Preparation and magnetic properties of barium ferrites substituted with manganese, cobalt, and tin

Barium ferrites substituted by Mn–Sn, Co–Sn, and Mn–Co–Sn with general formulae BaFe12−2xMnxSnxO19 (x=0.2–1.0), BaFe12−2xCoxSnxO19 (x=0.2–0.8), and BaFe12−2xCox/2Mnx/2SnxO19 (x=0.1–0.6), respectively, have been prepared by a previously reported co-precipitation method. The efficiency of the method was refined by lowering the reaction temperature and shortening the required reaction time, due to which crystallinity improved and the value of saturated magnetization increased as well. Low coercivity temperature coefficients, which are adjustable by doping, were achieved by Mn–Sn and Mn–Co–Sn doping. Synthesis efficiency and the effect of doping are discussed taking into account accumulated data concerning the synthesis and crystal structure of ferrites.

Preparation and ring-opening reactions of N-diphenylphosphinyl vinyl aziridines

Predominantly (E)-N-diphenylphosphinyl vinyl aziridines are prepared by a reaction of N-diphenylphosphinyl imines with α-bromoallyllithium in the presence of freshly fused ZnCl2. These aziridines undergo a ring-opening reaction with a variety of carbon and heteronucleophiles, in good yield, and generally with good regioselectivity.

Characterisation of Bolivian savanna ecosystems by their modern pollen rain and implications for fossil pollen records

The majority of vegetation reconstructions from the Neotropics are derived from fossil pollen records extracted from lake sediments. However, the interpretation of these records is restricted by limited knowledge of the contemporary relationships between the vegetation and pollen rain of Neotropical ecosystems, especially for more open vegetation such as savannas. This research aims to improve the interpretation of these records by investigating the vegetation and modern pollen rain of different savanna ecosystems in Bolivia using vegetation inventories, artificial pollen traps and surface lake sediments. Two types of savanna were studied, upland savannas (cerrado), occurring on well drained soils, and seasonally-inundated savannas occurring on seasonally water-logged soils. Quantitative vegetation data are used to identify taxa that are floristically important in the different savanna types and to allow modern pollen/vegetation ratios to be calculated. Artificial pollen traps from the upland savanna site are dominated by Moraceae (35%), Poaceae (30%), Alchornea (6%) and Cecropia (4%). The two seasonally-inundated savanna sites are dominated by Moraceae (37%), Poaceae (20%), Alchornea (8%) and Cecropia (7%), and Moraceae (25%), Cyperaceae (22%), Poaceae (19%) and Cecropia (9%), respectively. The modern pollen rain of seasonally-inundated savannas from surface lake sediments is dominated by Cyperaceae (35%), Poaceae (33%), Moraceae (9%) and Asteraceae (5%). Upland and seasonally-flooded savannas were found to be only subtly distinct from each other palynologically. All sites have a high proportion of Moraceae pollen due to effective wind dispersal of this pollen type from areas of evergreen forest close to the study sites. Modern pollen/vegetation ratios show that many key woody plant taxa are absent/under-represented in the modern pollen rain (e.g., Caryocar and Tabebuia). The lower-than-expected percentages of Poaceae pollen, and the scarcity of savanna indicators, in the modern pollen rain of these ecosystems mean that savannas could potentially be overlooked in fossil pollen records without consideration of the full pollen spectrum available.

Understanding the spatial mass transfer behaviour of a pulsating jet HMV system: vortex generation and characterisation

The flow patterns generated by a pulsating jet used to study hydrodynamic modulated voltammetry (HMV) are investigated. It is shown that the pronounced edge effect reported previously is the result of the generation of a vortex ring from the pulsating jet. This vortex behaviour of the pulsating jet system is imaged using a number of visualisation techniques. These include a dye system and an electrochemically generated bubble stream. In each case a toroidal vortex ring was observed. Image analysis revealed that the velocity of this motion was of the order of 250 mm s−1 with a corresponding Reynolds number of the order of 1200. This motion, in conjunction with the electrode structure, is used to explain the strong ‘ring and halo’ features detected by electrochemical mapping of the system reported previously.

Detection and molecular characterisation of Pyrenopeziza brassicae isolates resistant to methyl benzimidazole carbamates

BACKGROUND Methyl benzimidazole carbamate (MBC) fungicides are used to control the oilseed rape pathogen Pyrenopeziza brassicae. Resistance to MBCs has been reported in P. brassicae, but the molecular mechanism(s) associated with reductions in sensitivity have not been verified in this species. Elucidation of the genetic changes responsible for resistance, hypothesised to be target-site mutations in β-tubulin, will enable resistance diagnostics and thereby inform resistance management strategies. RESULTS P. brassicae isolates were classified as sensitive, moderately resistant or resistant to MBCs. Crossing P. brassicae isolates of different MBC sensitivities indicated that resistance was conferred by a single gene. The MBC-target encoding gene β-tubulin was cloned and sequenced. Reduced MBC sensitivity of field isolates correlated with β-tubulin amino acid substitutions L240F and E198A. The highest level of MBC resistance was measured for isolates carrying E198A. Negative cross-resistance between MBCs and the fungicides diethofencarb and zoxamide was only measured in E198A isolates. PCR-RFLP was used to screen isolates for the presence of L240F and E198A. The substitutions E198G and F200Y were also detected in DNA samples from P. brassicae populations after cloning and sequencing of PCR products. The frequencies of L240F and E198A in different P. brassicae populations were quantified by pyrosequencing. There were no differences in the frequencies of these alleles between P. brassicae populations sampled from different locations or after fungicide treatment regimes. CONCLUSIONS The molecular mechanisms affecting sensitivity to MBCs in P. brassicae have been identified. Pyrosequencing assays are a powerful tool for quantifying fungicide-resistant alleles in pathogen populations.

Statistical characterisation of the growth and spatial scales of the substorm onset arc

We present the first multi-event study of the spatial and temporal structuring of the aurora to provide statistical evidence of the near-Earth plasma instability which causes the substorm onset arc. Using data from ground-based auroral imagers, we study repeatable signatures of along-arc auroral beads, which are thought to represent the ionospheric projection of magnetospheric instability in the near-Earth plasma sheet. We show that the growth and spatial scales of these wave-like fluctuations are similar across multiple events, indicating that each sudden auroral brightening has a common explanation. We find statistically that growth rates for auroral beads peak at low wavenumber with the most unstable spatial scales mapping to an azimuthal wavelength λ≈1700 − 2500 km in the equatorial magnetosphere at around 9-12 RE. We compare growth rates and spatial scales with a range of theoretical predictions of magnetotail instabilities, including the cross-field current instability and the shear-flow ballooning instability. We conclude that, although the cross-field current instability can generate similar magnitude of growth rates, the range of unstable wavenumbers indicates that the shear-flow ballooning instability is the most likely explanation for our observations.

Neuromotor tolerability and behavioural characterisation of cannabidiolic acid, a phytocannabinoid with therapeutic potential for anticipatory nausea

Rationale: Anticipatory nausea (AN) is a poorly controlled side-effect experienced by chemotherapy patients. Currently, pharmacotherapy is restricted to benzodiazepine anxiolytics, which have limited efficacy, significant sedative effects, and induce dependency. The non-psychoactive phytocannabinoid, cannabidiolic acid (CBDA), has shown considerable efficacy in pre-clinical AN models, however determination of its neuromotor tolerability profile is crucial to justify clinical investigation. Provisional evidence for appetite-stimulating properties also requires detailed investigation. Objectives: To assess the tolerability of CBDA in locomotor activity, motor coordination and muscular strength tests, and additionally for ability to modulate feeding behaviours. Methods: Male Lister hooded rats administered CBDA (0.05-5 mg/kg; p.o.) were assessed in habituated open field (for locomotor activity), static beam and grip strength tests. A further study investigated whether these CBDA doses modulated normal feeding behaviour. Finally, evidence of anxiolytic-like effects in the habituated open field prompted testing of 5 mg/kg CBDA for anxiolytic-like activity in unhabituated open field, light/dark box and novelty-supressed feeding (NSF) tests. Results: CBDA had no adverse effects upon performance in any neuromotor tolerability test, however anxiolytic-like behaviour was observed in the habituated open field. Normal feeding behaviours were unaffected by any dose. CBDA (5 mg/kg) abolished the increased feeding latency in the NSF test induced by the 5-HT1AR antagonist, WAY-100,635, indicative of anxiolytic-like effects, but had no effect on anxiety-like behaviour in the novel open field or light/dark box. Conclusions: CBDA is very well tolerated and devoid of the sedative side-effect profile of benzodiazepines, justifying its clinical investigation as a novel AN treatment.

Characterisation of chicken riboflavin carrier protein gene structure and promoter regulation by estrogen

Estrogen is an important steroid hormone that mediates most of its effects on regulation of gene expression by binding to intracellular receptors. The consensus estrogen response element (ERE) is a 13 bp palindromic inverted repeat with a three nucleotide spacer. However, several reports suggest that many estrogen target genes are regulated by diverse elements, such as imperfect EREs and ERE half sites (ERE 1/2),which are either the proximal or the distal half of the palindrome. To gain more insight into ERE half site-mediated gene regulation, we used a region from the estrogen-regulated chicken riboflavin carrier protein (RCP) gene promoter that contains ERE half sites. Using moxestrol, an analogue of estrogen and transient transfection of deletion and mutation containing RCP promoter/reporter constructs in chicken hepatoma (LMH2A) cells, we identified an estrogen response unit (ERU) composed of two consensus ERE 1/2 sites and one non-consensus ERE 1/2 site. Mutation of any of these sites within this ERU abolishes moxestrol response. Further, the ERU is able to confer moxestrol responsiveness to a heterologous promoter. Interestingly, RCP promoter is regulated by moxestrol in estrogen responsive human MCF-7 cells, but not in other cell lines such as NIH3T3 and HepG2 despite estrogen receptor-alpha (ER-�) co transfection. Electrophoretic mobility shift assays (EMSAs) with promoter regions encompassing the half sites and nuclear extracts from LMH2A cells show the presence of a moxestrol-induced complex that is abolished by a polyclonal anti-ER� antibody. Surprisingly, estrogen receptor cannot bind to these promoter elements in isolation. Thus, there appears to be a definite requirement for some other factor(s) in addition to estrogen receptor, for the generation of a suitable response of this promoter to estrogen. Our studies therefore suggest a novel mechanism of gene regulation by estrogen, involving ERE half sites without direct binding of ER to the cognate elements.

A new method for the characterisation and verification of local spatial predictability for convective scale ensembles

The use of kilometre-scale ensembles in operational forecasting provides new challenges for forecast interpretation and evaluation to account for uncertainty on the convective scale. A new neighbourhood based method is presented for evaluating and characterising the local predictability variations from convective scale ensembles. Spatial scales over which ensemble forecasts agree (agreement scales, S^A) are calculated at each grid point ij, providing a map of the spatial agreement between forecasts. By comparing the average agreement scale obtained from ensemble member pairs (S^A(mm)_ij), with that between members and radar observations (S^A(mo)_ij), this approach allows the location-dependent spatial spread-skill relationship of the ensemble to be assessed. The properties of the agreement scales are demonstrated using an idealised experiment. To demonstrate the methods in an operational context the S^A(mm)_ij and S^A(mo)_ij are calculated for six convective cases run with the Met Office UK Ensemble Prediction System. The S^A(mm)_ij highlight predictability differences between cases, which can be linked to physical processes. Maps of S^A(mm)_ij are found to summarise the spatial predictability in a compact and physically meaningful manner that is useful for forecasting and for model interpretation. Comparison of S^A(mm)_ij and S^A(mo)_ij demonstrates the case-by-case and temporal variability of the spatial spread-skill, which can again be linked to physical processes.

Characterisation of synoptic conditions and cyclones associated with top ranking potential wind loss events over Iberia

Intense extra-tropical cyclones are often associated with strong winds, heavy precipitation and socio-economic impacts. Over southwestern Europe, such storms occur less often, but still cause high economic losses. We characterise the largescale atmospheric conditions and cyclone tracks during the top-100 potential losses over Iberia associated with wind events. Based on 65 years of reanalysis data,events are classified into four groups: (i) cyclone tracks crossing over Iberia on the event day (“Iberia”), (ii) cyclones crossing further north, typically southwest of the British Isles (“North”), (iii) cyclones crossing southwest to northeast near the northwest tip of Iberia (“West”), and (iv) so called “Hybrids”, characterised by a strong pressure gradient over Iberia due to the juxtaposition of low and high pressure centres. Generally, “Iberia” events are the most frequent (31% to 45% for top-100 vs.top-20), while “West” events are rare (10% to 12%). 70% of the events were primarily associated with a cyclone. Multi-decadal variability in the number of events is identified. While the peak in recent years is quite prominent, other comparably stormy periods occurred in the 1960s and 1980s. This study documents that damaging wind storms over Iberia are not rare events, and their frequency of occurrence undergoes strong multi-decadal variability.

Characterisation of anthracyclines from a cosmomycin D-producing species of Streptomyces by collisionally-activated dissociation and ion mobility mass spectrometry

Cultures of cosmomycin D-producing Streptomyces olindensis ICB20 that were propagated for many generations underwent mutations that resulted in production of a range of related anthracyclines by the bacteria. The anthracyclines that retained the two trisaccharide chains of the parent compound were separated by HPLC. Exact mass determination of these compounds revealed that they differed from cosmomycin D (CosD) in that they contained one to three fewer oxygen atoms (loss of hydroxyl groups). Some of the anthracyclines that were separated by HPLC had the same mass. The location from which the hydroxyl groups had been lost relative to CosD (on the aglycone and/or on the sugar residues) was probed by collisionally-activated dissociation using an electrospray ionisation linear quadrupole ion trap mass spectrometer. The presence of anthracyclines with the same mass, but different structure, was confirmed using an electrospray ionisation travelling wave ion mobility mass spectrometer.

Preparation and structural characterization of rare-earth doped lead lanthanum zirconate titanate ceramics

A new preparation route towards rare-earth (RE) doped polycrystalline lead lanthanum zirconate titanate (PLZT) ceramics (RE = Y(3+), Nd(3+), Yb(3+)), based on the use of doped lanthanum oxide or zirconia, is reported. Structural characterization by X-ray powder diffraction reveals that secondary phase formation can be substantially diminished in comparison to conventional preparation methods. The distribution of the rare-earth dopants was investigated as a function of concentration by static (207)Pb spin echo NMR spectra, using Fourier Transformation of Carr-Purcell-Meiboom-Gill spin echo trains. For the Nd- and Yb-doped materials, the interaction of the (207)Pb nuclei with the unpaired electron spin density results in significant broadening and shifting of the NMR signal, whereas these effects are absent in the diamagnetic Y(3+) doped materials. Based on different concentration dependences of the NMR lineshape parameters, we conclude that the structural role of the Nd(3+) dopants differs significantly from that of Yb(3+). While the Nd(3+) ions appear to be statistically distributed in the PLZT lattice, incorporation of Yb(3+) into PLZT appears to be limited by the appearance of doped cubic zirconia as a secondary phase. (C) 2009 Elsevier Masson SAS. All rights reserved.

Preparation and photoluminescence properties of functionalized silica materials incorporating europium complexes

In the present work, the surface of the Eu-BTC = [Eu(EMA)(H(2)O)(2)], [Eu(TLA)(H(2)O)(4)] and [Eu(TMA)(H(2)O)(6)] complexes (EMA = 1,2,3-benzenetricarboxylate, TLA = 1,2,4-benzenetricarboxylate and TMA = 1,3,5-benzenetricarboxylate) was modified using 3-aminopropyltriethoxysilane (APTES) by a new microwave assisted method that proved to be simple and efficient. According to our observations, the most efficient luminescence is the material based on APTES incorporating [Eu(TMA)(H(2)O)(6)] complexes, denoted as Eu-TMA-Si, shows the highest emission efficiency. Therefore, it is proposed as a promising material for molecular conjugation in clinical diagnosis. (C) 2011 Elsevier B.V. All rights reserved.

Microstructural, Mechanical and Tribological Characterisation of CVD and PVD Coatings for Metal Cutting Applications

The present thesis focuses on characterisation of microstructure and the resulting mechanical and tribological properties of CVD and PVD coatings used in metal cutting applications. These thin and hard coatings are designed to improve the tribological performance of cutting tools which in metal cutting operations may result in improved cutting performance, lower energy consumption, lower production costs and lower impact on the environment.  In order to increase the understanding of the tribological behaviour of the coating systems a number of friction and wear tests have been performed and evaluated by post-test microscopy and surface analysis. Much of the work has focused on coating cohesive and adhesive strength, surface fatigue resistance, abrasive wear resistance and friction and wear behaviour under sliding contact and metal cutting conditions. The results show that the CVD deposition of accurate crystallographic phases, e.g. α-Al2O3 rather than κ-Al2O3, textures and multilayer structures can increase the wear resistance of Al2O3. However, the characteristics of the interfaces, e.g. topography as well as interfacial porosity, have a strong impact on coating adhesion and consequently on the resulting properties.  Through the deposition of well designed bonding and template layer structures the above problems may be eliminated. Also, the presence of macro-particles in PVD coatings may have a significant impact on the interfacial adhesive strength, increasing the tendency to coating spalling and lowering the surface fatigue resistance, as well as increasing the friction in sliding contacts. Finally, the CVD-Al2O3 coating topography influences the contact conditions in sliding as well as in metal cutting. In summary, the work illuminates the importance of understanding the relationships between deposition process parameters, composition and microstructure, resulting properties and tribological performance of CVD and PVD coatings and how this knowledge can be used to develop the coating materials of tomorrow.

Emissions Characterisation of residential pellet boilers during start-up and stop periods

In this study, gaseous emissions and particles are measured during start-up and stop periods for an over-fed boiler and an under-fed boiler. Both gaseous and particulate matter emissions are continuously measured in the laboratory. The measurement of gaseous emissions includes oxygen (O2), carbon dioxide (CO2), carbon monoxide (CO), nitrogen oxide and (NO). The emissions rates are calculated from measured emissions concentrations and flue gas flow. The behaviours of the boilers during start-up and stop periods are analysed and the emissions are characterised in terms of CO, NO, TOC and particles (PM2.5 mass and number). The duration of the characterised periods vary between two boilers due to the difference in type of ignition and combustion control. The under-fed boiler B produces higher emissions during start-up periods than the over-fed boiler A. More hydrocarbon and particles are emitted by the under-fed boiler during stop periods. Accumulated mass of CO and TOC during start-up and stop periods contribute a major portion of the total mass emitted during whole operation. However, accumulated mass of NO and PM during start-up and stop periods are not significant as the duration of emission peak is relatively short.