Recent XAS studies into Homogeneous metal catalyst in fine chemical and pharmaceutical syntheses

A brief review of studies using X-ray Absorption Spectroscopy (XAS) to investigate homogeneous catalytic reactions in fine chemical and pharmaceutical context since 2010 is presented. The advantages of the techniques over traditional lab-based analytical tools, particularly when NMR spectroscopy fails to deliver mechanistic insights, are summarised using these examples. A discussion on the current limitations of the techniques and challenges in the near future is also included

Dietary intake, lung function and airway inflammation in Mexico City school children exposed to air pollutants

<p>Abstract</p> <p>Introduction</p> <p>Air pollutant exposure has been associated with an increase in inflammatory markers and a decline in lung function in asthmatic children. Several studies suggest that dietary intake of fruits and vegetables might modify the adverse effect of air pollutants.</p> <p>Methods</p> <p>A total of 158 asthmatic children recruited at the Children's Hospital of Mexico and 50 non-asthmatic children were followed for 22 weeks. Pulmonary function was measured and nasal lavage collected and analyzed every 2 weeks. Dietary intake was evaluated using a 108-item food frequency questionnaire and a fruit and vegetable index (FVI) and a Mediterranean diet index (MDI) were constructed. The impact of these indices on lung function and interleukin-8 (IL-8) and their interaction with air pollutants were determined using mixed regression models with random intercept and random slope.</p> <p>Results</p> <p>FVI was inversely related to IL-8 levels in nasal lavage (p < 0.02) with a significant inverse trend (test for trend p < 0.001), MDI was positively related to lung function (p < 0.05), and children in the highest category of MDI had a higher FEV₁(test for trend p < 0.12) and FVC (test for trend p < 0.06) than children in the lowest category. A significant interaction was observed between FVI and ozone for FEV₁and FVC as was with MDI and ozone for FVC. No effect of diet was observed among healthy children.</p> <p>Conclusion</p> <p>Our results suggest that fruit and vegetable intake and close adherence to the Mediterranean diet have a beneficial effect on inflammatory response and lung function in asthmatic children living in Mexico City.</p

Role of Surface Area, Primary Particle Size, and Crystal Phase on Titanium Dioxide Nanoparticle Dispersion Properties

Characterizing nanoparticle dispersions and understanding the effect of parameters that alter dispersion properties are important for both environmental applications and toxicity investigations. The role of particle surface area, primary particle size, and crystal phase on TiO2 nanoparticle dispersion properties is reported. Hydrodynamic size, zeta potential, and isoelectric point (IEP) of ten laboratory synthesized TiO2 samples, and one commercial Degussa TiO2 sample (P25) dispersed in different solutions were characterized. Solution ionic strength and pH affect titania dispersion properties. The effect of monovalent (NaCl) and divalent (MgCl2) inert electrolytes on dispersion properties was quantified through their contribution to ionic strength. Increasing titania particle surface area resulted in a decrease in solution pH. At fixed pH, increasing the particle surface area enhanced the collision frequency between particles and led to a higher degree of agglomeration. In addition to the synthesis method, TiO2 isoelectric point was found to be dependent on particle size. As anatase TiO2 primary particle size increased from 6 nm to 104 nm, its IEP decreased from 6.0 to 3.8 that also results in changes in dispersion zeta potential and hydrodynamic size. In contrast to particle size, TiO2 nanoparticle IEP was found to be insensitive to particle crystal structure

Glial Progenitor-Like Phenotype in Low-Grade Glioma and Enhanced CD133-Expression and Neuronal Lineage Differentiation Potential in High-Grade Glioma

Background: While neurosphere-as well as xenograft tumor-initiating cells have been identified in gliomas, the resemblance between glioma cells and neural stem/progenitor cells as well as the prognostic value of stem/progenitor cell marker expression in glioma are poorly clarified. Methodology/Principal Findings: Viable glioma cells were characterized for surface marker expression along the glial genesis hierarchy. Six low-grade and 17 high-grade glioma specimens were flow-cytometrically analyzed for markers characteristics of stem cells (CD133); glial progenitors (PDGFR alpha, A2B5, O4, and CD44); and late oligodendrocyte progenitors (O1). In parallel, the expression of glial fibrillary acidic protein (GFAP), synaptophysin and neuron-specific enolase (NSE) was immunohistochemically analyzed in fixed tissue specimens. Irrespective of the grade and morphological diagnosis of gliomas, glioma cells concomitantly expressed PDGFRa, A2B5, O4, CD44 and GFAP. In contrast, O1 was weakly expressed in all low-grade and the majority of high-grade glioma specimens analyzed. Co-expression of neuronal markers was observed in all high-grade, but not low-grade, glioma specimens analyzed. The rare CD133 expressing cells in low-grade glioma specimens typically co-expressed vessel endothelial marker CD31. In contrast, distinct CD133 expression profiles in up to 90% of CD45-negative glioma cells were observed in 12 of the 17 high-grade glioma specimens and the majority of these CD133 expressing cells were CD31 negative. The CD133 expression correlates inversely with length of patient survival. Surprisingly, cytogenetic analysis showed that gliomas contained normal and abnormal cell karyotypes with hitherto indistinguishable phenotype. Conclusions/Significance: This study constitutes an important step towards clarification of lineage commitment and differentiation blockage of glioma cells. Our data suggest that glioma cells may resemble expansion of glial lineage progenitor cells with compromised differentiation capacity downstream of A2B5 and O4 expression. The concurrent expression of neuronal markers demonstrates that high-grade glioma cells are endowed with multi-lineage differentiation potential in vivo. Importantly, enhanced CD133 expression marks a poor prognosis in gliomas

Additional investigations of a new kinetic method to follow transition-metal nanocluster formation, including the discovery of heterolytic hydrogen activation in nanocluster nucleation reactions

A few years ago we developed a new kinetic method for following transition-metal nanocluster formation in which the resultant nanocluster's catalytic activity was used as a reporter reaction via the pseudoelementary step concept. This method in turn yielded insights into a new, broadly applicable mechanism of nanocluster formation under H-2 consisting of (a) slow, continuous nucleation, A --> B, followed by (b) fast autocatalytic surface growth, A + B --> 2B (A = the nanocluster precursor, [Bu4N](5)Na-3[(1,5-COD)Ir .P2W15Nb3O62], B = the resultant nanocluster's surface metal atoms), in which the nanocluster behaves as a "living metal polymer". Herein, this new kinetic method is investigated and tested further: (i) by following the Ir(0)(similar to 300) nanocluster's kinetics of formation more directly via the H-2 uptake reaction of the [Bu4N](5)Na-3[(1,5-COD)Ir .P2W15Nb3O62] precursor-does this also show an autocatalytic Hz uptake curve?; (ii) by seeing if the predicted initially small, then larger (past the induction period) sizes of the nanoclusters are verifiable directly by TEM; (iii) by testing commercial nonlinear least-squares software (Microcal's ORIGIN) in the kinetic analysis and with the goal of making the new kinetic method readily available to others; (iv) by showing when it is necessary to correct for the solvent vapor pressure, and how to do so, in the H-2 pressure-loss measurements when more volatile solvents such as acetone are used in the nanocluster formation reaction; (iv) by showing whether the new kinetic method can be successfully used in other nanocluster formation reactions of different metals and for more difficult reactions such as arene hydrogenation; and (v) by numerical integration simulations of the first 45 or so steps in the nanocluster formation reaction-does this atomically detailed mechanism show autocatalysis or not, and if so can it be fit by the A B, A + B --> 2B mechanism? Tests of each of the issues (i)-(v) are reported in the present contribution. Finally, (vi) the new kinetic method has been exploited to yield insights into higher valent metals that undergo nucleation under H-2, namely, to discover and report for the first time the significance of heterolytic hydrogenation activation, with its requirement for added base in the nanocluster formation reactions of higher valent, electrophilic metals such as Pd(II), Pt(IV), Ru(III), Rh(III), Ag(I), Au(III), Cu(II), and Ir(III)

Ras is involved in nerve-activity-dependent regulation of muscle genes

Gene expression in skeletal muscle is regulated by the firing pattern of motor neurons, but the signalling systems involved in excitation-transcription coupling are unknown. Here, using in vivo transfection in regenerating muscle, we show that constitutively active Ras and a Ras mutant that selectively activates the MAPK(ERK) pathway are able to mimic the effects of slow motor neurons on expression of myosin genes. Conversely, the effect of slow motor neurons is inhibited by a dominant-negative Ras mutant. MAPK(ERK) activity is increased by innervation and by low-frequency electrical stimulation. These results indicate that Ras-MAPK signalling is involved in promoting nerve-activity-dependent differentiation of slow muscle fibres in vivo