Ab-Initio Investigation of Metal-Ceramic Bonding: M(001)/MgAl2O4(001), M = Al, Ag

The optimised adhesion geometry and the work of adhesion were determined for the interface systems Al(001)/MgAl₂O₄(001) and Ag(001)/MgAl₂O₄(001) by ab-initio density-functional calculations. Al is bound strongly on-top of oxygen at reduced lattice spacing, whereas weak adhesion and no unique optimum structure are obtained for Ag. An analysis of the electronic structure shows that in both systems the metal-ceramic interaction is spatially confined to a narrow range along the interface layers. The weak adhesion of Ag on spinel is mediated by a polarisation of the metal film, which may be classified as an image-charge interaction. In the case of Al a weak image-charge contribution is dominated by a strong electron-density redistribution perpendicular to the interface, which leads to the formation of directional Al—O bonds.     

Calibration of granular material parameters for DEM modelling and numerical verification by blade-granular material interaction

The discrete element method (DEM) is a promising approach to model blade-granular material interactions. The accuracy of DEM models depends on the model parameters. In this study, a calibration process was developed to determine the parameter values. The particle size was the same as the real material and the particle shape was modelled using two spherical particles rigidly clumped together to form a single grain. Laboratory shear tests and compressions tests were used to determine the material internal friction angle and stiffness, respectively. These tests were replicated numerically using DEM models with different sets of particle friction coefficients and particle stiffness values. The shear test results are found to be dependent on both the particle friction coefficient and the particle stiffness. The compression test results show that it is only dependent on the particle stiffness. The combination of shear test and compression test results can be used to determine a unique set of particle friction and particle stiffness values. The calibration process was validated experimentally and numerically by modelling a blade moving through granular material. Results show that the forces acting on the blade can be accurately modelled with DEM and the maximum error is found to be 26%. The relative particle-blade displacements were used to predict the position and shape of the shear lines in front of the blade. A good qualitative correlation was achieved between the experiments and the DEM simulations.     

Photophysics and Fluorimetric Titrations of Fluorescent Ion Indicators

A test based on time-resolved fluorescence experiments (Anal. Biochem. 245, 28–37, 1997) allows one to assess the interference of the excited-state association with the fluorimetric determination of the ground-state dissociation constant K _d of fluorescent ion:indicator complexes. If an inflection point occurs in the plot of the fluorescence signal vs – log[ion] in the ion concentration range where both decay times are invariant, this inflection point can be associated with the correct K _d. Here we apply this test to the fluorescent ion indicators SBFO (for Na⁺), Mag-fura-2 (for Mg²⁺), and APTRA-BTC (for Ca²⁺). In all three cases the decay times are invariant in the concentration ranges of the respective ions where the fluorescence titrations show unique inflection points, indicating that the fluorimetrically determined K _d values are the true K _d values.     

Time delay in a semi-active damper: modelling the bypass valve

Ride comfort and handling of off-road vehicles can be significantly improved by replacing the normal passive dampers in the vehicle suspension system with controllable, two-state, semi-active dampers. The hydraulic valve, which enables the semi-active damper characteristics to be controlled, is a critical component of a semi-active damper and has a marked influence on suspension performance. Models of the dynamics of a hydraulic bypass valve used on semi-active suspension systems for heavy vehicles were investigated. It is envisaged that similar models will eventually be incorporated into a full vehicle, three-dimensional simulation study. Valve response time (or time delay) is used as a measure of model accuracy because it is an important parameter in the performance of a semi-active damper. Models were created with AMESim, a commercial fluid power simulation environment, and MATLAB. AMESim was found to be capable of dealing with detailed and complex fluid power models. Attempts to solve models of similar complexity in the MATLAB environment were unsuccessful due to numerical stiffness. Experimental work was conducted to obtain dynamic performance data with which to validate model integrity. Several external factors influenced the valve behaviour during experiments. Test bench dynamics significantly influences results and obscures the absolute accuracy of the models and the experimental data. The investigation demonstrated an approach to creating fluid power models for this application that can be used in simulation, but also indicated that substantial effort is required in the process. The accuracy of the current model is not sufficient for design purposes.     

Nanobody‐Enabled Reverse Pharmacology on G‐Protein‐Coupled Receptors

The conformational complexity of transmembrane signaling of G‐protein‐coupled receptors (GPCRs) is a central hurdle for the design of screens for receptor agonists. In their basal states, GPCRs have lower affinities for agonists compared to their G‐protein‐bound active state conformations. Moreover, different agonists can stabilize distinct active receptor conformations and do not uniformly activate all cellular signaling pathways linked to a given receptor (agonist bias). Comparative fragment screens were performed on a β₂‐adrenoreceptor–nanobody fusion locked in its active‐state conformation by a G‐protein‐mimicking nanobody, and the same receptor in its basal‐state conformation. This simple biophysical assay allowed the identification and ranking of multiple novel agonists and permitted classification of the efficacy of each hit in agonist, antagonist, or inverse agonist categories, thereby opening doors to nanobody‐enabled reverse pharmacology.     

Modeling of mass and charge transfer in an inverted rotating disk electrode (IRDE) reactor

In this work, the validation of a newly constructed inverted rotating disk electrode (IRDE) reactor is reported. Compared to the rotating disk electrode (RDE) reactor, the working electrode is changed in position from the top to the bottom of the electrochemical cell. The IRDE reactor is designed to facilitate the actual study of gas evolution reactions. It is studied whether the first-order analytical expression for the velocity field in an RDE reactor is also acceptable for an IRDE configuration. To that purpose, the kinetic parameters of the well-known ferri/ferro cyanide redox system are determined in both configurations and compared. This is done qualitatively by comparing the polarization curves obtained in the inverted and the conventional RDE configuration. Additionally, a statistically founded fitting algorithm is used to quantitatively determine the model parameters of the oxidation and reduction reaction. Not only the diffusion coefficients of Fe²⁺ and Fe³⁺ are calculated, but also the rate constants (k_ox and k_red) and the transfer coefficients (α_ox and α_red) are quantified and compared together with their respective standard deviation. It is found that the parameters of mass and charge transfer in both configurations agree well. So it is concluded that the same analytical equations of mass and charge transfer can be used in both the RDE and the IRDE reactor.     

Fat retention at the tongue and the role of saliva: adhesion and spreading of 'protein-poor' versus 'protein-rich' emulsions

Fat perception of food emulsions has been found to relate to in-mouth friction. Previously, we have shown that friction under mouth-like conditions strongly depends on the sensitivity of protein-stabilized emulsion droplets to coalescence. Here, we investigated whether this also implies that oral fat retention depends in a similar manner on the stability of the emulsion droplets against coalescence. We investigate the separate contributions of droplet adhesion and droplet spreading to fat retention at the tongue, as well as the role of saliva. We perform ex vivo (Confocal Raman Spectroscopy; Confocal Scanning Laser Microscopy) experiments using pig's tongue surfaces in combination with human in vivo experiments. These reveal that protein-poor (unstable) emulsions are retained more at the tongue than protein-rich (stable) emulsions. Furthermore, the layer formed by adhering protein-poor droplets is more stable against rinsing. Saliva is found to be very efficient in removing fat and emulsion droplets from the oral surface but its role in fat retention needs further research. We relate our results to the colloidal forces governing droplet adhesion and spreading.