meso-Porphyrinylphosphine Oxides: Mono- and Bidentate Ligands for Supramolecular Chemistry and the Crystal Structures of Monomeric [10,20-Diphenylporphyrinatonickel(II)-5,15-diyl]-bis-[P(O)Ph2] and Polymeric Self-Coordinated ([10,20-Diphenylporphyrinatozinc(II)-5,15-diyl]-bis-[P(O)Ph2])

A series of porphyrins substituted in one or two meso-positions by diphenylphosphine oxide groups has been prepared by the palladium catalysed reaction of diphenylphosphine or its oxide with the corresponding bromoporphyrins. Compounds {MDPP-[P(O)Ph2]n} (M = H2, Ni, Zn; H2DPP = 5,15-diphenylporphyrin; n = 1, 2) were isolated in yields of 60-95%. The reaction is believed to proceed via the conventional oxidative addition, phosphination and reductive elimination steps, as the stoichiometric reaction of η1-palladio(II) porphyrin [PdBr(H2DPP)(dppe)] (H2DPP = 5,15-diphenylporphyrin; dppe = 1,2-bis(diphenylphosphino)ethane) with diphenylphosphine oxide also results in the desired mono-porphyrinylphosphine oxide [H2DPP-P(O)Ph2]. Attempts to isolate the tertiary phosphines failed due to their extreme air-sensitivity. Variable temperature 1H NMR studies of [H2DPP-P(O)Ph2] revealed an intrinsic lack of symmetry, while fluorescence spectroscopy showed that the phosphine oxide group does not behave as a "heavy atom" quencher. The electron withdrawing effect of the phosphine oxide group was confirmed by voltammetry. The ligands were characterised by multinuclear NMR and UV-visible spectroscopy as well as mass spectrometry. Single crystal X-ray crystallography showed that the bis(phosphine oxide) nickel(II) complex {[NiDPP-[P(O)Ph2]2} is monomeric in the solid state, with a ruffled porphyrin core and the two P=O fragments on the same side of the average plane of the molecule. On the other hand, the corresponding zinc(II) complex formed infinite chains through coordination of one Ph2PO substituent to the neighbouring zinc porphyrin through an almost linear P=O---Zn unit, leaving the other Ph2PO group facing into a parallel channel filled with disordered water molecules. These new phosphine oxides are attractive ligands for supramolecular porphyrin chemistry.

Electrospraying a reproducible method for production of polymeric microspheres for biomedical applications

The ability to reproducibly load bioactive molecules into polymeric microspheres is a challenge. Traditional microsphere fabrication methods typically provide inhomogeneous release profiles and suffer from lack of batch to batch reproducibility, hindering their potential to up-scale and their translation to the clinic. This deficit in homogeneity is in part attributed to broad size distributions and variability in the morphology of particles. It is thus desirable to control morphology and size of non-loaded particles in the first instance, in preparation for obtaining desired release profiles of loaded particles in the later stage. This is achieved by identifying the key parameters involved in particle production and understanding how adapting these parameters affects the final characteristics of particles. In this study, electrospraying was presented as a promising technique for generating reproducible particles made of polycaprolactone, a biodegradable, FDA-approved polymer. Narrow size distributions were obtained by the control of electrospraying flow rate and polymer concentration, with average particle sizes ranging from 10 to 20 um. Particles were shown to be spherical with a homogenous embossed texture, determined by the polymer entanglement regime taking place during electrospraying. No toxic residue was detected by this process based on preliminary cell work using DNA quantification assays, validating this method as suitable for further loading of bioactive components.

Sound in the Aboriginal Australian Films of Rolf de Heer

Anna Hickey-Mody and Melissa Iocca invented a new name for the cinema-goer at "Bad Boy Bubby" (1993) when they wrote: "In de Heer's film, the viewer is primarily a listener, or aurator, and secondly a spectator" and I have argued the label 'aurator' can also be used for the person experiencing "Ten Canoes" (2006). This Aboriginal Australian Dreamtime fable features dialogue recorded entirely in the Ganalbingu language of the Indigenous people it stars, and is a prime example of what I would suggest can be labeled 'The Aboriginal Australian Films of Rolf de Heer'. "The Tracker" (2002) and "Dr. Plonk" (2007) have also included depictions of Aboriginal Australians and each of the trio utilizes Cat Hope's "innovative sound ideas" to present what I argue is an aural auteur's signature revealing a post-colonial Australian world-view that privileges the justice system and eco-spirituality of Aboriginal Australians.

Drug diffusion from polymeric delivery devices : a problem with two moving boundaries

An existing model for solvent penetration and drug release from a spherically-shaped polymeric drug delivery device is revisited. The model has two moving boundaries, one that describes the interface between the glassy and rubbery states of polymer, and another that defines the interface between the polymer ball and the pool of solvent. The model is extended so that the nonlinear diffusion coefficient of drug explicitly depends on the concentration of solvent, and the resulting equations are solved numerically using a front-fixing transformation together with a finite difference spatial discretisation and the method of lines. We present evidence that our scheme is much more accurate than a previous scheme. Asymptotic results in the small-time limit are presented, which show how the use of a kinetic law as a boundary condition on the innermost moving boundary dictates qualitative behaviour, the scalings being very different to the similar moving boundary problem that arises from modelling the melting of an ice ball. The implication is that the model considered here exhibits what is referred to as ``non-Fickian'' or Case II diffusion which, together with the initially constant rate of drug release, has certain appeal from a pharmaceutical perspective.

The relationship between building characteristics and the chemical composition of surface films found on glass windows in Brisbane, Australia

Films found on the windows of residential buildings have been studied. The main aim of the paper was to assess the roles of the films in the accumulation of potentially toxic chemicals in residential buildings. Thus the elemental and polycyclic aromatic hydrocarbon compositions of the surface films from the glass windows of eighteen residential buildings were examined. The presence of sample amounts of inorganic elements (4.0–1.2 × 106 μg m−2) and polycyclic aromatic hydrocarbons in the films (BDL - 620.1 ng m−2) has implications for human exposure and the fate of pollutants in the urban environment. To facilitate the interpretation of the results, data matrices consisting of the chemical composition of the films and the building characteristics were subjected to multivariate data analysis methods, and these revealed that the accumulation of the chemicals was strongly dependent on building characteristics such as the type of glass used for the window, the distance from a major road, age of the building, distance from an industrial activity, number of smokers in the building and frequency of cooking in the buildings. Thus, building characteristics which minimize the accumulation of pollutants on the surface films need to be encouraged.

Asymptotic and numerical results for a model of solvent-dependent drug diffusion through polymeric spheres

A model for drug diffusion from a spherical polymeric drug delivery device is considered. The model contains two key features. The first is that solvent diffuses into the polymer, which then transitions from a glassy to a rubbery state. The interface between the two states of polymer is modelled as a moving boundary, whose speed is governed by a kinetic law; the same moving boundary problem arises in the one-phase limit of a Stefan problem with kinetic undercooling. The second feature is that drug diffuses only through the rubbery region, with a nonlinear diffusion coefficient that depends on the concentration of solvent. We analyse the model using both formal asymptotics and numerical computation, the latter by applying a front-fixing scheme with a finite volume method. Previous results are extended and comparisons are made with linear models that work well under certain parameter regimes. Finally, a model for a multi-layered drug delivery device is suggested, which allows for more flexible control of drug release.

Enhanced photoconduction of free-standing ZnO nanowire films by L-lysine treatment

Flexible paper-like ZnO nanowire films are fabricated and the effect of L-lysine passivation of the nanowire surfaces on improving the UV photoresponse is studied. We prepare three types of nanowires with different defect contents, and find that the L-lysine treatment can suppress the oxygen-vacancy-related photoluminescence as well as enhance the UV photoconduction. The nanowires with fewer defects gain larger enhancement of UV photoconduction after L-lysine treatment. Reproducible UV photoresponse of the devices in humid air is obtained due to L-lysine surface passivation, ruling out the influence of water molecules in degrading the UV photocurrent.

Transition from n- to p-type of spray pyrolysis deposited Cu doped ZnO thin films for NO2 sensing

The structural, optical, and gas-sensing properties of spray pyrolysis deposited Cu doped ZnO thin films were investigated. Gas response of the undoped and doped films to N02 (oxidizing) gas shows an increase and decrease in resistance, respectively, indicating p-type conduction in doped samples. The UV-Vis spectra of the films show decrease in the bandgap with increasing Cu concentration in ZnO. The observed p-type conductivity is attributed to the holes generated by incorporated Cu atoms on Zn sites in ZnO thin films. The X-ray diffraction spectra showed that samples are polycrystalline with the hexagonal wurtzite structure and increasing the concentration of Cu caused a decrease in the intensity of the dominant (002) peak. The surface morphology of films was studied by scanning electron microscopy and the presence of Cu was also confirmed by X-ray photoelectron spectroscopy. Seebeck effect measurements were utilized to confirm the p-type conduction of Cu doped ZnO thin films. Copyright © 2009 American Scientific Publishers All rights reserved.