Temporal and spatial transcriptional programs in murine kidney development

We have performed a systematic temporal and spatial expression profiling of the developing mouse kidney using Compugen long-oligonucleotide microarrays. The activity of 18,000 genes was monitored at 24-h intervals from 10.5-day-postcoitum (dpc) metanephric mesenchyme (MM) through to neonatal kidney, and a cohort of 3,600 dynamically expressed genes was identified. Early metanephric development was further surveyed by directly comparing RNA from 10.5 vs. 11.5 vs. 13.5dpc kidneys. These data showed high concordance with the previously published dynamic profile of rat kidney development (Stuart RO, Bush KT, and Nigam SK. Proc Natl Acad Sci USA 98: 5649-5654, 2001) and our own temporal data. Cluster analyses were used to identify gene ontological terms, functional annotations, and pathways associated with temporal expression profiles. Genetic network analysis was also used to identify biological networks that have maximal transcriptional activity during early metanephric development, highlighting the involvement of proliferation and differentiation. Differential gene expression was validated using whole mount and section in situ hybridization of staged embryonic kidneys. Two spatial profiling experiments were also undertaken. MM (10.5dpc) was compared with adjacent intermediate mesenchyme to further define metanephric commitment. To define the genes involved in branching and in the induction of nephrogenesis, expression profiling was performed on ureteric bud (GFP+) FACS sorted from HoxB7-GFP transgenic mice at 15.5dpc vs. the GFP- mesenchymal derivatives. Comparisons between temporal and spatial data enhanced the ability to predict function for genes and networks. This study provides the most comprehensive temporal and spatial survey of kidney development to date, and the compilation of these transcriptional surveys provides important insights into metanephric development that can now be functionally tested.

delta O-18, Sr/Ca and Mg/Ca records of Porites lutea corals from Leizhou Peninsula, northern South China Sea, and their applicability as paleoclimatic indicators

Combined seasonal to monthly resolution coral skeletal delta(18)O, Sr/Ca, and Mg/Ca records are reported for one modem and two late Holocene Porites lutea corals from a fringing reef at Leizhou Peninsula, the northern coast of the South China Sea (SCS). All the profiles for the period 1989-2000 reveal annual cycles well correlated with instrumental sea surface temperatures (SST), and display broad peaks in summer and narrow troughs in winter, reflecting seasonal growth rate variations. Calibration against instrumental SST yields the following equations: delta(18)O=-0.174(+/- 0.010)xSST(degrees C)-1.02(+/- 0.27) (MSWD=5.8), Sr/Ca-(mmol/mol)=-0.0424(+/- 0.0031)xSST(degrees C)+9.836(+/- 0.082) (MSWD=8.6), and Mg/Ca-(mmol/mol)=0.110(+/- 0.009)XSST(degrees C)+ 1.32(+/- 0.23) (MSWD=55). The scatter in the Mg/Ca-SST relationship is much larger than analytical uncertainties can account for, suggesting the presence of SST-unrelated components in the Mg/Ca variation. Calculated Sr/Ca-SST values for two later Holocene Porites lutea samples (U-series ages similar to 541 BC and similar to 487 AD, respectively) from the same reef suggest that SST in the SCS at similar to 541 BC was nearly as warm as in the 1990s (the warmest decade of the last century), but at similar to 487 AD, it was significantly cooler. This observation is consistent with climatic data reported in Chinese historic documents, confirming that the Sr/Ca-SST relationship is a reliable thermometer. Removing the SST component in the delta(18)O variation based on calculated Sr/Ca-SST values, the residual delta(18)O reflects the deviation of the Holocene seawater delta(18)O from the modem value, which is also a measure of the Holocene sea surface salinity (SSS) or the summer monsoon moisture level in mainland China. Such residual delta(18)O was close to zero at similar to 541 BC and -0.3 parts per thousand at similar to 487 AD, suggesting that it was as wet as in the 1990s at similar to 541 BC but significantly drier at similar to 487 AD in mainland China, which are also consistent with independent historic records. Calculated Mg/Ca-SST values for the two late Holocene corals are significantly lower than the Sr/Ca-SST values and are also in conflict with Chinese historic records, suggesting that coral Mg/Ca is not reliable proxy for SST. At comparable Sr/Ca ranges, fossil corals always display negative Mg/Ca offsets if compared with the modem coral of the same site. We interpret this observation as due to preferential loss of Mg during meteoric dissolution of cryptic Mg-calcite-bearing microbialites in the exposed fossil corals. Microbialites (MgO up to 17%, Sr only 100-300 ppm) are ubiquitous during reef-building processes and their presence in only a trace amount will have a significant impact on coral Mg/Ca ratios without detectable influence on coral Sr/Ca ratios. (c) 2004 Elsevier B.V. All rights reserved.

Effect of growing site, moisture stress and seed size on viability and dormancy of Sporobolus pyramidalis (giant rats tail grass) seed

Sporobolus pyramidalis P. Beauv (giant rats tail grass) is a serious agricultural and environmental weed in tropical and subtropical areas of Australia. Infestations of this unpalatable plant reduce the productivity of pastures and the profitability of industries dependent on grazing animals. This paper reports a series of studies undertaken to assist in the development of control strategies for this species. In particular, these studies measured the viability and dormancy status of fresh seed of S. pyramidalis and the decline of dormancy with time. Variability in these characteristics was determined in seeds collected from several sites within south-east Queensland. The effect of moisture availability during the inflorescence and seed production phases on seed viability and dormancy was also determined. The dormancy of freshly collected seed from several sites ranged from 15 to 95%, but decreased to negligible levels after 4-6 months. Seeds that matured under conditions of high moisture availability were initially more dormant than seeds matured where moisture was less readily available. The proportion of viable seeds was significantly lower in smaller than larger seeds even though viability for all seed sizes exceeded 90%. This study has shown that seed of S. pyramidalis generally has high viability with a large proportion of the seed germinable soon after maturity.

Onset of sheath extension and duration of lamina extension are major determinants of the response of maize lamina length to plant density

Background and Aims Plants regulate their architecture strongly in response to density, and there is evidence that this involves changes in the duration of leaf extension. This questions the approximation, central in crop models, that development follows a fixed thermal time schedule. The aim of this research is to investigate, using maize as a model, how the kinetics of extension of grass leaves change with density, and to propose directions for inclusion of this regulation in plant models. • Methods Periodic dissection of plants allowed the establishment of the kinetics of lamina and sheath extension for two contrasting sowing densities. The temperature of the growing zone was measured with thermocouples. Two-phase (exponential plus linear) models were fitted to the data, allowing analysis of the timing of the phase changes of extension, and the extension rate of sheaths and blades during both phases. • Key Results The duration of lamina extension dictated the variation in lamina length between treatments. The lower phytomers were longer at high density, with delayed onset of sheath extension allowing more time for the lamina to extend. In the upper phytomers—which were shorter at high density—the laminae had a lower relative extension rate (RER) in the exponential phase and delayed onset of linear extension, and less time available for extension since early sheath extension was not delayed. • Conclusions The relative timing of the onset of fast extension of the lamina with that of sheath development is the main determinant of the response of lamina length to density. Evidence is presented that the contrasting behaviour of lower and upper phytomers is related to differing regulation of sheath ontogeny before and after panicle initiation. A conceptual model is proposed to explain how the observed asynchrony between lamina and sheath development is regulated.

Pattern analysis on protein properties of Chinese and CIMMYT spring wheat cultivars sown in China and CIMMYT

Improvement of processing quality is a very important objective for Chinese wheat breeding programs. Twenty-five CIMMYT and Chinese spring wheat cultivars were grown at four managed conditions by CIMMYT in Cd. Obregon, Sonora, Mexico and in nine environments in China, over two successive wheat seasons from 2000 to 2002. These trials were used to identify patterns of cultivar, environment and cultivar x environment interactions, and to determine opportunities for indirect selection for protein content and the protein-quality related parameter, SDS sedimentation (SDSS) value. The cultivar Inqalab 91 showed low levels of interaction with environments in the 2000-01 crop cycle for protein content, and expressed intermediate levels for both protein content and SDSS value, across most of the environments in both years. Longmai 26 had consistently high protein content and SDSS value across environments in both years, indicating that it is possible to breed cultivars expressing high yields with good protein properties. Cluster analyses revealed that cultivars grouped differently for protein content and SDSS value. Besides photoperiod, water availability appeared to influence the ranking of cultivars for protein content and SDSS value. Temperature and soil type may underlie the observed interactions for protein content, while temperature may also be a factor associated with interactions for SDSS value. The full irrigation managed environment in Mexico, with the cultivars sown on raised beds two months later than optimum and exposing them to late heat, clustered together with the Chinese environments Huhhot, Yongning, and Hejin in the 2000-01 season for SDSS value. This indicates that there is an opportunity to exploit indirect responses to selection in the CIMMYT management environments for SDSS value with relevance for China's spring wheat regions. However, there seemed little chance for positive indirect selection in CIMMYT's managed environments for China in regard to protein content, as environments clustered distinctly. Pattern analyses permitted a sensible and useful summary for this multi environment experiment, helping in understanding natural relationships and variations in cultivar performance among the various environment groups, and assisting in the structuring of environments.

Transport of simple fluids in nanopores: Theory and simulation

A theory is discussed of single-component transport in nanopores, recently developed by Bhatia and coworkers. The theory considers the oscillatory motion of molecules between diffuse wall collisions, arising from the fluid-wall interaction, along with superimposed viscous flow due to fluid-fluid interaction. The theory is tested against molecular dynamics simulations for hydrogen, methane, and carbon tetrafluoride flow in cylindrical nanopores in silica. Although exact at low densities, the theory performs well even at high densities, with the density dependency of the transport coefficient arising from viscous effects. Such viscous effects are reduced at high densities because of the large increase in viscosity, which explains the maximum in the transport coefficient with increase in density. Further, it is seen that in narrow pore sizes of less than two molecular diameters, where a complete monolayer cannot form on the surface, the mutual interference of molecules on opposite sides of the cross section can reduce the transport coefficient, and lead to a maximum in the transport coefficient with increasing density. The theory is also tested for the case of partially diffuse reflection and shows the viscous contribution to be negligible when the reflection is nearly specular. (c) 2005 American Institute of Chemical Engineers AIChE J, 52: 29-38, 2006.

OS SENTIDOS DO FUTEBOL ESPETÁCULO PARA ESTUDANTES DE DISTINTAS CLASSES SOCIAIS

O presente estudo busca identificar em que medida o pertencimento de classe social interfere nos sentidos e perspectivas do jovem brasileiro frente ao futebol espetáculo, bem como compreender os mecanismos sociais que determinam a decisão de os sujeitos investirem na carreira profissional esportiva em detrimento da trajetória escolar longa. Começamos com uma abordagem sociológica, a análise crítica dos processos de difusão, massificação e profissionalização do futebol ocorridas no contexto da sociedade pós-industrial. Enfocamos a conflituosa mutação da modalidade, inicialmente elitizada com fins social-distintivos para esporte de massa ideal de ascensão social da classe popular , além da dependência com a mídia, das razões que levaram a caracterizar-se como produto da indústria cultural, culminando com a transformação do futebol em mercadoria submetida às leis e lógica da sociedade de consumo. Em seguida, entrelaçamos as relações de poder, aliança e concorrência dos agentes sociais que participam do complexo campo das práticas esportivas com os canais com que o público jovem estabelece contato com o esporte espetáculo. Neste aspecto, especial atenção foi dada à mídia, difusora da ideologia de uma sociedade capitalista aberta, que reforça a idéia do esporte como via de ascensão social para indivíduos de baixa renda, na mesma medida em que oculta em seu discurso as reais probabilidades de concretização do sucesso esportivo. A pesquisa de campo foi realizada em duas escolas do município de São Bernardo do Campo (SP), uma da rede pública estadual e outra da rede particular de ensino. Assim, constituímos dois grupos com alunos de distintas classes sociais, compostos por estudantes do 1º ano do Ensino Médio, sexo masculino, com 15 anos de idade e praticantes de futebol nas aulas de Educação Física. Metodologicamente, fizemos uso da observação participante e de entrevistas como instrumentos para a coleta de dados. Conjugadas aos objetivos do estudo, estruturamos a análise do material colhido em seis categorias, articulando questões sobre o prosseguimento nos estudos e o trabalho, as tendências para a pratica esportiva profissional, as representações sociais em torno do futebol, os usos e costumes no tempo livre e as expectativas da pratica esportiva implicadas pela herança cultural familiar. Como referencial teórico de análise, utilizamos de Pierre Bourdieu os conceitos de campo, habitus, estratégia, capital econômico, social e, principalmente, capital cultural, partindo da hipótese de que o nível cultural dos alunos e seus familiares interferem nos sentidos e formas de apropriação do esporte. Entre outras conclusões, obtivemos como resultado a configuração de uma trajetória esportiva profissional voltada para os alunos de baixa classe social, em oposição à trajetória escolar longa, estrategicamente adotada pelos alunos de classe social alta.(AU)

Oxidation of organic compounds in molten salts

The objective of this research was to investigate the oxidation of organic compounds in molten alkali metal hydroxides containing manganates. It has been shown that controlled oxidation can be readily achieved with high specificity to give products in high yield with very short reaction times. The concurrent changes in the melt were monitored using a vibrating platinum indicator electrode with a quazi-reference electrode which was successfully developed for use in molten (Na-K)OH eutectic at 523K. Henry's Law constants for water in the molten eutectic system (Na-K)OH have been measured and used to calculate the water concentration in the melt. The electrochemistry of manganates in molten (Na-K)OH eutectic at 523K has been studied using the vibrating platinum electrode, and the existence of the species Mn(II), Mn(II!), Mn(IV), Mn(V) and Mn(VI) in such melts has been investigated at various water concentrations. The half-wave potentials of the voltammetric waves were measured versus the cathodic limit of the melt. The stability of Mn(V) or Mn(VI) in the melt was achieved by varying the water concentration. A range of organic chemicals has been passed through molten (Na-K)OH at 523K and the reactions of these chemicals with the melt have been studied. The same organics were then passed through molten (Na-K)OH containing stabilized Mn(V) or Mn{VI) without violent reaction. Methanol, allyl alcohol, propane 1, 2 diol, I-heptene and acetone were oxidized by Mn(V) and Mn(VI). Ethanol was only oxidized by Mn(VI), isopropanol and benzyl alcohol were only oxidized by Mn(V). Npropanol, butanol, 2 methyl propan-2-ol, n-hexane, n-heptane toluene and cyclohexane were unchanged by both Mn(V) and Mn(VI). Detailed experiments have been performed on the reactions of ethanol, iso-propanol and methanol in molten (Na-K)OH containing stabilized Mrt(V) or Mn(VI), and reaction mechanisms have been postulated. Ethanol and iso-propanol were oxidized to acetaldehyde and acetone respectively with a potential for useful chemical process. The oxidation of methanol could be developed as a basis for an industrial methanol disposal process.

Myopia:precedents for research in the twenty-first century

The myopic eye is generally considered to be a vulnerable eye and, at levels greater than 6 D, one that is especially susceptible to a range of ocular pathologies. There is concern therefore that the prevalence of myopia in young adolescent eyes has increased substantially over recent decades and is now approaching 10-25% and 60-80%, respectively, in industrialized societies of the West and East. Whereas it is clear that the major structural correlate of myopia is longitudinal elongation of the posterior vitreous chamber, other potential correlates include profiles of lenticular and corneal power, the relationship between longitudinal and transverse vitreous chamber dimensions and ocular volume. The most potent predictors for juvenile-onset myopia continue to be a refractive error ≤+0.50 D at 5 years of age and family history. Significant and continuing progress is being made on the genetic characteristics of high myopia with at least four chromosomes currently identified. Twin studies and genetic modelling have computed a heritability index of at least 80% across the whole ametropic continuum. The high index does not, however, preclude an environmental precursor, sustained near work with high cognitive demand being the most likely. The significance of associations between accommodation, oculomotor dysfunction and human myopia is equivocal despite animal models that have demonstrated that sustained hyperopic defocus can induce vitreous chamber growth. Recent optical and pharmaceutical approaches to the reduction of myopia progression in children are likely precedents for future research, for example progressive addition spectacle lens trials and the use of the topical MI muscarinic antagonist pirenzepine.

Carbomer-modified spray-dried respirable powders for pulmonary delivery of salbutamol sulphate

The present study investigates the feasibility of using two types of carbomer (971 and 974) to prepare inhalable dry powders that exhibit modified drug release properties. Powders were prepared by spray-drying formulations containing salbutamol sulphate, 20-50% w/w carbomer as a drug release modifier and leucine as an aerosolization enhancer. Following physical characterization of the powders, the aerosolization and dissolution properties of the powders were investigated using a Multi-Stage Liquid Impinger and a modified USP II dissolution apparatus, respectively. All carbomer 974-modified powders and the 20% carbomer 971 powder demonstrated high dispersibility, with emitted doses of at least 80% and fine particle fractions of approximately 40%. The release data indicated that all carbomer-modified powders displayed a sustained release profile, with carbomer 971-modified powders obeying first order kinetics, whereas carbomer 974-modified powders obeyed the Higuchi root time kinetic model; increasing the amount of carbomer 971 in the formulation did not extend the duration of drug release, whereas this was observed for the carbomer 974-modified powders. These powders would be anticipated to deposit predominately in the lower regions of the lung following inhalation and then undergo delayed rather than instantaneous drug release, offering the potential to reduce dosing frequency and improve patient compliance.

The chemical modification of polymer blends by reactive processing

The primary objective of this research was to examine the concepts of the chemical modification of polymer blends by reactive processing using interlinking agents (multi-functional, activated vinyl compounds; trimethylolpropane triacrylates {TRIS} and divinylbenzene {DVD}) to target in-situ interpolymer formation between immiscible polymers in PS/EPDM blends via peroxide-initiated free radical reactions during melt mixing. From a comprehensive survey of previous studies of compatibility enhancement in polystyrene blends, it was recognised that reactive processing offers opportunities for technological success that have not yet been fully realised; learning from this study is expected to assist in the development and application of this potential. In an experimental-scale operation for the simultaneous melt blending and reactive processing of both polymers, involving manual injection of precise reactive agent/free radical initiator mixtures directly into molten polymer within an internal mixer, torque changes were distinct, quantifiable and rationalised by ongoing physical and chemical effects. EPDM content of PS/EPDM blends was the prime determinant of torque increases on addition of TRIS, itself liable to self-polymerisation at high additions, with little indication of PS reaction in initial reactively processed blends with TRIS, though blend compatibility, from visual assessment of morphology by SEM, was nevertheless improved. Suitable operating windows were defined for the optimisation of reactive blending, for use once routes to encourage PS reaction could be identified. The effectiveness of PS modification by reactive processing with interlinking agents was increased by the selection of process conditions to target specific reaction routes, assessed by spectroscopy (FT-IR and NMR) and thermal analysis (DSC) coupled dichloromethane extraction and fractionation of PS. Initiator concentration was crucial in balancing desired PS modification and interlinking agent self-polymerisation, most particularly with TRIS. Pre-addition of initiator to PS was beneficial in the enhancement of TRIS binding to PS and minimisation of modifier polymerisation; believed to arise from direct formation of polystyryl radicals for addition to active unsaturation in TRIS. DVB was found to be a "compatible" modifier for PS, but its efficacy was not quantified. Application of routes for PS reaction in PS/EPDM blends was successful for in-situ formation of interpolymer (shown by sequential solvent extraction combined with FT-IR and DSC analysis); the predominant outcome depending on the degree of reaction of each component, with optimum "between-phase" interpolymer formed under conditions selected for equalisation of differing component reactivities and avoidance of competitive processes. This was achieved for combined addition of TRIS+DVB at optimum initiator concentrations with initiator pre-addition to PS. Improvements in blend compatibility (by tensiles, SEM and thermal analysis) were shown in all cases with significant interpolymer formation, though physical benefits were not; morphology and other reactive effects were also important factors. Interpolymer from specific "between-phase" reaction of blend components and interlinking agent was vital for the realisation of positive performance on compatibilisation by the chemical modification of polymer blends by reactive processing.

Antibody detection of Burkholderia pseudommallei and Burkholderia mallei

Monoclonal and polyclonaI antibodies have been produced for use in immunological assays for the detection of Burkholderia pseudomallei and Burkholderia mallei. Monoclonal antibodies recognising a high molecular weight polysaccharide material found in some strains of both species have been shown to be effective in recognising B. pseudomallei and B. mallei and distinguishing them from other organisms. The high molecular weight polysaccharide material is thought to be the capsule of B. pseudomallei and B. mallei and may have important links with virulence. B. pseudomallei and B. mallei are known to be closely related, sharing many epitopes, but antigenic variation has been demonstrated within both the species. The lipopolysaccharide from strains of B. pseudomal/ei and B. mallei has been isolated and the silver stain profiles found to be visually very similar. A monoclonal antibody raised to B. mallei LPS has been found to recognise both B. mallei and B. pseudomallei strains. However, in a small number of B. pseudomallei strains a visually atypical LPS profile has been demonstrated. A monoclonal ant ibody rai sed against this atypical LPS showed no recognition of the typical LPS profile of either B. mallei or B. pseudomallei. This atypical LPS structure has not been reported and may be immunologically distinct from the typical LPS. Molecular biology and antibody engineering techniques have been used in an attempt to produce single-chain antibody fragments reactive to B. pseudomallei. Sequencing of one of the single-chain antibody fragments produced showed high homology with murine immunoglobulin genes, but none of the single-chain antibody fragments were found to be specific to B. pselldomallei.

Improving the function of islet and beta-cell grafts

Background: Human islet transplantation would offer a less invasive and more physiological alternative than whole pancreas transplantation and insulin injections respectively for the treatment of diabetes mellitus if islet graft survival can be improved. Initial recipient post-transplant insulin independence declines to <10% after 5 years. Factors contributing to graft failure include enzymatic disruption of the islet microenvironment during isolation, diabetogenic effects of immunosuppressants and metabolic stress resulting from slow revascularisation. Aims: To investigate the effect of co-culture in both static (SC) and rotational culture (RC) of BRINBDII beta-cells (Dl1) and human umbilical vein endothelial cells (HUVEC) on Dl1 insulin secretion; and the effect of a thiazolidinedione (TZD) on DII function and HUVEC proliferation. To assess the effect of culture media, SC, RC and a TZD on human islet morphology, insulin secretion and VEGF production. To initiate in vivo protocol development for assessment of revascularisation of human islet grafts. Methods: D11 cells were cultured +/-TZD and co-cultured with HUVEC +/-TZD in SC and RC. Dl1 insulin secretion was induced by static incubation with low glucose (1.67mM), high glucose (l6.7mM: and high glucose with 10mM theophylline (G+T) and determined by ELISA. HUVEC were cultured +/-TZD in SC and RC and proliferation was assessed by ATP luminescence assay and VEGF ELISA. D II and HUVEC morphology was determined by immunocytochemistry. Human islets were cultured in SC and RC in various media +/-TZD. Insulin secretion was determined as above and VEGF production by fluorescence immunocytochemistry (FI) and ELISA. Revascularisation of islet grafts was assessed by vascular corrosion cast and FI. Results: Dll cultures showed significantly increased insulin secretion in response to 16.7mM and G+T over basal; this was enhanced by RC and further improved by adding 10mM TZD. Untreated Dll/HUVEC co-cultures displayed significantly increased insulin secretion in response to 16.7mM and G+T over basal, again enhanced by RC and improved with 10mM TZD. 10mM TZD significantly increased HUVEC proliferation over control. Human islets maintained in medium 199 (mI99) in SC and RC exhibited comparable maintenance of morphology and insulin secretory profiles compared to islets maintained in RPMI, endothelial growth media and dedicated islet medium Miami# I. All cultures showed significantly increased insulin secretion in response to 16.7mM and G+T over basal; this was enhanced by RC and in certain instances further improved by adding 25mM TZD. TZD increased VEGF production and release as determined by ELISA. Post-implant vascular corrosion casts of mouse kidneys analysed by x-ray micro tomography indicates a possible TZD enhancement of microvessel growth via VEGF upregulation. Conclusions: D II /HUVEC co-culture in SC or RC does not alter the morphology of either cell type and supports D 11 function. TZD improves 0 I I and D I I/HUVEC SC and RC co-culture insulin secretion while increasing HUVEC proliferation. Human islet RC supports islet functional viability and structural integrity compared to SC while the addition of TZD occasionally further improves secretagogue induced insulin secretion. Expensive, 'dedicated' islet media showed no advantage over ml99 in terms of maintaining islet morphology or function. TZD upregulates VEGF in islets as shown by ELISA and suggested by x-ray micro tomography analysis of vascular corrosion casts. Maintenance of islets in RC and treatment with TZD prior to transplant may improve the functional viability and revascularisation rate of islet grafts.

Fast reconstruction of harmonic functions from Cauchy data using the Dirichlet-to-Neumann map and integral equations

We propose and investigate a method for the stable determination of a harmonic function from knowledge of its value and its normal derivative on a part of the boundary of the (bounded) solution domain (Cauchy problem). We reformulate the Cauchy problem as an operator equation on the boundary using the Dirichlet-to-Neumann map. To discretize the obtained operator, we modify and employ a method denoted as Classic II given in [J. Helsing, Faster convergence and higher accuracy for the Dirichlet–Neumann map, J. Comput. Phys. 228 (2009), pp. 2578–2576, Section 3], which is based on Fredholm integral equations and Nyström discretization schemes. Then, for stability reasons, to solve the discretized integral equation we use the method of smoothing projection introduced in [J. Helsing and B.T. Johansson, Fast reconstruction of harmonic functions from Cauchy data using integral equation techniques, Inverse Probl. Sci. Eng. 18 (2010), pp. 381–399, Section 7], which makes it possible to solve the discretized operator equation in a stable way with minor computational cost and high accuracy. With this approach, for sufficiently smooth Cauchy data, the normal derivative can also be accurately computed on the part of the boundary where no data is initially given.

In situ studies of titania-supported Au shell-Pd core nanoparticles for the selective aerobic oxidation of crotyl alcohol

The thermal evolution of titania-supported Au shell–Pd core bimetallic nanoparticles, prepared via colloidal routes, has been investigated by in situ XPS, DRIFTS, EXAFS and XRD and ex situ HRTEM. As-prepared nanoparticles are terminated by a thin (∼5 layer) Au shell, encapsulating approximately 20 nm diameter cuboctahedral palladium cores, with the ensemble stabilised by citrate ligands. The net gold composition was 40 atom%. Annealing in vacuo or under inert atmosphere rapidly pyrolyses the citrate ligands, but induces only limited Au/Pd intermixing and particle growth <300 °C. Higher temperatures promote more dramatic alloying, accompanied by significant sintering and surface roughening. These changes are mirrored by the nanoparticle catalysed liquid phase selective aerobic oxidation of crotyl alcohol to crotonaldehyde; palladium surface segregation enhances both activity and selectivity, with the most active surface alloy attainable containing ∼40 atom% Au.