Photofragment Coincidence Imaging of Small I- (H2O)n Clusters Excited to the Charge-transfer-to-solvent State

The photodissociation dynamics of small I{sup -}(H{sub 2}O){sub n} (n = 2-5) clusters excited to their charge-transfer-to-solvent (CTTS) states have been studied using photofragment coincidence imaging. Upon excitation to the CTTS state, two photodissociation channels were observed. The major channel ({approx}90%) is a 2-body process forming neutral I + (H{sub 2}O){sub n} photofragments, and the minor channel is a 3-body process forming I + (H{sub 2}O){sub n-1} + H{sub 2}O fragments. Both process display translational energy (P(E{sub T})) distributions peaking at E{sub T} = 0 with little available energy partitioned into translation. Clusters excited to the detachment continuum rather than to the CTTS state display the same two channels with similar P(E{sub T}) distributions. The observation of similar P(E{sub T}) distributions from the two sets of experiments suggests that in the CTTS experiments, I atom loss occurs after autodetachment of the excited (I(H{sub 2}O){sub n}{sup -})* cluster, or, less probably, that the presence of the excess electron has little effect on the departing I atom

Secondary organic aerosol formation from photooxidation of naphthalene and alkylnaphthalenes: implications for oxidation of intermediate volatility organic compounds (IVOCs)

Current atmospheric models do not include secondary organic aerosol (SOA) production from gas-phase reactions of polycyclic aromatic hydrocarbons (PAHs). Recent studies have shown that primary emissions undergo oxidation in the gas phase, leading to SOA formation. This opens the possibility that low-volatility gas-phase precursors are a potentially large source of SOA. In this work, SOA formation from gas-phase photooxidation of naphthalene, 1-methylnaphthalene (1-MN), 2-methylnaphthalene (2- MN), and 1,2-dimethylnaphthalene (1,2-DMN) is studied in the Caltech dual 28-m^3 chambers. Under high-NO_x conditions and aerosol mass loadings between 10 and 40μgm^(−3), the SOA yields (mass of SOA per mass of hydrocarbon reacted) ranged from 0.19 to 0.30 for naphthalene, 0.19 to 0.39 for 1-MN, 0.26 to 0.45 for 2-MN, and constant at 0.31 for 1,2-DMN. Under low-NO_x conditions, the SOA yields were measured to be 0.73, 0.68, and 0.58, for naphthalene, 1- MN, and 2-MN, respectively. The SOA was observed to be semivolatile under high-NO_x conditions and essentially nonvolatile under low-NO_x conditions, owing to the higher fraction of ring-retaining products formed under low-NO_x conditions. When applying these measured yields to estimate SOA formation from primary emissions of diesel engines and wood burning, PAHs are estimated to yield 3–5 times more SOA than light aromatic compounds over photooxidation timescales of less than 12 h. PAHs can also account for up to 54% of the total SOA from oxidation of diesel emissions, representing a potentially large source of urban SOA

Chemical Composition of Gas- and Aerosol-Phase Products from the Photooxidation of Naphthalene

The current work focuses on the detailed evolution of the chemical composition of both the gas- and aerosol-phase constituents produced from the OH-initiated photooxidation of naphthalene under low- and high-NO_x conditions. Under high-NO_x conditions ring-opening products are the primary gas-phase products, suggesting that the mechanism involves dissociation of alkoxy radicals (RO) formed through an RO_2 + NO pathway, or a bicyclic peroxy mechanism. In contrast to the high-NO_x chemistry, ring-retaining compounds appear to dominate the low-NO_x gas-phase products owing to the RO_2 + HO_2 pathway. We are able to chemically characterize 53−68% of the secondary organic aerosol (SOA) mass. Atomic oxygen-to-carbon (O/C), hydrogen-to-carbon (H/C), and nitrogen-to-carbon (N/C) ratios measured in bulk samples by high-resolution electrospray ionization time-of-flight mass spectrometry (HR-ESI-TOFMS) are the same as the ratios observed with online high-resolution time-of-flight aerosol mass spectrometry (HR-ToF-AMS), suggesting that the chemical compositions and oxidation levels found in the chemically-characterized fraction of the particle phase are representative of the bulk aerosol. Oligomers, organosulfates (R-OSO_3), and other high-molecular-weight (MW) products are not observed in either the low- or high-NO_x SOA; however, in the presence of neutral ammonium sulfate seed aerosol, an organic sulfonic acid (R-SO_3), characterized as hydroxybenzene sulfonic acid, is observed in naphthalene SOA produced under both high- and low-NO_x conditions. Acidic compounds and organic peroxides are found to account for a large fraction of the chemically characterized high- and low-NO_x SOA. We propose that the major gas- and aerosol-phase products observed are generated through the formation and further reaction of 2-formylcinnamaldehyde or a bicyclic peroxy intermediate. The chemical similarity between the laboratory SOA and ambient aerosol collected from Birmingham, Alabama (AL) and Pasadena, California (CA) confirm the importance of PAH oxidation in the formation of aerosol within the urban atmosphere

Secondary organic aerosol formation from biomass burning intermediates: phenol and methoxyphenols

The formation of secondary organic aerosol from oxidation of phenol, guaiacol (2-methoxyphenol), and syringol (2,6-dimethoxyphenol), major components of biomass burning, is described. Photooxidation experiments were conducted in the Caltech laboratory chambers under low-NO_x (< 10 ppb) conditions using H_2O_2 as the OH source. Secondary organic aerosol (SOA) yields (ratio of mass of SOA formed to mass of primary organic reacted) greater than 25% are observed. Aerosol growth is rapid and linear with the primary organic conversion, consistent with the formation of essentially non-volatile products. Gas- and aerosol-phase oxidation products from the guaiacol system provide insight into the chemical mechanisms responsible for SOA formation. Syringol SOA yields are lower than those of phenol and guaiacol, likely due to novel methoxy group chemistry that leads to early fragmentation in the gas-phase photooxidation. Atomic oxygen to carbon (O : C) ratios calculated from high-resolution-time-of-flight Aerodyne Aerosol Mass Spectrometer (HR-ToF-AMS) measurements of the SOA in all three systems are ~ 0.9, which represent among the highest such ratios achieved in laboratory chamber experiments and are similar to that of aged atmospheric organic aerosol. The global contribution of SOA from intermediate volatility and semivolatile organic compounds has been shown to be substantial (Pye and Seinfeld, 2010). An approach to representing SOA formation from biomass burning emissions in atmospheric models could involve one or more surrogate species for which aerosol formation under well-controlled conditions has been quantified. The present work provides data for such an approach

Knowledge and Perceptions of Couples' Voluntary Counseling and Testing in Urban Rwanda and Zambia: A Cross-Sectional Household Survey

Most incident HIV infections in sub-Saharan Africa occur between cohabiting, discordant, heterosexual couples. Though couples' voluntary HIV counseling and testing (CVCT) is an effective, well-studied intervention in Africa, <1% of couples have been jointly tested.We conducted cross-sectional household surveys in Kigali, Rwanda (n = 600) and Lusaka, Zambia (n = 603) to ascertain knowledge, perceptions, and barriers to use of CVCT.Compared to Lusaka, Kigali respondents were significantly more aware of HIV testing sites (79% vs. 56%); had greater knowledge of HIV serodiscordance between couples (83% vs. 43%); believed CVCT is good (96% vs. 72%); and were willing to test jointly (91% vs. 47%). Stigma, fear of partner reaction, and distance/cost/logistics were CVCT barriers.Though most respondents had positive attitudes toward CVCT, the majority were unaware that serodiscordance between cohabiting couples is possible. Future messages should target gaps in knowledge about serodiscordance, provide logistical information about CVCT services, and aim to reduce stigma and fear

Sox2 regulates astrocytic and vascular development in the retina

Sox2 is a transcriptional regulator that is highly expressed in retinal astrocytes, yet its function in these cells has not previously been examined. To understand its role, we conditionally deleted Sox2 from the population of astrocytes and examined the consequences on retinal development. We found that Sox2 deletion does not alter the migration of astrocytes, but it impairs their maturation, evidenced by the delayed upregulation of glial fibrillary acidic protein (GFAP) across the retina. The centro-peripheral gradient of angiogenesis is also delayed in Sox2-CKO retinas. In the mature retina, we observed lasting abnormalities in the astrocytic population evidenced by the sporadic loss of GFAP immunoreactivity in the peripheral retina as well as by the aberrant extension of processes into the inner retina. Blood vessels in the adult retina are also under-developed and show a decrease in the frequency of branch points and in total vessel length. The developmental relationship between maturing astrocytes and angiogenesis suggests a causal relationship between the astrocytic loss of Sox2 and the vascular architecture in maturity. We suggest that the delay in astrocytic maturation and vascular invasion may render the retina hypoxic, thereby causing the abnormalities we observe in adulthood. These studies uncover a novel role for Sox2 in the development of retinal astrocytes and indicate that its removal can lead to lasting changes to retinal homeostasis