Reaction of Ba with ICl and IBr

The chemiluminescence from the reactions of Ba with ICl and IBr have been studied. Emission could be observed only from BaCl and BaBr. A broad emission in the near-IR could not be unambiguously assigned. The formation of IX-Ar (X = Cl, Br) van der Waals complexes quenched the chemiluminescence channel.     

Rapid Autoxidation Forms Highly Oxidized RO2 Radicals in the Atmosphere

Gas‐phase oxidation routes of biogenic emissions, mainly isoprene and monoterpenes, in the atmosphere are still the subject of intensive research with special attention being paid to the formation of aerosol constituents. This laboratory study shows that the most abundant monoterpenes (limonene and α‐pinene) form highly oxidized RO₂ radicals with up to 12 O atoms, along with related closed‐shell products, within a few seconds after the initial attack of ozone or OH radicals. The overall process, an intramolecular ROO→QOOH reaction and subsequent O₂ addition generating a next R′OO radical, is similar to the well‐known autoxidation processes in the liquid phase (QOOH stands for a hydroperoxyalkyl radical). Field measurements show the relevance of this process to atmospheric chemistry. Thus, the well‐known reaction principle of autoxidation is also applicable to the atmospheric gas‐phase oxidation of hydrocarbons leading to extremely low‐volatility products which contribute to organic aerosol mass and hence influence the aerosol–cloud–climate system.     

Visual spatial memory is enhanced in female rats (but inhibited in males) by dietary soy phytoestrogens

Background  

In learning and memory tasks, requiring visual spatial memory (VSM), males exhibit superior performance to females (a difference attributed to the hormonal influence of estrogen). This study examined the influence of phytoestrogens (estrogen-like plant compounds) on VSM, utilizing radial arm-maze methods to examine varying aspects of memory. Additionally, brain phytoestrogen, calbindin (CALB), and cyclooxygenase-2 (COX-2) levels were determined.     

Mass spectral evidence that small changes in composition caused by oxidative aging processes alter aerosol CCN properties

Oxidative processing (i.e., "aging") of organic aerosol particles in the troposphere affects their cloud condensation nuclei (CCN) activity, yet the chemical mechanisms remain poorly understood. In this study, oleic acid aerosol particles were reacted with ozone while particle chemical composition and CCN activity were simultaneously monitored. The CCN activated fraction at 0.66 +/- 0.06% supersaturation was zero for 200 nm mobility diameter particles exposed to 565 to 8320 ppmv O3 for less than 30 s. For greater exposure times, however, the particles became CCN active. The corresponding chemical change shown in the particle mass spectra was the oxidation of aldehyde groups to form carboxylic acid groups. Specifically, 9-oxononanoic acid was oxidized to azelaic acid, although the azelaic acid remained a minor component, comprising 3-5% of the mass in the CCN-inactive particles compared to 4-6% in the CCN-active particles. Similarly, the aldehyde groups of alpha-acyloxyalkylhydroperoxide (AAHP) products were also oxidized to carboxylic acid groups. On a mass basis, this conversion was at least as important as the increased azelaic acid yield. Analysis of our results with K?hler theory suggests that an increase in the water-soluble material brought about by the aldehyde-to-carboxylic acid conversion is an insufficient explanation for the increased CCN activity. An increased concentration of surface-active species, which decreases the surface tension of the aqueous droplet during activation, is an interpretation consistent with the chemical composition observations and K?hler theory. These results suggest that small changes in particle chemical composition caused by oxidation could increase the CCN activity of tropospheric aerosol particles during their atmospheric residence time.     

Nucleation of bulk phases in the HCl/H2O system

We report experimental results on the low-temperature uptake of HCl on H(2)O ice (ice). HCl was deposited on the surface at greater than monolayer amounts at 85 K, and the ice substrate was heated. The temperature dependence of the HCl vapor pressure from this phase was measured from 110 to 150 K, with the nucleation of a bulk hydrate phase observed at 150 K. Measurements were conducted in a closed system by simultaneous application of gas phase mass spectrometry and surface spectroscopy to characterize vapor/solid equilibrium and the nucleation of bulk hydrate phases. Combining the nucleation data reported here with data we reported previously (180 to 200 K) and data from two other laboratories (165 and 170 K), the thermodynamic boundaries for the nucleation of both the metastable bulk solution and bulk hydrate phases subsequent to monolayer adsorption of HCl have been determined. The nucleation of the metastable bulk solution phase occurs promptly at monolayer coverage at the ice/liquid coexistence boundary on the binary bulk phase diagram. The nucleation of the bulk hexahydrate occurs from this metastable solution along a locus of points defining a state of constant solution free energy. This measured free energy is -51.2 +/- 0.9 kJ/mol. Finally, the temperature dependence of the HCl vapor pressure from the low-temperature phase is reported here for the first time and is consistent with that of the metastable solution predicted by this thermodynamic model of uptake, extending the range of validity of this model of adsorption followed by bulk solution and hydrate nucleation to a lower bound in temperature of 110 K.     

Field detachment of the negatively charged water dimer

Beams of Ar _m (H₂O) ₂ ^? ,m=0 to 4, are passed through an electric field and separated with a quadrupole mass spectrometer. Form<=2 the signal disappears at 31±1 kV/cm. Form=3 and 4 and larger (H₂O) _n ^? (n≧6) no field detachment is observed up to 40 kV/cm. The application of these results to the binding of excess electron in water clusters is discussed.