Characterization of inclusion complexes of betamethasone-related steroids with cyclodextrins using high-performance liquid chromatography

HPLC was used to study the inclusion complexes formed between various beta- and gamma-cyclodextrins and a series of corticosteroids related to betamethasone. Apparent association constants were measured in acetonitrile-water for a set of 13 steroids. An increase in the stability of the steroid-cyclodextrin complex is observed at lower concentrations of acetonitrile. The effects of the nature of the halide at the 9-position, the location of a double bond within the C-ring, substitution at the 9- and 11-positions, and modification of the D-ring of the steroid backbone were studied. The 11- and 17-positions were found to be critically involved in the inclusion process. Larger apparent association constants were obtained with gamma-cyclodextrin (gamma-CD) than with beta-cyclodextrin (beta-CD) due to the increased diameter of the gamma-CD cavity. Van't Hoff plots were constructed to examine the thermodynamic properties of the inclusion process. Plots constructed using retention factors were found to be nonlinear when gamma-CD was present in the mobile phase. This is due to an increase in the strength of the inclusion complex as temperature decreases. Plots constructed using apparent association constants were linear, indicating that the mechanism of inclusion does not change over the range of temperatures studied (10 to 80 degrees C). Enthalpy-entropy compensation was observed for 11 of the 13 steroids studied. The usefulness of cyclodextrins to achieve the separation of steroids in HPLC is discussed and a practical application for the analysis of a steroid and three potential impurities is described.     

Hydrodynamics of a bounded vertical film with nonlinear surface properties

The drainage of a thin liquid film with an insoluble monolayer down a vertical wall is studied. Lubrication theory is used to develop a model where the film is pinned at the top with a given thickness and the film drains into a bath at the bottom. A nonlinear equation of state is used for the surface tension and the surface viscosity is a nonlinear function of the surfactant concentration; these are appropriate for some aqueous systems. The three partial differential equations are solved via discretization in space and then the resulting differential algebraic system is solved. Results are described for a wide range of parameters, and the conditions under which the free surface is immobilized are discussed.     

Synthesis of substituted 5-aminomethyl tetrahydro-isoquinolines and dihydro-isoindoles

The synthesis of ten substituted aminomethylene tetrahydro-isoquinolines is described, proceeding in eight steps from 5-hydroxyisoquinoline via reductive amination of N-Boc tetrahydro-isoquinoline 5-carboxaldehyde. Likewise, reductive amination was used to prepare four substituted dihydro-isoindoles from the corresponding aldehyde. The dihydro-isoindole ring system was conveniently accessed via a 2+2+2 cycloaddition reaction.     

Determination of total polyvinylpyrrolidone (PVP) in ophthalmic solutions by size exclusion chromatography with ultraviolet-visible detection

A straightforward size exclusion chromatography (SEC) method was developed and validated for the determination of total polivinylpyrrolidone (PVP) in ophthalmic solutions using the unusual combination of size exclusion chromatography (SEC), ultraviolet-visible detection and quantitation of an analyte peak that elutes in the total exclusion volume of the column. Samples of opthalmic solutions are diluted with water and injected onto a TSKgel G1000PW, 7.5 mm i.d. × 30 cm, 12 μm column at 50°C, with 80:20 0.1M sodium acetate-methanol mobile phase and UV detection at 220 nm. Validation was successful for a stability indicating pharmaceutical method, with parameters including specificity, accuracy, linearity, and precision within typical pharmaceutical acceptance criteria. A stress study with acid, base, peroxide, heat, and light indicates that there is no interference from drug, product, or excipients.     

Light emission from porous silicon single and multiple cavities

Experimental and theoretical techniques are used to examine the effects of microstructuring on the optical properties of multilayer, single and multiple microcavity structures fabricated from porous silicon. Measurements of the reflectivity and photoluminescence spectra of three multilayer samples are presented. The results are modelled using a transfer matrix technique including a negative absorption term to represent the effect of spontaneous emission which gives luminescence. The emitted light is strongly controlled by the optical modes of the structures and very good agreement is observed between theory and experiment.     

Imploding conical shock waves

The behaviour of conical shock waves imploding axisymmetrically was first studied numerically by Hornung (J Fluid Mech 409:1–12, 2000) and this prompted a limited experimental investigation into these complex flow patterns by Skews et al. (Shock Waves 11:323–326, 2002). Modification of the simulation boundary conditions, resulting in the loss of self-similarity, was necessary to image the flow experimentally. The current tests examine the temporal evolution of these flows utilising a converging conical gap of fixed width fed by a shock wave impinging at its entrance, supported by CFD simulations. The effects of gap thickness, angle and incident shock strength were investigated. The wave initially diffracts around the outer lip of the gap shedding a vortex which, for strong incident shock cases, can contain embedded shocks. The converging shock at exit reflects on the axis of symmetry with the reflected wave propagating outwards resulting in a triple point developing on the incident wave together with the associated shear layer. This axisymmetric shear layer rolls up into a mushroom-shaped toroidal vortex ring and forward-facing jet. For strong shocks, this deforms the Mach disk to the extent of forming a second triple point with the primary shock exhibiting a double bulge. Separate features resembling the Richtmeyer–Meshkov and Kelvin–Helmholtz instabilities were noted in some tests. Aside from the incident wave curvature, the reflection patterns demonstrated correspond well with the V- and DV-types identified by Hornung although type S was not clearly seen, possibly due to the occlusion of the reflection region by the outer diffraction vortex at these early times. Some additional computational work explicitly exploring the limits of the parameter space for such systems has demonstrated the existence of a possible further reflection type, called vN-type, which is similar to the von Neumann reflection for plane waves. It is recommended that the parameter space be more thoroughly explored experimentally.     

An ESR study of the acetaldehyde radical cation in freon matrices: Evidence for halogen superhyperfine interaction

The substructure associated with the doublet ESR spectrum of the acetaldehyde radical cation in Freon matrices below 100 K is shown to arise from a matrix interaction and not, as previously proposed, from coupling to the hydrogens of the methyl group. Since the reversible loss of this substructure at higher temperature is accompanied by almost no change in the large isotropic ¹H coupling(136 G) to the aldehydic hydrogen, the matrix perturbation appears to have a negligible effect on the spin distribution in the radical cation and is according interpreted as a superhyperfine interaction     

Primary electron reflections in discharges surrounded by magnetic multipole walls

By observing the primary electron trajectories and studying experimentally the equilibrium of an argon plasma in the pressure range 0.8 × 10^?4 – 8 × 10^?4 torr, we show that the main effect of the surrounding magnetic wall is not the confinement of the plasma but the confinement of the primary electrons in the discharge.