.2°C, close to the natural variability inside the area itself

Poor Oral Health as a Determinant of Malnutrition and Sarcopenia

Aging is accompanied by profound changes in many physiological functions, leading to a decreased ability to cope with stressors. Many changes are subtle, but can negatively affect nutrient intake, leading to overt malnutrition. Poor oral health may affect food selection and nutrient intake, leading to malnutrition and, consequently, to frailty and sarcopenia. On the other hand, it has been highlighted that sarcopenia is a whole-body process also affecting muscles dedicated to chewing and swallowing. Hence, muscle decline of these muscle groups may also have a negative impact on nutrient intake, increasing the risk for malnutrition. The interplay between oral diseases and malnutrition with frailty and sarcopenia may be explained through biological and environmental factors that are linked to the common burden of inflammation and oxidative stress. The presence of oral problems, alone or in combination with sarcopenia, may thus represent the biological substratum of the disabling cascade experienced by many frail individuals. A multimodal and multidisciplinary approach, including personalized dietary counselling and oral health care, may thus be helpful to better manage the complexity of older people. Furthermore, preventive strategies applied throughout the lifetime could help to preserve both oral and muscle function later in life. Here, we provide an overview on the relevance of poor oral health as a determinant of malnutrition and sarcopenia

Geometric and analytic views in existence theorems for optimal control. II. Distributed and boundary controls

Existence theorems are proved for Lagrange problems of optimization in a given domain G with possibly unbounded distributed controls in G and on the boundary of G , and with functional relations on G and on the boundary represented by closed operators, not necessarily linear. The case where the functional relations are partial differential equations is emphasized. Recent work concerning the reduction or elimination of seminormality requirements is taken into account. Many examples are given.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/45200/1/10957_2004_Article_BF00933208.pd