Trans-amidate platinum complexes anchoring water and N-donor molecules. The importance of hydrogen bonding

The square planar bisnitrile platinum(II) derivatives PtCl2(NCR)2 (R=Ph (1 a); Et (1 b); p-C6H4F (1 c); p-C6H4tBu (1 d); m-C6H3Me2 (1 e); o, p-C6H2Me3 (1 f)) react with tetrabutylammonium hydroxide to render the monoaquo NBu4]trans-PtCl(HNCOR)2(OH2)] (2 a–2 f). The water molecule is s-coordinated to platinum and the binding is reinforced by two strong hydrogen bonds to the neighboring amidate ligands (OH···OC). Substitution of water in 2 a by N-donor ligands can be efficiently achieved only in the presence of a dehydrating agent as magnesium sulphate or 4 Å molecular sieves. By following this strategy, compounds NBu4]trans-PtCl(HNCOPh)2(NH2R’)] (R’=H (3), NH2 (4), tBu (5 a), p-C6H4Me (5 b) have been isolated. The incoming ligands are s-coordinated to platinum and also establish strong hydrogen bonds to the amidates (NH···OC). Treatment of 2 a with halogens causes oxidation at the metal center, rendering the platinum(IV) derivatives NBu4]PtClX2(HNCOPh)2(OH2)] (X=Cl (6 a), Br (6 b), I (6 c))

Constraining late-time transitions in the dark energy equation of state

One of the most compelling goals of observational cosmology is the characterisation of the properties of the dark energy component thought to be responsible for the recent acceleration of the universe, including its possible dynamics. In this work we study phenomenological but physically motivated classes of models in which the dark energy equation of state can undergo a rapid transition at low redshifts, perhaps associated with the onset of the acceleration phase itself. Through a standard statistical analysis we have used low-redshift cosmological data, coming from Type Ia supernova and Hubble parameter measurements, to set constraints on the steepness of these possible transitions as well as on the present-day values of the dark energy equation of state and in the asymptotic past in these models. We have also studied the way in which these constraints depend on the specific parametrisation being used. Our results confirm that such late-time transitions are strongly constrained. If one demands a matter-like pre-transition behaviour, then the transition is constrained to occur at high redshifts (effectively in the matter era), while if the pre-transition equation of state is a free parameter then it is constrained to be close to that of a cosmological constant. In any case, the value of dark energy equation of state near the present day must also be very similar to that of a cosmological constant. The overall conclusion is that any significant deviations from this behaviour can only occur in the deep matter era, so there is no evidence for a transition associated with the onset of acceleration. Observational tools capable of probing the dynamics of the universe in the deep matter era are therefore particularly important.Comment: 9 pages, 7 figures; Astronomy & Astrophysics (in press

Electrical conditioning of adipose-derived stem cells in a multi-chamber culture platform

In tissue engineering, several factors play key roles in providing adequate stimuli for cells differentiation, in particular biochemical and physical stimuli, which try to mimic the physiological microenvironments. Since electrical stimuli are important in the developing heart, we have developed an easy-to-use, cost-effective cell culture platform, able to provide controlled electrical stimulation aimed at investigating the influence of the electric field in the stem cell differentiation process. This bioreactor consists of an electrical stimulator and 12 independent, petri-like culture chambers and a 3-D computational model was used to characterize the distribution and the intensity of the electric field generated in the cell culture volume. We explored the effects of monophasic and biphasic square wave pulse stimulation on a mouse adipose-derived stem cell line (m17.ASC) comparing cell viability, proliferation, protein, and gene expression. Both monophasic (8V, 2ms, 1Hz) and biphasic (+4V, 1ms and -4V, 1ms; 1Hz) stimulation were compatible with cell survival and proliferation. Biphasic stimulation induced the expression of Connexin 43, which was found to localize also at the cell membrane, which is its recognized functional mediating intercellular electrical coupling. Electrically stimulated cells showed an induced transcriptional profile more closely related to that of neonatal cadiomyocytes, particularly for biphasic stimulation. The developed platform thus allowed to set-up precise conditions to drive adult stem cells toward a myocardial phenotype solely by physical stimuli, in the absence of exogenously added expensive bioactive molecules, and can thus represent a valuable tool for translational applications for heart tissue engineering and regeneration

Mean flow instabilities of two-dimensional convection in strong magnetic fields

The interaction of magnetic fields with convection is of great importance in astrophysics. Two well-known aspects of the interaction are the tendency of convection cells to become narrow in the perpendicular direction when the imposed field is strong, and the occurrence of streaming instabilities involving horizontal shears. Previous studies have found that the latter instability mechanism operates only when the cells are narrow, and so we investigate the occurrence of the streaming instability for large imposed fields, when the cells are naturally narrow near onset. The basic cellular solution can be treated in the asymptotic limit as a nonlinear eigenvalue problem. In the limit of large imposed field, the instability occurs for asymptotically small Prandtl number. The determination of the stability boundary turns out to be surprisingly complicated. At leading order, the linear stability problem is the linearisation of the same nonlinear eigenvalue problem, and as a result, it is necessary to go to higher order to obtain a stability criterion. We establish that the flow can only be unstable to a horizontal mean flow if the Prandtl number is smaller than order , where B0 is the imposed magnetic field, and that the mean flow is concentrated in a horizontal jet of width in the middle of the layer. The result applies to stress-free or no-slip boundary conditions at the top and bottom of the layer

Critical point network for drainage between rough surfaces

In this paper, we present a network method for computing two-phase flows between two rough surfaces with significant contact areas. Low-capillary number drainage is investigated here since one-phase flows have been previously investigated in other contributions. An invasion percolation algorithm is presented for modeling slow displacement of a wetting fluid by a non wetting one between two rough surfaces. Short-correlated Gaussian process is used to model random rough surfaces.The algorithm is based on a network description of the fracture aperture field. The network is constructed from the identification of critical points (saddles and maxima) of the aperture field. The invasion potential is determined from examining drainage process in a flat mini-channel. A direct comparison between numerical prediction and experimental visualizations on an identical geometry has been performed for one realization of an artificial fracture with a moderate fractional contact area of about 0.3. A good agreement is found between predictions and observations

Application of the MM5 and the analogous method to heavy rainfall event, the case of 16?18 October 2003 in Catalonia (NE Spain)

International audienceBetween the 16 and 18 October 2003, some amounts of precipitation greater than 225mm and sea waves higher than 8.5m were recorded in Catalonia (NE Spain) and near its coast. Some rivers in the NE of the region were overflowed and the sea swell produced several damages near the coast. In order to analyse this case and to improve the forecasting of events like this, two methodologies have been applied: one deterministic and another one, probabilistic. The deterministic analysis has been made by using the MM5 mesoscale model. A 48 h simulation has been designed for three domains connected with two way nesting and having 54, 18, 6 km horizontal grid resolution and vertical resolution of 23 levels, and it has been initialised with the NCEP Analyses. The simulation suggests that orography played an important role on the precipitation generation (maxima were located where the wind at low levels impinged on the mountain ranges perpendicularly). The strong pressure gradient produced in the North of Catalonia and West part of the Gulf of Lyon, was the responsible of the great marine alteration. On the other hand, the 6 km resolution precipitation forecast for Catalonia is accurate, since it shows a spatial distribution and amounts quite similar to the observations obtained from 315 automatic rain gauges. The analogous technique applied here, considers the meteorological situations similar to the current one, in terms of the 850 and 1000 hPa geopotential fields at 00:00 UTC and 12:00 UTC from the NCEP/NCAR meteorological reanalysis for the period 1958?2003. Two windows have been considered, the first one from 60° N to 30° N and from 30° W to 30° E, and the second one, centred in Catalonia, from 45° N to 37.5° N and from 5° W to 10° E. The best 100 analogous have been selected and the comparison of the results with those obtained for other heavy rainfall events has been also done

Voxel-lesion symptom mapping of coarse coding and suppression deficits in right hemisphere damaged patients

Several accounts of narrative comprehension deficits in adults with right hemisphere damage (RHD) focus on the basic comprehension processes of coarse semantic coding (CC) and suppression (SUP)1,2. CC activates wide-ranging aspects of word meaning, independent of the surrounding context. In RHD, CC deficits impair processing of more remote meanings/features of lexical-semantic representations (e.g., “rotten” as a feature of “apple”)3. The normal SUP process reduces mental activation of concepts that become contextually incompatible. SUP impairment in RHD is indexed by prolonged processing interference from contextually-inappropriate interpretations (e.g., the “ink” meaning of “pen,” in “He built a pen”)4,5. Adults with RHD may have deficits in CC, SUP, both, or neither6. Voxel-based lesion symptom mapping was used to identify right hemisphere (RH) anatomical correlates of CC and SUP deficits. Lesion-deficit correspondence data should help predict which RHD patients have which deficits and may be candidates for a deficit-focused treatment approach that simultaneously improves narrative comprehension7-9. The Bilateral Activation, Integration, and Selection (BAIS) framework of language processing10 suggests some basic hypotheses1. CC, related to the activation component, is hypothesized to involve posterior MTG and STG10,11. SUP, related to the attentionally-driven selection component, modulates lexical-level activation and message-level semantic integration to narrow representations to those most relevant to a comprehender’s goal. Selection is strongly associated with left IFGe.g,12 but RH IFG also is crucial for semantic filtering and selection13,14, especially for information more strongly active in the RH15. Basal ganglia circuits are likely involved, as well13,16