Ozone Oxidizes Glutathione to a Sulfonic Acid

Biosurfaces are universally covered with fluid microfilms containing reduced glutathione (GSH) and other antioxidants whose putative roles include the detoxification of ambient ozone (O_3). It is generally believed that O_3 accepts an electron from the thiolate GS^(2-) function [pK_a(GS^-) = 8.8] of GSH to produce thiyl GS^(•-) radicals en route to the disulfide GSSG. Here, we report novel electrospray mass spectrometry experiments showing that sulfonates (GSO_3^-/GSO_3^(2-)), not GSSG, are the exclusive final products on the surface of aqueous GSH microdroplets exposed to dilute O_3(g) for ~1 ms. The higher reactivity of the thiolate GS^(2-) toward O_3(g) over the thiol GS^- is kinetically resolved in this time frame due to slow GS^- acid dissociation. However, our experiments also show that O_3 will be largely scavenged by the more reactive ascorbate coantioxidant in typical interfacial biofilms. The presence of GSSG and the absence of GSO_3^-/GSO_3^(2-) in extracellular lining fluids are therefore evidence of GSH oxidation by species other than O_3

Enrichment Factors of Perfluoroalkyl Oxoanions at the Air/Water Interface

The refractory, water-bound perfluoro-n-alkyl carboxylate F(CF_2)_nCO_2^− and sulfonate F(CF_2)_nSO_3^− surfactant anions reach remote locations by mechanisms that are not well understood. Here we report experiments in which the relative concentrations of these anions on the surface of microdroplets produced by nebulizing their aqueous solutions are measured via electrospray ionization mass spectrometry. Enrichment factors f (relative to Br^−: f(Br^−) ≡ 1) increase with n, asymptotically reaching f[F(CF_2)_nSO_3^−] ~2f[F(CF_2)_nCO_2^−] ~200 f(Br^−) values above n ~ 8. The larger f values for F(CF_2)_nSO_3^− over their F(CF_2)_nCO_2^− congeners are consistent with a closer approach of the bulkier, less hydrated −SO_3^− headgroup to the air/water interface. A hyperbolic, rather than the predicted linear log f[F(CF_2)_nCO_2^−] vs n dependence suggests the onset of conformational restrictions to interfacial enrichment above n ~4. Marine aerosols produced from contaminated ocean surface waters are therefore expected to be highly enriched in F(CF_2)_nCO_2^−/F(CF_2)_nSO_3^− species

Thermochromism of Model Organic Aerosol Matter

Laboratory experiments show that the optical absorptivity of model organic matter is not an intrinsic property, but a strong function of relative humidity, temperature, and insolation. Suites of representative polyfunctional C_(x)H_(y)O_(z) oligomers in water develop intense visible absorptions upon addition of inert electrolytes. The resulting mixtures reach mass absorption cross sections σ(532 nm) ~ 0.1 m^(2)/gC in a few hours, absorb up to 9 times more solar radiation than the starting material, can be half-bleached by noon sunlight in ~ 1 h, and can be repeatedly recycled without carbon loss. Visible absorptions red-shift and evolve increasingly faster in subsequent thermal aging cycles. Thermochromism and its strong direct dependences on ionic strength and temperature are ascribed to the dehydration of >CH−C(OH)C═C< unsaturations by a polar E1 mechanism, and bleaching to photoinduced retrohydration. These transformations are deemed to underlie the daily cycles of aerosol absorption observed in the field, and may introduce a key feedback in the earth’s radiative balance

Scattering hypervolume for ultracold bosons from weak to strong interactions

The elastic scattering properties of three bosons at low energy enter the many-body description of ultracold Bose gases via the three-body scattering hypervolume $D$. We study this quantity for identical bosons that interact via a pairwise finite-range potential. Our calculations cover the regime from strongly repulsive potentials towards attractive potentials supporting multiple two-body bound states and are consistent with the few existing predictions for $D$. We present the first numerical confirmation of the universal predictions for $D$ in the strongly interacting regime, where Efimov physics dominates, for a local nonzero-range potential. Our findings highlight how $D$ is influenced by three-body quasibound states with strong $d$-wave or $g$-wave characteristics in the weakly interacting regime.Comment: 13 pages, 8 figure

Analise semiotica de um ava (ambiente virtual de ensino aprendizagem) : características cts através da escada semotica de Stamper

Este artigo demonstra um estudo e aplicação da análise semiótica, para a avaliação de interfaces de ambientes virtuais de ensino-aprendizagem (AVA), de acordo com a escada semiótica de Stamper. Com base nas características CTS (Ciência,Tecnologia e Sociedade) encontrada nas camadas “degrais” da escada. Em específico, usamos a metodologia para qualidade de interfaces definida por Schimiguel, que instancia critérios de qualidade para cada uma das camadas da escada semiótica de Stamper. Com base nos resultados dessa investigação foi possível sugerir algumas recomendações nas seis camadas analisadas, sinalizando ainda para cada uma dessas recomendações um enfoque CTS, uma descrição que tem como propósito facilitar a implementação e otimização de AVAS