Peter M. Brodersen

Rapid oxygen ion diffusion and surface exchange kinetics in PrBaCo2O5+x with a perovskite related structure and ordered A cations

As part of an investigation of new cathode materials for intermediate temperature solid oxide fuel cells, we have investigated particular perovskite oxides with ordered A cations which, in turn, localize the oxygen vacancies into layers. The oxygen exchange kinetics of polycrystalline samples of the oxygen-deficient double perovskite PrBaCo2O5+x (PBCO) have been determined by electrical conductivity relaxation (ECR) and by oxygen-isotope exchange and depth profiling (IEDP). The ECR and IEDP measurements reveal that PBCO has high electronic conductivity and rapid oxygen ion diffusion and surface exchange kinetics. Both techniques demonstrate that the oxygen kinetics in this structure type are significantly faster than in corresponding disordered perovskites.

Oxygen exchange kinetics of epitaxial PrBaCo2O5+δ thin films

The oxygen exchange kinetics of thin films of the oxygen-deficient double perovskite PrBaCo2O5+δ (PBCO) have been determined by electrical conductivity relaxation (ECR) and by oxygen-isotope exchange and depth profiling (IEDP). Microstructural studies indicate that the PBCO films, prepared by pulsed laser deposition, have excellent single-crystal quality and epitaxial nature. The ECR and IEDP measurements reveal that the PBCO films have high electronic conductivity and rapid surface exchange kinetics, although the ECR data indicate the presence of two distinct kinetic pathways. The rapid surface kinetics compared with those of other perovskites suggest the application of PBCO as a cathode material in intermediate-temperature solid oxide fuel cells.

Ordered 2D arrays of ferromagnetic Fe/Co nanoparticle rings from a highly metallized metallopolymer precursor

Ordered 2D arrays of ferromagnetic Fe/Co alloy nanoparticle rings with diameters of 2–12 µm were fabricated via plasma etching and subsequent pyrolytic treatment of template directed self-assembled rings of a highly metallized polyferrocenylsilane metallopolymer precursor.

Enhancing drug delivery for boron neutron capture therapy of brain tumors with focused ultrasound

BACKGROUND Glioblastoma is a notoriously difficult tumor to treat because of its relative sanctuary in the brain and infiltrative behavior. Therapies need to penetrate the CNS but avoid collateral tissue injury. Boron neutron capture therapy (BNCT) is a treatment whereby a (10)B-containing drug preferentially accumulates in malignant cells and causes highly localized damage when exposed to epithermal neutron irradiation. Studies have suggested that (10)B-enriched L-4-boronophenylalanine-fructose (BPA-f) complex uptake can be improved by enhancing the permeability of the cerebrovasculature with osmotic agents. We investigated the use of MRI-guided focused ultrasound, in combination with injectable microbubbles, to noninvasively and focally augment the uptake of BPA-f. METHODS With the use of a 9L gliosarcoma tumor model in Fisher 344 rats, the blood-brain and blood-tumor barriers were disrupted with pulsed ultrasound using a 558 kHz transducer and Definity microbubbles, and BPA-f (250 mg/kg) was delivered intravenously over 2 h. (10)B concentrations were estimated with imaging mass spectrometry and inductively coupled plasma atomic emission spectroscopy. RESULTS The tumor to brain ratio of (10)B was 6.7 ± 0.5 with focused ultrasound and only 4.1 ± 0.4 in the control group (P < .01), corresponding to a mean tumor [(10)B] of 123 ± 25 ppm and 85 ± 29 ppm, respectively. (10)B uptake in infiltrating clusters treated with ultrasound was 0.86 ± 0.10 times the main tumor concentration, compared with only 0.29 ± 0.08 in controls. CONCLUSIONS Ultrasound increases the accumulation of (10)B in the main tumor and infiltrating cells. These findings, in combination with the expanding clinical use of focused ultrasound, may offer improvements in BNCT and the treatment of glioblastoma.

Spatially Confined Redox Chemistry in Periodic Mesoporous Hydridosilica–Nanosilver Grown in Reducing Nanopores

Periodic mesoporous hydridosilica, PMHS, is shown for the first time to function as both a host and a mild reducing agent toward noble metal ions. In this archetypical study, PMHS microspheres react with aqueous Ag(I) solutions to form Ag(0) nanoparticles housed in different pore locations of the mesostructure. The dominant reductive nucleation and growth process involves SiH groups located within the pore walls and yields molecular scale Ag(0) nanoclusters trapped and stabilized in the pore walls of the PMHS microspheres that emit orange-red photoluminescence. Lesser processes initiated with pore surface SiH groups produce some larger spherical and worm-shaped Ag(0) nanoparticles within the pore voids and on the outer surfaces of the PMHS microspheres. The intrinsic reducing power demonstrated in this work for the pore walls of PMHS speaks well for a new genre of chemistry that benefits from the mesoscopic confinement of Si-H groups.

Insulating polymer additives in small molecule and polymer photovoltaics: how they are tolerated and their use as potential interlayers

Additives are key to achieving optimal morphologies and efficient performance in bulk heterojunction organic photovoltaics. In this work we analyze the impact of three insulating polymers [ethylene acrylic elastomers, polystyrene and poly(methyl methacrylate)] in prototypical small molecule and polymer photovoltaic devices. We find that small molecule–semiconductors and polymer–semiconductors vary remarkably in their tolerance of the type of insulator as well as the degree of insulator incorporation. Insulating polymers capable of self-assembly or infiltration into the organic–semiconductor matrix have a positive or negligible impact on the performance of both small molecule and polymer devices. The spontaneous migration of ethylene acrylic elastomers to the device surface make them adverse additives, however our preliminary data indicates their potential application as a spontaneously forming cathode interlayer in small molecule devices where they match or exceed the performance of evaporated LiF interlayers.

ToF-SIMS and other surface spectroscopies applied to the study of ancient artifacts: Preliminary investigation of a tetradrachm of Claudius

A group of ancient coins is among the Diniacopoulos collection of Central and Eastern Mediterranean antiquities housed at Queens University. At first glance, nine coins in the collection appear to be billon tetradrachms minted in Alexandria, Egypt, dating to the period of the Emperor Claudius (41–54 AD). On the obverse, there is a portrait of the Emperor Claudius, on the reverse his wife Messalina is holding their two children. A closer examination reveals, however, that each of these coins weighs substantially less than the majority of specimens belonging to the same issues. All of the coins appear to have silver-rich plated surfaces with copper-rich cores. Questions are raised, therefore, about their authenticity and methods of manufacture. The surfaces display a variety of corrosion products, some of which may also indicate past restoration treatments. A single coin was selected for time-of-flight secondary ion mass spectrometry (ToF-SIMS), X-ray photoelectron spectroscopy (XPS), and energy dispersive...