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

Survival of eclogite xenolith in a Cretaceous granite intruding the Central Dabieshan migmatite gneiss dome (Eastern China) and its tectonic implications.

International audienceInvestigation of an eclogite xenolith, discovered in a Cretaceous granite from the Central Domain of the Dabieshan massif in eastern China, yields new petrological insights into the high to ultrahigh-pressure metamorphism, experienced by the Qinling-Dabie orogen. Prior to inclusion as a xenolith in the granite during the Early Cretaceous, this eclogite xenolith had recorded a complex metamorphic evolution that complies with subduction and exhumation processes experienced by the continental crust of the South China Block. Well-preserved mineral parageneses substantiate the prograde and retrograde stages revealed by inclusions in porphyroblastic garnet and zoned minerals such as garnet, comphacite and amphibole in the matrix. The relatively low P/T re-equilibration during a latemetamorphic stage was textually inferred by the presence of aluminous and calcic-subcalcic amphiboles such as katophorite, edenite, taramite and pargasite as main matrix phases. According to our U/Pb, Rb/Sr and new 40Ar/39Ar geochronological results, namely 109 ± 1 and 112 ± 2 Ma plateau ages for muscovite and amphiboles, respectively, two successive but distinct cooling stages account for the thermal history of the granite–migmatite gneiss dome that forms the Central Dabieshan Domain. We argue that prior to the Cretaceous doming, the Central Dabieshan Domain experienced a tectono-metamorphic evolution similar to that observed in the high-pressure to ultra high-pressure units developed in the Southern Dabieshan Domain and Hong'an massif

Anomalous phonon behavior in the high temperature shape memory alloy: TiPd:Cr

Ti50 Pd50-xCrx is a high temperature shape memory alloy with a martensitic transformation temperature strongly dependent on the Cr composition. Prior to the transformation a premartensitic phase is present with an incommensurate modulated cubic lattice with wave vector of q0=(0.22, 0.22, 0). The temperature dependence of the diffuse scattering in the cubic phase is measured as a function temperature for x=6.5, 8.5, and 10 at. %. The lattice dynamics has been studied and reveals anomalous temperature and q-dependence of the [110]-TA2 transverse phonon branch. The phonon linewidth is broad over the entire Brillouin zone and increases with decreasing temperature, contrary to the behavior expected for anharmonicity. No anomaly is observed at q0. The results are compared with first principles calculation of the phonon structure.Comment: 26 pages, 11 figure

Generator Coordinate Truncations

We investigate the accuracy of several schemes to calculate ground-state correlation energies using the generator coordinate technique. Our test-bed for the study is the $sd$ interacting boson model, equivalent to a 6-level Lipkin-type model. We find that the simplified projection of a triaxial generator coordinate state using the $S_3$ subgroup of the rotation group is not very accurate in the parameter space of the Hamiltonian of interest. On the other hand, a full rotational projection of an axial generator coordinate state gives remarkable accuracy. We also discuss the validity of the simplified treatment using the extended Gaussian overlap approximation (top-GOA), and show that it works reasonably well when the number of boson is four or larger.Comment: 19 pages, 6 eps figure

Electrospray Mass Spectrometric Detection of Products and Short-Lived Intermediates in Aqueous Aerosol Microdroplets Exposed to a Reactive Gas

The intermediates ISO_3^- (m/z = 207) and IS2O3- (m/z = 239) generated in aqueous (NaI/Na_2S2O_3) microdroplets traversing dilute O_3 gas plumes are detected via online electrospray mass spectrometry within ∼1 ms, and their stabilities gauged by collisionally induced dissociation. The simultaneous detection of anionic reactants and the S_2O_6^(2-), HSO_4^-, IO_3^-, and I_3^- products as a function of experimental conditions provides evidence of genuinely interfacial reaction kinetics. Although O_3(aq) reacts about 3 times faster with I- than with S_2O_3^(2-) in bulk solution, only S_2O_3^(2-) is significantly depleted in the interfacial layers of [I^-]/[S_2O_3^(2-)] = 10 microdroplets below [O_3(g)] ∼ 50 ppm

Ozonolysis of Uric Acid at the Air/Water Interface

Uric acid (UA) epoxide, peroxide, and ozonide species produced in aqueous UA microdroplets exposed to O3(g) are detected by online mass spectrometry within ∼1 ms. UA conversions are independent of its initial concentration below ∼0.1 mM and are unaffected by addition of excess H2O2 or t-butanol. UA reactivity increases ∼380 times from pH 4 to 7, which is at variance with the pH-independent rates reported for the UA + O3(aq) reaction in bulk water. At pH ∼7, UA and ascorbic acid (AH2) microdroplets react with O3(g) at similar rates, although UA is ∼40 times more reactive than AH2 toward O3(aq) in bulk water. Only the UA epoxide, plus traces of UA peroxide, are formed upon mixing UA(aq) and O3(aq) solutions. We infer that the gas−liquid ozonolysis of UA proceeds in an interfacial aqueous medium quite distinct from bulk water. Thus, UA, a component of the pulmonary epithelial lining fluid that scavenges atmospheric O3(g) into less deleterious species (similar to AH2), is rendered inactive below pH ∼5. The potential implications of these findings on synergistic health effects between tropospheric ozone and acidic particulates are briefly analyzed

Syntaxin of Plant Proteins SYP123 and SYP132 Mediate Root Hair Tip Growth in Arabidopsis thaliana

Root hairs are fast-growing tubular protrusions on root epidermal cells that play important roles in water and nutrient uptake in plants. The tip-focused polarized growth of root hairs is accomplished by the secretion of newly synthesized materials to the tip via the polarized membrane trafficking mechanism. Here, we report the function of two different types of plasma membrane (PM) Qa-SNAREs (soluble N-ethylmaleimide-sensitive factor attachment protein receptors), SYP123 and SYP132, in the growth of root hair in Arabidopsis. We found that SYP123, but not SYP132, localizes in the tip region of root hairs by recycling between the brefeldin A (BFA)-sensitive endosomes and the PM of the expanding tip in an F-actin-dependent manner. The vesicle-associated membrane proteins VAMP721/722/724 also exhibited tip-focused localization in root hairs and formed ternary SNARE complexes with both SYP123 and SYP132. These results demonstrate that SYP123 and SYP132 act in a coordinated fashion to mediate tip-focused membrane trafficking for root hair tip growth. © 2014 The Author