Structural,Magnetic and Catalytic Properties of a New Vacancy Ordered Perovskite Type Barium Cobaltate BaCoO2.67

A new vacancy ordered, anion deficient perovskite modification with composition of BaCoO_2.67 (Ba₃Co₃O₈□₁) has been prepared via a two-step heating process. Combined Rietveld analysis of neutron and X-ray powder diffraction data shows a novel ordering of oxygen vacancies not known before for barium cobaltates. A combination of neutron powder diffraction, magnetic measurements, and density functional theory (DFT) studies confirms G-type antiferromagnetic ordering. From impedance measurements, the electronic conductivity of the order of 10⁻⁴ S cm⁻¹ is determined. Remarkably, the bifunctional catalytic activity for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is found to be comparable to that of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3–y, confirming that charge-ordered anion deficient non-cubic perovskites can be highly efficient catalysts.     

Synthesis and characterisation of the SrxBa1−xFeO3−y-system and the fluorinated phases SrxBa1−xFeO2F

Compounds in the system Sr_xBa_1?xFeO_3?y have been prepared under different partial pressures of oxygen. In this system, different perovskite-type structures are found depending highly on the values of x and y. Fluorination using polyvinylidenedifluoride (PVDF) gives oxyfluoride materials of composition Sr_xBa_1?xFeO₂F, which normally crystallize in the cubic perovskite structure. Rietveld refinement results provide information about the packing density for oxide and oxyfluoride samples and allow a general comparison between these two different types of materials. Furthermore, the determination of the average iron oxidation state also showed that the oxygen deficiency, y, depends significantly on the value of x and the structure determined by the Sr/Ba ratio.     

Electrophoresis in the presence of gradients: I. Viscosity gradients

In many cases, the resolution provided by capillary electrophoresis systems approaches that predicted for diffusion-limited separations. Once all device-related sources of band broadening have been eliminated or minimized, only thermal diffusion remains. In principle, peaks can be sharpened using gradients of various system characteristics such as gel concentration, buffer viscosity and electric field. However, it is not clear whether this can actually increase the resolution of the system. In this article, we focus our attention on viscosity gradients and we examine both continuous and step-like variations. Our results indicate that the performance of electrophoretic systems cannot be improved by viscosity gradients. They may provide extra stacking, and thus improve the resolution, when the injection width is non-negligible. However, for the systems considered here, the best resolution is obtained when the viscosity is uniform and the stacking is entirely performed at injection. We conclude by discussing the link between these results, the fundamental laws of thermodynamics, the nature of the detection process and the importance of having nonlinear effects in nonuniform systems.     

Analysis of 13C-mixed triacylglycerol in stool by bulk (EA-IRMS) and compound specific (GC/MS) methods

This paper was presented in poster form at the 17th International Congress of Nutrition, August 27-31, Vienna, Austria (Annals of Nutrition & Metabolism 2001; 45(Suppl.1):349). Some of the data were also presented in poster form at the British Society of Gastroenterology Meeting, March 18-21, Glasgow, UK (Gut 2001; 48(Suppl.1):A91). The 13C-mixed triacylglycerol (MTG) breath test is used to measure intraluminal fat digestion. In normal digestion, 20-40% of the ingested 13C label is recovered in breath CO2. We aimed to identify the proportions of ingested label excreted in stool, as well as breath following ingestion of 13C-MTG by children with impaired exocrine pancreatic function and healthy controls. 13C enrichment of breath samples was measured by continuous flow isotope ratio mass spectrometry (IRMS) and cumulative percent dose recovered (cPDR) in 10 h was calculated. Total 13C of a faecal fat extract from each stool was measured by elemental analyser-IRMS, and 13C enrichment and concentration of the TBDMS derivative of octanoic acid was measured by GC/MS after hydrolysis of the fat extract. Stool 5-day cPDR was calculated. Mean breath cPDR was 35%. Mean cPDR in stool by combustion-IRMS and GC/ MS, respectively, was 0.8% and 1.0%. Therefore, the remaining 64% of the 13C label must remain in the body and variability in breath cPDR is due to postabsorptive rather than predigestive factors.     

Production of 13C labelled pea flour for use in human digestion and fermentation studies

Stable isotope breath tests offer a new approach to the study of digestion and fermentation of carbohydrates in man. In this study, 13C labelled peas were grown by pulsing 250 ml 13CO2 into a sealed growth chamber. A second pulse was added to a portion of the peas to increase the 13C enrichment. This generated pea flour with an enrichment of 2.36 at.% excess (range 2.09-2.71 n = 3) and 8.64 atom % excess (range 7.37-9.78 n = 3) respectively. This represented incorporation of an absolute yield of 3.8% of the 13CO2 into peas in the 'once-labelled' treatment and 7.5% in the 'twice-labelled' treatment. Ingestion of a mixture of the labelled pea flour (300 mg) by two volunteers generated measurable 13CO2 excretion for breath test analysis. The profile of breath 13CO2 enrichment increased to a maximum within three hours after consuming the pea flour followed by a decrease almost back to baseline by 13 hours. Breath 13CO2 appeared to rise again after this apparent nadir at 13 hours until the end of the sampling period. Mathematical analysis of the data suggested that two peaks best described the profile of breath 13CO2 up to 13 hours. A third peak was necessary to describe the late rise in breath 13CO2 enrichment. This use of 13C enriched pea flour may provide a useful non invasive method for measurement of digestion and fermentation in vivo.     

A linear algorithm for a core of a tree

A core of a graph G is a path P in G that is central with respect to the property of minimizing d(P) = Σ_υ?V(G)d(υ, P), where d(υ, P) is the distance from vertex υ to path P. We present a linear algorithm for finding a core of a tree. Since the core of a graph is not necessarily unique, we also output a list of all the vertices which are in some core.     

Malaria chemotherapy and the "kaleidoscopic" organisation of biomedical research during world war II

The paper describes the organisational and scientific evolution of the US antimalarial program during World War II. This program screened some 14,000 compounds for antimalarial activity, selected atabrine as the drug of choice in 1943, and later identified chloroquine as a superior compound. It became, arguably, the largest biomedical research effort of the first half of the twentieth century, involving chemical and pharmaceutical companies, diverse university researchers, and non-profit and government laboratories. Beyond scientific research, the innovations of the wartime antimalarial program were chiefly in three areas, communication, scale and administration. The program drew on resources - intellectual, material and organisational - created in Germany by researchers at Bayer, and in the US by the Rockefeller Foundation and Institutes. The paper examines the antimalarial program as one of the formative models for later programs such as the National Institutes of Health. This account supports the claim that wartime work was essential to the development of NIH, if only because the confused and faltering structures of the early war years, 1939-1943, do not suggest that all the organisational infrastructure for large scale, multi-centre co-operative research was in place prior to World War II.     

Structural studies of apatite-type oxide ion conductors doped with cobalt

A series of Co doped lanthanum silicate apatite-type phases, La9.83Si4.5Co1.5O26, La9.66Si5CoO26, La10Si5CoO26.5 and La8BaCoSi6O26, have been synthesised, and neutron diffraction, EXAFS and XANES used to investigate their structures in detail. All compositions were shown to possess the hexagonal apatite structure, and the results confirmed that cobalt can be doped onto both the La and Si sites within the structure depending on the starting composition. The Co doping is shown to cause considerable local distortions within the apatite structure. In the case of Si site doping two compositions showed anisotropic peak broadening, which has been attributed to incommensurate ordering of oxygen within the apatite channels.     

A determination of the Cabibbo-Kobayashi-Maskawa parameter |V us| using KL decays

We present a determination of the Cabibbo-Kobayashi-Maskawa parameter |V(us)| based on new measurements of the six largest K(L) branching fractions and semileptonic form factors by the KTeV (E832) experiment at Fermilab. We find |V(us)|=0.2252+/-0.0008(KTeV)+/-0.0021(ext), where the errors are from KTeV measurements and from external sources. We also use the measured branching fractions to determine the CP violation parameter |eta(+-)|=(2.228+/-0.005(KTeV)+/-0.009(ext))x10(-3).     

Measurements of the Decay KL-->e+ e- mu+ mu-

The KTeV experiment at Fermilab has isolated a total of 132 events from the rare decay K(L)-->e+ e- mu+ mu-, with an estimated background of 0.8 events. The branching ratio of this mode is determined to be [2.69+/-0.24(stat)+/-0.12(syst)]x10(-9), with a radiative cutoff of M(2)(ee mu mu)/M(2)(K)>0.95. The first measurement using this mode of the parameter alpha from the D'Ambrosio-Isidori-Portolès (DIP) model of the K(L)gamma*gamma* vertex yields a result of -1.59+/-0.37, consistent with values obtained from other decay modes. Because of the limited statistics, no sensitivity is found to the DIP parameter beta. We use this decay mode to set limits on CP and lepton violation.