Effect of nanoparticles on the interfacial properties of liquid/liquid and liquid/air surface layers

An investigation is reported on the interfacial properties of nanometric colloidal silica dispersions in the presence of a cationic surfactant. These properties are the result of different phenomena such as the particle attachment at the interface and the surfactant adsorption at the liquid and at the particle interfaces. Since the latter strongly influences the hydrophobicity/lipophilicity of the particle, i.e., the particle affinity for the fluid interfacial environment, all those phenomena are closely correlated. The equilibrium and dynamic interfacial tensions of the liquid/air and liquid/oil interfaces have been measured as a function of the surfactant and particle concentration. The interfacial rheology of the same systems has been also investigated by measuring the dilational viscoelasticity as a function of the area perturbation frequency. These results are then crossed with the values of the surfactant adsorption on the silica particles, indirectly estimated through experiments based on the centrifugation of the dispersions. In this way it has been possible to point out the mechanisms determining the observed kinetic and equilibrium features. In particular, an important role in the mixed particle-surfactant layer reorganization is played by the Brownian transport of particles from the bulk to the interface and by the surfactant redistribution between the particle and fluid interface.     

Modulation of hydrophobic effect by cosolutes

This work concerns a comparison of the hydration properties and self-association behavior in aqueous solution of three biologically relevant simple molecules: tert-butyl alcohol (TBA), trimethylamine-n-oxide (TMAO), and glycine betaine (GB). These molecules were used as a model to study hydrophobic behavior in water solutions. In particular, water perturbation induced by TBA, TMAO, and GB molecules was studied as a function of the solute molar fraction X(2) (0 < X(2) < 0.04) by Raman spectra of water in the fundamental OH-stretching region (3,800-2,800 cm(-1)). Furthermore, possible hydrophobic clustering of these molecules was investigated by studying the behavior of the alkyl CH stretching band in the 3,100-2,900 cm(-1) frequency region as a function of X(2). To establish the existence of a correlation between the effects of these three solutes on the micellization process and changes in the properties of the solvent, the behavior of the critical micelle concentration of sodium dodecyl sulfate was also investigated as a function of the added amount of TBA, TMAO, and GB. On the whole, these data show that there is no direct correlation between a solute's effect on the water structure and its effect on micelle or protein stability. Results indicate that, while TBA starts to self-aggregate at approximately X(2) = 0.025, both TMAO and GB do not exhibit any significant self-aggregation up to the highest concentration considered. In addition, nonadditive perturbations of the H-bonded networks of solvent water are observed in the case of TBA solutions, but are absent in both the TMAO and GB cases. The absence of these nonlinear effects in TMAO and GB water solutions allow for tracing the microscopical mechanism of the neutrality of these osmolytes toward hydrophobic effects. This confers the compatibility to these two osmolytes, which can be accumulated at high concentrations without interfering with biochemical processes in the cell.     

Double excitations of helium in weak static electric fields

A dramatic electric field dependence has been observed in the fluorescence yield spectrum of the doubly excited states in helium, where a rich phenomenology is encountered below the threshold. Fluorescence yields of certain states can be tuned to zero, while other dipole-forbidden states are significantly enhanced, for fields much weaker than 1 kV/cm. Using an R-matrix multichannel quantum defect theory, spherical-to-parabolic frame transformation method, we are able to reproduce the main features of the observed spectrum, and we discuss the qualitative behavior in terms of weak electric field mixing.     

The unexpected reactivity of Zeise's anion in strong basic medium discloses new substitution patterns at the platinum centre

Zeise's anion in strongly basic hydroxylated solvents undergoes unprecedented nucleophilic addition of OR- (R = H, Me, Et) to the eta2-ethene giving trans-[PtCl2(eta1-C2H4OR)(OR)]2- which readily reacts with bidentate nitrogen donors N-N to give Cl- and OR- substitution and formation of [PtCl(CH2CH2OR)(N-N)]. Protonolysis of this stable organometallic species offers a versatile route to cationic [PtCl(eta2-C2H4)(N-N)]+ complexes.     

Changes in cerebral activity after decreased upper-limb hypertonus: an EMG-fMRI study

Objective

Whereas several studies have used functional magnetic resonance imaging (fMRI) to investigate motor recovery, whether therapy to decrease post-stroke hypertonus alters central motor patterns remains unclear. In this study, we used continuous electromyography (EMG)-fMRI to investigate possible changes in movement-related brain activation in patients receiving Botulinum toxin (BoNT-A) for hand-muscle hypertonus after chronic stroke.

Methods

We studied eight stroke patients all of whom had hemiparesis and associated upper-limb hypertonus. All patients underwent an fMRI-EMG recording and clinical-neurological assessment before BoNT-A and 5 weeks thereafter. The handgrip motor task during imaging was fixed across both patients and controls. The movements were metronome paced, movement amplitude and force were controlled with a plastic orthosis, dynamometer and EMG recording. An age-matched control group was recruited from among healthy volunteers underwent the same fMRI-EMG recording.

Results

Before BoNT-A, while patients moved the paretic hand, fMRI detected wide bilateral activation in the sensorymotor areas (SM1), in the supplementary motor area (SMA) and cerebellum. After BoNT-A blood oxygenation level-dependent (BOLD) activation decreased in ipsilateral and contralateral motor areas and became more lateralized. BOLD activation decreased also in ipsilateral cerebellar regions and in the SMA.

Conclusion

Changes in peripheral upper-limb hypertonus after BoNT-A were associated to an improvement in active movements and more lateralized and focalized activation of motor areas. The clinical and EMG-fMRI coregistration technique we used to study hand-muscle hypertonus in patients receiving BoNT-A after chronic stroke should be useful in future studies seeking improved strategies for post-stroke neurorehabilitation.     

Electro-oxidation of ethanol using PtSnRh/C electrocatalysts prepared by an alcohol-reduction process

PtRh/C (90:10), PtRh/C (50:50), PtSn/C (50:50), and PtSnRh/C (50:40:10) electrocatalysts were prepared by an alcohol-reduction process using ethylene glycol as solvent and reduction agent and Vulcan Carbon XC72 as supports. The electrocatalysts were characterized by energy-dispersive X-ray analysis, X-ray diffraction, and transmission electron microscopy. The electro-oxidation of ethanol was studied by cyclic voltammetry chronoamperometry at room temperature and on a single cell of a direct ethanol fuel cell at 100 °C. Cyclic voltammetry and chronoamperometry experiments showed that PtSnRh/C and PtSn/C electrocatalysts have similar performance for ethanol oxidation at room temperature, while the activity of PtRh/C electrocatalysts was very low. At 100 °C on a single cell, PtSnRh/C showed superior performance compared to PtSn/C and PtRh/C electrocatalysts.     

Long-Time Behavior and Critical Limit of Subcritical SQG Equations in Scale-Invariant Sobolev Spaces

We consider the subcritical SQG equation in its natural scale-invariant Sobolev space and prove the existence of a global attractor of optimal regularity. The proof is based on a new energy estimate in Sobolev spaces to bootstrap the regularity to the optimal level, derived by means of nonlinear lower bounds on the fractional Laplacian. This estimate appears to be new in the literature and allows a sharp use of the subcritical nature of the \(L^\infty \) bounds for this problem. As a by-product, we obtain attractors for weak solutions as well. Moreover, we study the critical limit of the attractors and prove their stability and upper semicontinuity with respect to the strength of the diffusion.     

Bridging between short-range and long-range dependence with mixed spatio-temporal Ornstein–Uhlenbeck processes

While short-range dependence is widely assumed in the literature for its simplicity, long-range dependence is a feature that has been observed in data from finance, hydrology, geophysics and economics. In this paper, we extend a Lévy-driven spatio-temporal Ornstein–Uhlenbeck process by randomly varying its rate parameter to model both short-range and long-range dependence. This particular set-up allows for non-separable spatio-temporal correlations which are desirable for real applications, as well as flexible spatial covariances which arise from the shapes of influence regions. Theoretical properties such as spatio-temporal stationarity and second-order moments are established. An isotropic g-class is also used to illustrate how the memory of the process is related to the probability distribution of the rate parameter. We develop a simulation algorithm for the compound Poisson case which can be used to approximate other Lévy bases. The generalized method of moments is used for inference and simulation experiments are conducted with a view towards asymptotic properties.     

Easy knapsacks and the complexity of energy allocation problems in the smart grid

Motivated by the growing interest in the smart grid and intelligent energy management mechanisms we study two classes of domestic energy allocation problems. In the first case we work with a system that is tasked with scheduling the work on a number of appliances over a given time window. In the second one a collection of air conditioning appliances is used to control the temperature of a given domestic environment. Our framework for this case includes a simplified mechanism for modelling the heat exchange between the interior and the exterior of the given environment. We present various polynomial time algorithms and NP-hardness proofs. In particular the main result of the paper is a proof that although it is NP-hard to schedule the operation of a single air-conditioning unit, working at various temperature levels in a variable energy price regime, there is a polynomial time algorithm for controlling one such device working at a single temperature level, for houses with low thermal inertia. The algorithm analysis hinges on the properties of a polynomial time variant of the minimisation version of the knapsack problem which may be of independent interest.