Medicinal Organometallic Chemistry: Designing Metal Arene Complexes as Anticancer Agents

The field of medicinal inorganic chemistry is rapidly advancing. In particular organometallic complexes have much potential as therapeutic and diagnostic agents. The carbon‐bound and other ligands allow the thermodynamic and kinetic reactivity of the metal ion to be controlled and also provide a scaffold for functionalization. The establishment of structure–activity relationships and elucidation of the speciation of complexes under conditions relevant to drug testing and formulation are crucial for the further development of promising medicinal applications of organometallic complexes. Specific examples involving the design of ruthenium and osmium arene complexes as anticancer agents are discussed.     

On the dynamic electromechanical loading of dielectric elastomer membranes

Dielectric elastomer actuators (DEAs) have received considerable attention recently due to large voltage-induced strains, which can be over 100%. Previously, a large deformation quasi-static model that describes the out-of-plane deformations of clamped diaphragms was derived. The numerical model results compare well with quasi-static experimental results for the same configuration. With relevance to dynamic applications, the time-varying response of initially planar dielectric elastomer membranes configured for out-of-plane deformations has not been reported until now. In this paper, an experimental investigation and analysis of the dynamic response of a dielectric elastomer membrane is reported. The experiments were conducted with prestretched DEAs fabricated from 0.5 mm thick polyacrylate films and carbon grease electrodes. The experiments covered the electromechanical spectrum by investigating membrane response due to (i) a time-varying voltage input and (ii) a time-varying pressure input, resulting in a combined electromechanical loading state in both cases. For the time-varying voltage experiments, the membrane had a prestretch of three and was passively inflated to various predetermined states, and then actuated. The pole strains incurred during the inflation were as high as 25.6%, corresponding to slightly less than a hemispherical state. On actuation, the membrane would inflate further, causing a maximum additional strain of 9.5%. For the time-varying pressure experiments, the prestretched membrane was inflated and deflated mechanically while a constant voltage was applied. The membrane was cycled between various predetermined inflation states, the largest of which was nearly hemispherical, which with an applied constant voltage of 3 kV corresponded to a maximum polar strain of 28%. The results from these experiments reveal that the response of the membrane is a departure from the classical dynamic response of continuum membrane structures. The dynamic response of the membrane is that of a damped system with specific deformation shapes reminiscent of the classical membrane mode shapes but without same-phase oscillation, that is to say all parts of the system do not pass through the equilibrium configuration at the same time. Of particular interest is the ability to excite these deformations through a varying electrical load at constant mechanical pressure.     

Experimental Evaluation of Strain Shielding in Distal Femur in Revision TKA

Theoretical concerns about the use of cemented and press-fit stems in revision total knee arthroplasty (TKA) include stress shielding with adverse effects on prosthesis fixation. Radiological studies have showed distal femoral bone resorption after revision TKA. The revision with use of stems can place abnormal stresses. These stresses can promote the effect of bone stress shielding and may contribute to bone loss. Experimental quantification of strain shielding in the distal synthetic femur following TKA is the main purpose of the present study. Three different constructs of TKA were assessed. The first construct included a stemless femoral component. The other two included a press-fit and a cemented femoral stem. Cortical bone strains were measured experimentally with tri-axial strain gauges in synthetic femurs before and after in-vitro knee surgery. The difference between principal strains of implanted and intact femur was calculated for each strain gauge position. This study indicates that the use of stems in distal femur changes the distribution and magnitude of bone strains. The press-fit stem provoked relevant bone area (stem length) subjected to strain shielding and also originated the highest reduction of strains in the distal region, which can potentially induce bone resorption. The stemless implanted femur produced minor bone strain changes relatively to the intact femur. The use of distal femur stems increases initial stability in the bone, but the observed reduction of strains in this region, relative to the intact femur, provokes strain shielding that can induce bone resorption and may compromise the long term implant stability.     

An Experimental Investigation into the Acoustic Characteristics of Fluid-filled Porous Structures—A Simplified Model of the Human Skull Cancellous Structure

In nature, shape and structure evolve from the struggle for better performance. Often, biological structures combine multiple beneficial properties, making research into mimicking them very complex. Presented here is a summary of observations from a series of experiments performed on a material that closely resembles the human skull bone’s cancellous structure under acoustic loads. Transmission loss through flat and curved open-cell polyurethane foam samples is observed using air and water as the two interstitial fluids. Reduction in strength and stiffness caused by porosity can be recovered partially by filling the interstitial pores with a fluid. The test findings demonstrate the influence of the interstitial fluid on the mechanical characteristics of a porous structure in a quantitative manner. It is also demonstrated that the transmission loss does not depend only on the mass per unit area of the structure as predicted by acoustic mass law. Current tests also demonstrate that the transmission loss is more sensitive to the interstitial fluid than the shape and support conditions of the structures. Test observations thus support the concepts of “moisture-sensitivity of biological design” and the “law of hierarchy in natural design”.     

Modeling of the diffraction pattern of 1D-disordered silicon carbide

A method for calculating the diffraction pattern of a 1D-disordered crystal structure is considered by the example of silicon carbide. One-dimensional disordering is described using a cell setting the mutual position of all close-packed crystal layers. Two models of structure disordering during the polytypic transformation of the silicon carbide cubic modification into hexagonal are discussed. The results of the calculation of the diffraction spectrum in different stages of polytypic transformation are reported. It is shown that 1D disordering leads to the formation of a set of weak diffraction reflections. The experimentally observed changes in the diffraction pattern can be interpreted within the hypothesis on crystal structure disordering through displacement of adjacent close-packed layers.     

Growth of Sb-Bi gradient single crystals

The growth conditions and structural quality of Sb-Bi gradient single crystals with Bi content from 2 to 18 at %, grown by the Czochralski method with solid phase feed, are investigated. Bi distribution in the crystals along their pulling direction are studied by electron probe microanalysis and the change in the interplanar spacing is analyzed by double-crystal X-ray diffraction. It is established that the pulling rate and feed mass affect the Bi distribution in Sb-Bi single crystals.     

Effect of Pressure on Fluid Damping in MEMS Torsional Resonators with Flow Ranging from Continuum to Molecular Regime

High quality factor of dynamic structures at micro and nano scale is exploited in various applications of micro electro-mechanical systems (MEMS) and nano electro-mechanical system. The quality factor of such devices can be very high in vacuum. However, when vacuum is not desirable or not possible, the tiny structures must vibrate in air or some other gas at pressure levels that may vary from atmospheric to low vacuum. The interaction of the surrounding fluid with the vibrating structure leads to dissipation, thus bringing down the quality factor. Depending on the ambient fluid pressure or the gap between the vibrating and the fixed structure, the fluid motion can range from continuum flow to molecular flow giving a wide range of dissipation. The relevant fluid flow characteristics are determined by the Knudsen number which is the ratio of the mean free path of the gas molecule to the characteristic flow length of the device. This number is very small for continuum flow and reasonably big for molecular flow. In this paper, we study the effect of fluid pressure on the quality factor by carrying out experiments on a MEMS device that consists of a double gimbaled torsional resonator. Such devices are commonly used in optical cross-connects and switches. We only vary fluid pressure to make the Knudsen number go through the entire range of continuum flow, slip flow, transition flow, and molecular flow. We experimentally determine the quality factor of the torsional resonator at different air pressures ranging from 760 Torr to 0.001 Torr. The variation of this pressure over six orders of magnitude ensures required rarefaction to range over all flow conditions. Finally, we get the variation of quality factor with pressure. The result indicates that the quality factor, Q, follows a power law, Q ∝P ^–r , with different values of the exponent r in different flow regimes. In the second part of the paper, we propose the use of effective viscosity for considering velocity slip conditions in solving Navier–Stokes equation numerically. This concept is validated with analytical results for a simple case and then compared with the experimental results presented in this paper. The study shows that the effective viscosity concept can be used effectively even for the molecular regime if the air-gap to length ratio is sufficiently small (h ₀/L<0.01). As this ratio increases, the range of validity decreases.     

Iteration scheme for accelerometer unit calibration by a guaranteeing approach

Methods for accelerometer unit calibration are usually based on sufficiently strict requirements on the knowledge of the gravity orientation with respect to the unit (of the order of fractions of an arc minute). But it is not always possible to know the orientation with such high accuracy. In the present paper, we consider an approach to accelerometer unit calibration for whose implementation it suffices to have rough angular information (of the order of tens of arc minutes). We use a guaranteeing approach to calculate optimal schemes calibration experiments and propose an iterative scheme of calibration.