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.     

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”.     

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.     

Simulation of the instability of an accelerating gaseous envelope

The development of perturbations of the parameters of a dense gaseous envelope traveling with an acceleration driven by a difference in the pressures on either side is investigated numerically. Plane and axisymmetric time-dependent flows of a compressible medium are considered. The effect of both the density of the envelope and the form of the initial perturbations of its shape and motion on the mass cumulation in the compactions formed is studied. The evolutions of the perturbations of a layer and the surface of a contact discontinuity accelerated by an impinging plane shock wave are compared.     

Similar quartz crystallographic textures in rocks of continental earth’s crust (by neutron diffraction data): II. Quartz textures in monophase rocks

The types of quartz textures found in a large collection of multiphase rocks from different regions of the earth are analyzed. Crystallographic textures of granulite, amphibolite, slate, and gneiss samples are measured, classified, and compared with the similar textures of monomineral rocks.     

Shapes of a rotating rheonomic rod

The case of a rotating fluid mass is one of the classical fields of mechanics [1]. In particular, the solution of creep problems for a rotating mass is actual in geophysics in connection with Earth gravity force simulation on rotating samples under laboratory conditions [2]. A special case of a rheonomic rod in a potential field was studied in [3], where it was shown that the main problem about the rod shapes is the problem of determining the relations between the Lagrangian and Euler coordinates in the creep process.In what follows, we show how this problem can be solved for a rotating rod.     

Dynamic stability of uncertain laminated beams subjected to subtangential loads

Because of the inherent complexity of fiber-reinforced laminated composites, it can be challenging to manufacture composite structures according to their exact design specifications, resulting in unwanted material and geometric uncertainties. Thus the understanding of the effect of uncertainties in laminated structures on their static and dynamic responses is highly important for a reliable design of such structures. In this research, we focus on the probabilistic stability analysis of laminated structures subject to subtangential loading, a combination of conservative and nonconservative tangential loads, using the dynamic criterion. In order to study the dynamic behavior by including uncertainties into the problem, three models were developed: exact Monte Carlo simulation, sensitivity-based Monte Carlo simulation, and probabilistic FEA. These methods were integrated into the existing finite element analysis. Also, perturbation and sensitivity analysis have been used to study nonconservative problems to study the stability analysis using the dynamic criterion.     

New sources of “active” halogen bis(dialkylamide)hydrogen dibromobromates, efficient reagents for destruction of ecotoxicants

Bis(dialkylamide)hydrogen dibromobromates were synthesized and their reactivity was investigated in decomposition of diethylphosphonic, diethylphosphoric, and 4-toluenesulfonic acids 4-nitrophenyl esters. The nucleophilic reactivity of a typical α-nucleophile, hypobromite ion, is independent of the source of the active bromine. The cetyltrimethylammonium dibromobromate is a unique reagent for destruction of ecotoxicants. In weakly alkaline media the half-life of 4-nitrophenyl diethylphosphonate did not exceed 6 s at [BrO^?] 0.02 mol l^?1, and the apparent reaction rate compared to water increased ～40-fold. The main factor governing the micellar effects of surfactants is concentrating the substrate in the micellar pseudophase.     

Genetically Encoded Bioluminescent Indicator for ERK2 Dimer in Living Cells

In this study, a genetically encoded bioluminescent indicator for ERK2 dimer was developed with the split Renilla luciferase complementation method, in which the formation of ERK2 dimer induces a spontaneous emission of bioluminescence in living cells. In response to extracellular stimuli, such as epidermal growth factor (EGF) or 17β‐estradiol (E2), extracellular signal‐regulated kinase 2 (ERK2) is phosphorylated by its upstream kinase MEK, and also phosphorylates its substrates in various regions of the cell, including the nucleus. Phosphorylated ERK2 is led to form its dimer, thereby transporting itself into the nucleus. We demonstrated with the indicator that stimulation with EGF or E2 induces the formation of ERK2 dimer in living MCF‐7 cells. The dynamics of this dimer formation was examined and discussed.     

Weak Attractive Ligand–Polymer and Related Interactions in Catalysis and Reactivity: Impact,Applications, and Modeling

The notion of weak attractive ligand–polymer interactions is introduced, and its potential application, importance, and conceptual links with “cooperative” ligand–substrate interactions are discussed. Synthetic models of weak attractive ligand–polymer interactions are described, in which intramolecular weak C? H???F? C interactions (the existence of which remains contentious) have been detected by NMR spectroscopy and neutron and X‐ray diffraction experiments. These C? H???F? C interactions carry important implications for the design of catalysts for olefin polymerization, because they provide support for the practical feasibility of ortho‐F???H_β ligand–polymer contacts proposed for living Group 4 fluorinated phenoxyimine catalysts. The notion of weak attractive noncovalent interactions between an “active” ligand and the growing polymer chain is a novel concept in polyolefin catalysis.