Comparison of different methodologies for the computation of damped nonlinear normal modes and resonance prediction of systems with non-conservative nonlinearities

Nonlinear Dynamics - The nonlinear modes of a non-conservative nonlinear system are sometimes referred to as damped nonlinear normal modes (dNNMs). Because of the non-conservative...     

A Switch in the Hydrophobic/Hydrophilic Gas-Adsorption Character of Prussian Blue Analogues: An Affinity Control for Smart Gas Sorption

Porous coordination polymers are molecule-based materials presenting a high degree of tunability, which offer many advantages for targeted applications over conventional inorganic materials. This work demonstrates that the hydrophilic/hydrophobic character of Prussian blue analogues having a lipophilic feature may be tuned to optimize the gas adsorption properties. The role of the coordinatively unsaturated metal sites is emphasized through a combination of theoretical and experimental study of water, ethanol, and n-hexane adsorption.     

Exploring the self-assembly of dumbbell-shaped polyoxometalate hybrids,from molecular building units to nanostructured soft materials

The formation of hierarchical nanostructures using preformed dumbbell-like species made of covalent organic–inorganic polyoxometalate (POM)-based hybrids is herein described. In this system, the presence of charged subunits (POM, metal linkers, and counter ions) in the complex molecular architecture can drive their aggregation, which results from a competition between the solvation energy of the discrete species and intermolecular electrostatic interactions. We show that the nature of the POM and the charge of the metal linker are key parameters for the hierarchical nanoorganization. The experimental findings were corroborated with a computational investigation combining DFT and molecular dynamics simulation methods, which outlines the importance of solvation of the counter ion and POM/counter ion association in the aggregation process. The dumbbell-like species can also form gels, in the presence of a poorer solvent, displaying similar nanoorganization of the aggregates. We show that starting from the designed molecular building units whose internal charges can be controlled by redox trigger we can achieve their implementation into soft nanostructured materials through the control of their supramolecular organization.

The formation of hierarchical nanostructures using supramolecular dumbbell-like species made of organic–inorganic polyoxometalate-based hybrids is investigated by combination of SAXS and computational methods.     

MRI of thermally denatured blood: methemoglobin formation and relaxation effects

Focal regions of T₁-shortening have been observed in magnetic resonance imaging (MRI)-monitored thermal ablations of perfused tissues. The aims of this study were two-fold: to find evidence for heat-induced conversion of hemoglobin (Hb) to methemoglobin (mHb), and to investigate the effects of heat treatment of in-vitro blood components upon their MR relaxation times. Spectrophotometric studies were performed to confirm the heat-induced formation of methemoglobin. Preparations of whole and fractionated blood, previously submitted to elevated temperatures of 40°C to 80°C, were imaged and the relaxation times were calculated. Optical absorption spectra of samples containing free Hb, heated to 60°C, showed increased light absorption at 630 nm, evident of mHb presence. Short T₁ values in whole blood (1.13 s) and packed red blood cell (0.65 s) compartments, heated at 60°C, compared to their baseline values (1.62 s and 0.83 s, respectively), were attributed to mHb formation. In relation to MRI-guided thermal interventions, these results suggest a possible explanation for observation of hyperintense regions on T₁-weighted images.     

Bismuth Modified Gold Microelectrode for Pb(II) Determination in Wine Using Alkaline Medium

Electrodeposition of bismuth on gold microelectrodes for determination of Pb(II) by square wave anodic stripping voltammetry (SWASV) was accomplished by an in situ procedure in alkaline solution. A linear calibration plot for Pb(II) in the concentration range 40 to 6700 nmol L^?1 (r=0.998) was obtained, the detection limit was found to be 12.5 nmol L^?1 (S/N=3) and the relative standard deviation in solutions containing 1 μmol L^?1 Pb(II) was 4% (n=12). The analytical performance of the proposed sensor was tested by measuring the Pb(II) concentration in a wine sample. The result was in good agreement with the one obtained by GFAAS.     

The use of a gold disc microelectrode for the determination of copper in human sweat

A novel approach of using a gold disc microelectrode to analyze sweat samples for copper ions by anodic square wave stripping voltammetry (SW stripping voltammetry) is described. Sweat was collected from the lower back of four subjects after physical exercise and the sample volume required for the determinations was 100 μL. Under the optimized conditions, the calibration plot was linear over the range 1-100 μmol L⁻¹ Cu(II) with a limit of detection of 0.25 μmol L⁻¹. The precision was evaluated by carrying out five replicate measurements in a 1 μmol L⁻¹ Cu(II) solution and the standard deviation was found to be 1.5%. Measurements were performed by inserting the microelectrode into sweat drops and Cu(II) concentrations in the analyzed samples ranged from 0.9 to 28 μmol L⁻¹. Values obtained by the proposed voltammetric method agreed well with those found using graphite furnace atomic absorption spectroscopy (GFAAS).     

Bound nonlocality and activation

We investigate nonlocality distillation using measures of nonlocality based on the Elitzur-Popescu-Rohrlich decomposition. For a certain number of copies of a given nonlocal box, we define two quantities of interest: (i) the nonlocal cost and (ii) the distillable nonlocality. We find that there exist boxes whose distillable nonlocality is strictly smaller than their nonlocal cost. Thus nonlocality displays a form of irreversibility which we term "bound nonlocality." Finally, we show that nonlocal distillability can be activated.     

Dynamic analysis of fretting-wear in friction contact interfaces

A numerical treatment of fretting-wear under vibratory loading is proposed. The method is based on the Dynamic Lagrangian Frequency Time method. It models unilateral contact by using Coulomb’s friction law. The basic idea is to separate time into two scales, a slow scale for tribological phenomena and a fast scale for dynamics. For a given number of vibration periods, a steady state is assumed and the variables are decomposed into Fourier series. An Alternating Frequency Time procedure is performed to calculate the non-linear forces. Then, a hybrid Powell solver is used. Numerical investigations on a beam with friction contact interfaces illustrate the performances of this method and show the coupling between dynamic and tribological phenomena.