Rhodium-catalyzed asymmetric hydrogenation of olefins with PhthalaPhos, a new class of chiral supramolecular ligands

A library of 19 binol-derived chiral monophosphites that contain a phthalic acid diamide group (Phthala- Phos) has been designed and synthesized in four steps. These new ligands were screened in the rhodium-catalyzed enantioselective hydrogenation of prochiral dehydroamino esters and enamides. Several members of the library showed excellent enantioselectivity with methyl 2-acetamido acrylate (6 ligands gave >97% ee), methyl (Z)-2- acetamido cinnamate (6 ligands gave >94% ee), and N-(1-phenylvinyl)acetamide (9 ligands gave >95% ee), whilst only a few representatives afforded high enantioselectivities for challenging and industrially relevant substrates N-(3,4-dihydronaphthalen-1- yl)-acetamide (96% ee in one case) and methyl (E)-2-(acetamidomethyl)-3- phenylacrylate (99% ee in one case). In most cases, the new ligands were more active and more stereoselective than their structurally related monodentate phosphites (which are devoid of functional groups that are capable of hydrogen-bonding interactions). Control experiments and kinetic studies were carried out that allowed us to demonstrate that hydrogen-bonding interactions involving the diamide group of the PhthalaPhos ligands strongly contribute to their outstanding catalytic properties. Computational studies carried out on a rhodium precatalyst and on a conceivable intermediate in the hydrogenation catalytic cycle shed some light on the role played by hydrogen bonding, which is likely to act in a substrate-orientation effect. \ua9 2012 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim

Emotional imagination of negative situations: Functional neuroimaging in anorexia and bulimia

AimThe present study aims to extend the knowledge of the neural correlates of emotion processing in first episode subjects affected by anorexia nervosa (AN) or bulimia nervosa (BN). We applied an emotional distress paradigm targeting negative emotions thought to be relevant for interpersonal difficulties and therapeutic resistance mechanisms.MethodsThe current study applied to 44 female participants with newly diagnosed AN or BN and 20 matched controls a neuroimaging paradigm eliciting affective responses. The measurements also included an extensive assessment comprising clinical scales, neuropsychological tests, measures of emotion processing and empathy.ResultsAN and BN did not differ from controls in terms of emotional response, emotion matching, self-reported empathy and cognitive performance. However, eating disorder and psychopathological clinical scores, as well as alexithymia levels, were increased in AN and BN. On a neural level, no significant group differences emerged, even when focusing on a region of interest selected a priori: the amygdala. Some interesting findings put in relation the hippocampal activity with the level of Body Dissatisfaction of the participants, the relative importance of the key nodes for the common network in the decoding of different emotions (BN = right amygdala, AN = anterior cingulate area), and the qualitative profile of the deactivations.ConclusionsOur data do not support the hypothesis that participants with AN or BN display reduced emotional responsiveness. However, peculiar characteristics in emotion processing could be associated to the three different groups. Therefore, relational difficulties in eating disorders, as well as therapeutic resistance, could be not secondary to a simple difficulty in feeling and identifying basic negative emotions in AN and BN participants

Restraint of appetite and reduced regional brain volumes in anorexia nervosa: a voxel-based morphometric study

<p>Abstract</p> <p>Background</p> <p>Previous Magnetic Resonance Imaging (MRI) studies of people with anorexia nervosa (AN) have shown differences in brain structure. This study aimed to provide preliminary extensions of this data by examining how different levels of appetitive restraint impact on brain volume.</p> <p>Methods</p> <p>Voxel based morphometry (VBM), corrected for total intracranial volume, age, BMI, years of education in 14 women with AN (8 RAN and 6 BPAN) and 21 women (HC) was performed. Correlations between brain volume and dietary restraint were done using Statistical Package for the Social Sciences (SPSS).</p> <p>Results</p> <p>Increased right dorsolateral prefrontal cortex (DLPFC) and reduced right anterior insular cortex, bilateral parahippocampal gyrus, left fusiform gyrus, left cerebellum and right posterior cingulate volumes in AN compared to HC. RAN compared to BPAN had reduced left orbitofrontal cortex, right anterior insular cortex, bilateral parahippocampal gyrus and left cerebellum. Age negatively correlated with right DLPFC volume in HC but not in AN; dietary restraint and BMI predicted 57% of variance in right DLPFC volume in AN.</p> <p>Conclusions</p> <p>In AN, brain volume differences were found in appetitive, somatosensory and top-down control brain regions. Differences in regional GMV may be linked to levels of appetitive restraint, but whether they are state or trait is unclear. Nevertheless, these discrete brain volume differences provide candidate brain regions for further structural and functional study in people with eating disorders.</p

Correlational structure of ‘frontal’ tests and intelligence tests indicates two components with asymmetrical neurostructural correlates in old age

AbstractBoth general fluid intelligence (gf) and performance on some ‘frontal tests’ of cognition decline with age. Both types of ability are at least partially dependent on the integrity of the frontal lobes, which also deteriorate with age. Overlap between these two methods of assessing complex cognition in older age remains unclear. Such overlap could be investigated using inter-test correlations alone, as in previous studies, but this would be enhanced by ascertaining whether frontal test performance and gf share neurobiological variance. To this end, we examined relationships between gf and 6 frontal tests (Tower, Self-Ordered Pointing, Simon, Moral Dilemmas, Reversal Learning and Faux Pas tests) in 90 healthy males, aged ~73years. We interpreted their correlational structure using principal component analysis, and in relation to MRI-derived regional frontal lobe volumes (relative to maximal healthy brain size). gf correlated significantly and positively (.24≤r≤.53) with the majority of frontal test scores. Some frontal test scores also exhibited shared variance after controlling for gf. Principal component analysis of test scores identified units of gf-common and gf-independent variance. The former was associated with variance in the left dorsolateral (DL) and anterior cingulate (AC) regions, and the latter with variance in the right DL and AC regions. Thus, we identify two biologically-meaningful components of variance in complex cognitive performance in older age and suggest that age-related changes to DL and AC have the greatest cognitive impact

Preliminary numerical solutions of the evolution of free jets. IMECE2012-86730

The present paper presents preliminary numerical solutions of the flow evolution of a two dimensional rectangular free jet. The numerical simulations in a two-dimensional domain are carried out with Open-FOAM, the open-source code, and compare the numerical results with the experimental visualizations performed in the same laboratory with the shadowgraph technique. The evolution of a two-dimensional submerged free jet is reported in the literature by the presence of two regions of flow: the potential core, where the centerline velocity maintains equal to that on the slot exit, and the turbulent or mixing region, where the centerline velocity decreases with the distance from the exit. Previous anemometric measurements, carried out in this laboratory with an air jet emerging from a rectangular channel, showed the presence of a region of flow, just outside the exit and before the potential core, where velocity and turbulence remain almost equal to those measured on the exit, and it has been called “undisturbed region of flow” because is present also in turbulent conditions. Previous and present shadowgraph visualizations show a jet which has the same height along the undisturbed region of flow and increases its height afterwards. The length of the undisturbed region depends on the Reynolds number of the flow and on the presence of turbulence promoters, e.g. metallic grids, at the exit of the slot. The undisturbed region is becoming nil with the increase of the Reynolds numbers, in agreement to the literature. The present two dimensional numerical solutions, carried out at Re numbers equal to 25,000 and 60,000 confirm the results obtained with the shadow visualizations

Three-dimensional numerical simulation of the fluid dynamics in a coronary stent

Stents are commonly used to restore blood flow in patients with severe coronary artery disease. Local hemodynamic variables, as wall shear stress, have an important role in the restenosis and their distribution depends on the stent geometry. The objective of the present study is to carry out CFD simulations in a realistic 3D geometry of a coronary stent in physiological conditions. A comparison is performed between two reconstructed stents, made of 12 rings and similar to the real coronary ones, which differ by the position of the struts, where the first type is with closed cells and the second one with open cells. The artery is modeled as a cylinder with rigid walls and the blood is assumed as incompressible Newtonian fluid in laminar flow with constant physical properties. The commercial computational fluid dynamic code FLUENT is used with a mesh composed of non uniform tetrahedrons. The simulations are performed in steady and unsteady state. Wall shear stresses, WSS, as well as its time variations, are investigated in unsteady state with the conclusion that the stent with closed cells have a better fluid dynamic behavior

Numerical solution of three-dimensional rectangular submerged jets with the evidence of the undisturbed region of flow

The evolution of turbulent rectangular submerged free jets has been investigated numerically with a two-dimensional (2D) approach by the present authors and, by using the large eddy simulations (LES) at several Reynolds numbers. The average numerical results confirmed the presence of the undisturbed region of flow (URF) located between the slot exit and the beginning of the potential core region (PCR) previously observed experimentally at the University of Rome “Tor Vergata” by Gori and coworkers. The 2D study of the present authors carried out under the conditions previously investigated in the literature, showed that the URF has a self-similar behavior, and proposed a new law for the evolution of the momentum. The present paper extends the LES to three-dimensional (3D) rectangular submerged free jets, in the range from Re = 5,000 to Re = 40,000, showing that the self-similar behavior of URF is also present in the 3D numerical simulations, as well as in the PCR and in the fully developed region (FDR).</p