Characterization of the aeolian aerosol from Cape Verde by k 0-INAA and PIXE

Due to its location on West Coast of Africa, Cape Verde is highly influenced by Sahara Desert dust events being an optimum place to observe and study the African aeolian aerosol. During 2011, particulate matter with an aerodynamic diameter lower than 10 μm (PM₁₀) was sampled in Santiago Island and its chemical composition was evaluated by k ₀-instrumental neutron activation analysis (k ₀-INAA) and particle induced X-ray emission (PIXE). This study showed the existence of a seasonal intrusion of dust from Africa (that occurred from October to March) characterized by significant increases of PM₁₀, mineral elements and anthropogenic particles concentrations. In 2011, the PM₁₀ health-based air quality guidelines defined by WHO, EU and USEPA were exceeded. Cape Verde PM₁₀ composition was characterized essentially by high concentrations of elements originating from the soil (Ca, Ce, Co, Fe, K, Mg, Mn, Rb, S, Sc, Si, Sm, and Ti) and sea (Br, Cl, and Na); and low concentrations of anthropogenic elements (As, Cr, Cu, Ni, Pb, Sb, V, and Zn). k ₀-INAA and PIXE were fundamental tools for the determination of airborne chemical elements in Cape Verde. Their multi-elemental capabilities in association with low detection limits made it possible to determine the majority of the element concentrations of environmental interest.     

Graphene CVD growth on copper and nickel: role of hydrogen in kinetics and structure

Understanding the chemical vapor deposition (CVD) kinetics of graphene growth is important for advancing graphene processing and achieving better control of graphene thickness and properties. In the perspective of improving large area graphene quality, we have investigated in real-time the CVD kinetics using CH(4)-H(2) precursors on both polycrystalline copper and nickel. We highlighted the role of hydrogen in differentiating the growth kinetics and thickness of graphene on copper and nickel. Specifically, the growth kinetics and mechanism is framed in the competitive dissociative chemisorption of H(2) and dehydrogenating chemisorption of CH(4), and in the competition of the in-diffusion of carbon and hydrogen, being hydrogen in-diffusion faster in copper than nickel, while carbon diffusion is faster in nickel than copper. It is shown that hydrogen acts as an inhibitor for the CH(4) dehydrogenation on copper, contributing to suppress deposition onto the copper substrate, and degrades quality of graphene. Additionally, the evidence of the role of hydrogen in forming C-H out of plane defects in CVD graphene on Cu is also provided. Conversely, resurfacing recombination of hydrogen aids CH(4) decomposition in the case of Ni. Understanding better and providing other elements to the kinetics of graphene growth is helpful to define the optimal CH(4)/H(2) ratio, which ultimately can contribute to improve graphene layer thickness uniformity even on polycrystalline substrates.     

Synthesis and Macrodomain Binding of Mono‐ADP‐Ribosylated Peptides

Mono‐ADP‐ribosylation is a dynamic posttranslational modification (PTM) with important roles in signaling. Mammalian proteins that recognize or hydrolyze mono‐ADP‐ribosylated proteins have been described. We report the synthesis of ADP‐ribosylated peptides from the proteins histone H2B, RhoA and, HNP‐1. An innovative procedure was applied that makes use of pre‐phosphorylated amino acid building blocks. Binding assays revealed that the macrodomains of human MacroD2 and TARG1 exhibit distinct specificities for the different ADP‐ribosylated peptides, thus showing that the sequence surrounding ADP‐ribosylated residues affects the substrate selectivity of macrodomains.     

Influence of the Temperature on the Crystal Structure of Poly(p‐phenylene sulfide): A Study by X‐Ray Measurements and Molecular Mechanics

The crystal structure of poly(p‐phenylene sulfide) (PPS) has been investigated by X‐ray analysis on fiber samples and by molecular mechanics calculations over a wide range of temperatures, from 0 K to 548 K, showing that all the structural parameters remain substantially constant. The thermal expansion coefficients of the a and b axes have been evaluated. Structural parameters experimentally obtained at the various temperatures have been used in calculations by molecular mechanics. The crystal structures calculated by various methods and using several potential functions are in very good agreement. New parameters are proposed for the nonbonded terms of the potential functions.     

Spectroscopic study of the water-soluble organic matter isolated from atmospheric aerosols collected under different atmospheric conditions

The composition of the water-soluble organic matter from fine aerosols collected in a rural location during two different meteorological conditions (summer and autumn) was investigated by UV-vis, synchronous fluorescence (with Δλ = 20 nm), FT-IR and CPMAS-¹³C NMR spectroscopies. A seasonal variation in the concentration of total carbon, organic carbon and water-soluble organic carbon was confirmed, with higher values during the autumn and lower values during the summer season. The chemical characterisation of the water-soluble organic matter showed that both samples are dominated by a high content of aliphatic structures, carboxyl groups and aliphatic carbons single bonded to one oxygen or nitrogen atom. However, the autumn sample exhibits a higher aromatic content than the summer sample, plus signals due to carbons of phenol, ketones and methoxyl groups. These signals were attributed to lignin breakdown products which are likely to be released during wood combustion processes. The obtained results put into evidence the major contribution of biomass burning processes in domestic fireplaces during low temperature conditions into both the concentration and the bulk chemical properties of the WSOC from fine aerosols.     

Crosslinking of a fibrous sample to a macro-oriented mesomorphic network

Preliminary results on the synthesis and characterization of anisotropic networks, oriented on a macroscopic scale, are reported. Fiber samples of segmented thermotropic liquid-crystalline polymers bearing the oxypentenyl lateral substituent have been crosslinked via thermally activated radical reaction. This was made possible by immersion of fiber samples in dichloromethane containing t-butylperoxybenzoate as activating agent, thus allowing its diffusion in the samples. Subsequent annealing at 145°C brings us to an anisotropic network with no loss of the original orientation. A mesophase is stabilized and no structural modification is observed by heating samples from room temperature up to 400°C, where thermal decomposition takes place. Crosslinked fibers exhibit good tensile properties, at both room temperature and at 150°C. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 433–438, 1998     

Association between monthly-reported rhinitis by children from basic schools and monthly-averaged air pollutants,at Lisbon (Portugal)

3-(4-[¹⁸F]fluorobenzyl)-8-hydroxy-1,2,3,4-tetrahydrochromeno[3,4-c]pyridin-5-one ([¹⁸F]FHTP) was in vitro and in vivo evaluated as a putative dopamine D₄ receptor radioligand. Its inhibition constant (K _i ) for cloned human dopamine D_4.2 receptor was determined to be 2.9 nM and it displayed a 2000-fold D₄-selectivity over the D_2long subtype. Its partition coefficient (logP) was measured to be 1.11. Biodistribution, blocking distribution and metabolism studies in rats demonstrated that the specific distribution of [¹⁸F]FHTP in brain regions, suggesting that [¹⁸F]FHTP may be a suitable PET imaging agent for in vivo studies of the dopamine D₄ receptor.     

Letter: radical ion and protonated molecule formation with retinal in electrospray and nanospray

This paper reports a preliminary study of the nanospray ionisation mass spectrometry analyses of retinoic acid and retinal. The results are compared and contrasted to the results normally observed with electrospray ionisation. A significant difference in behaviour was observed for the balance between radical ion formation and protonated molecule formation for retinal. The results suggest that the influence of the very different ionisation conditions present in nanospray is very important in determining how ionisation is achieved and has potentially wide ranging applications in the fields of mass spectral analysis of biological and medical extracts.     

Molar melting enthalpy in an homologous series of mesophasic polymers

The melting point depression of polymer-solvent mixtures as a function of the concentration has been measured by DSC methods for a group of semiflexible linear mesophasic polymers of formula

$\text{[OOC(CH}{}_2\text{)}{}_{\mathrm{n-2}}\text{COOøC(CH}{}_3\text{)CHø]}{}_{\mathrm{\chi }}$

The molar enthalpic changes associated with the phase transitions have been determined. The values of the ratio between the molar isotropization entropy and the total molar entropic change relative to the sequence of phase transitions leading from the crystal phase to the isotropic liquid have been taken into account as an indication of the order of the mesophase. A particularly high value of this ratio has been found for the even members of the homologous series of polymers.