Is either direct photolysis or photocatalysed H-shift of peroxyl radicals a competitive pathway in the troposphere?

Peroxyl radicals (ROO.) are key intermediates in atmospheric chemistry, with relatively long lifetimes compared to most other radical species. In this study, we use multireference quantum chemical methods to investigate whether photolysis can compete with well-established ROO. sink reactions. We assume that the photolysis channel is always ROO. + h nu => RO + O(P-3). Our results show that the maximal value of the cross-section for this channel is sigma = 1.3 x 10(-18) cm(2) at 240 nm for five atmospherically representative peroxyl radicals: CH3OO., C(O)HCH2OO., CH3CH2OO., HC(O)OO. and CH3C(O)OO.. These values agree with experiments to within a factor of 2. The rate constant of photolysis in the troposphere is around 10(-5) s(-1) for all five ROO.. As the lifetime of peroxyl radicals in the troposphere is typically less than 100 s, photolysis is thus not a competitive process. Furthermore, we investigate whether or not electronic excitation to the first excited state (D-1) by infrared radiation can facilitate various H-shift reactions, leading, for example, in the case of CH3OO. to formation of O.H and CH2O or HOO. and CH2 products. While the activation barriers for H-shifts in the D-1 state may be lower than in the ground state (D-0), we find that H-shifts are unlikely to be competitive with decay back to the D-0 state through internal conversion, as this has a rate of the order of 10(13) s(-1) for all studied systems.Peer reviewe

TGFβ1 single-nucleotide polymorphism C-509T alters mucosal cell function in pediatric eosinophilic esophagitis.

Eosinophilic esophagitis (EoE) is a chronic Th2 antigen-driven disorder associated with tissue remodeling. Inflammation and remodeling lead to esophageal rigidity, strictures, and dysphagia. TGFβ1 drives esophageal remodeling including epithelial barrier dysfunction and subepithelial fibrosis. A functional SNP in the TGFβ1 gene that increases its transcription (C-509T) is associated with elevated numbers of esophageal TGFβ1-expressing cells. We utilized esophageal biopsies and fibroblasts from TT-genotype EoE children to understand if TGFβ1 influenced fibroblast and epithelial cell function in vivo. Genotype TT EoE esophageal fibroblasts had higher baseline TGFβ1, collagen1α1, periostin, and MMP2 (p < 0.05) gene expression and distinct contractile properties compared with CC genotype (n = 6 subjects per genotype). In vitro TGFβ1 exposure caused greater induction of target gene expression in genotype CC fibroblasts (p < 0.05). Esophageal biopsies from TT-genotype subjects had significantly less epithelial membrane-bound E-cadherin (p < 0.01) and wider cluster distribution at nanometer resolution. TGFβ1 treatment of stratified primary human esophageal epithelial cells and spheroids disrupted transepithelial resistance (p < 0.001) and E-cadherin localization (p < 0.0001). A TGFβ1-receptor-I inhibitor improved TGFβ1-mediated E-cadherin mislocalization. These data suggest that EoE severity can depend on genotypic differences that increase in vivo exposure to TGFβ1. TGFβ1 inhibition may be a useful therapy in subsets of EoE patients

Calculating rate constants for intersystem crossing and internal conversion in the Franck-Condon and Herzberg-Teller approximations

Effective and fast algorithms for calculating rate constants for internal conversion (IC) and intersystem crossing (ISC) in the Franck-Condon and Herzberg-Teller approximations have been developed and implemented. The methods have been employed for calculating IC and ISC rate constants for the pyrromethene-567 dye (PM567), hetero[8]circulene (4B) and free-base porphyrin (H2P). The fluorescence quantum yields obtained by comparing calculated rate constants for the radiative and non-radiative processes are in good agreement with experimental data.Peer reviewe

Aromaticity of Even-Number Cyclo[n]carbons (n=6-100)

The recently synthesized cyclo[18]carbon molecule has been characterized in a number of studies by calculating electronic, spectroscopic, and mechanical properties. However, cyclo[18] carbon is only one member of the class of cyclo[n]carbons-standalone carbon allotrope representatives. Many of the larger members of this class of molecules have not been thoroughly investigated. In this work, we calculate the magnetically induced current density of cyclo[n]carbons in order to elucidate how electron delocalization and aromatic properties change with the size of the molecular ring (n), where n is an even number between 6 and 100. We find that the Hiickel rules for aromaticity (4k + 2) and antiaromaticity (4k) become degenerate for large C-n rings (n > 50), which can be understood as a transition from a delocalized electronic structure to a nonaromatic structure with localized current density fluxes in the triple bonds. Actually, the calculations suggest that cyclo[n]carbons with n > 50 are nonaromatic cyclic polyalkynes. The influence of the amount of nonlocal exchange and the asymptotic behavior of the exchange-correlation potential of the employed density functionals on the strength of the magnetically induced ring current and the aromatic character of the large cyclo[n]carbons is also discussed.Peer reviewe

Computed Pre-reactive Complex Association Lifetimes Explain Trends in Experimental Reaction Rates for Peroxy Radical Recombinations

The lifetimes of pre-reactive complexes, although implicitly part of the equations used to model many gas-phase bimolecular reactions, have seldom been included in quantitative calculations of rate coefficients. Here, we demonstrate the application of empirical molecular dynamics simulations of collisions between peroxy radicals to model association lifetimes. With the exception of the methyl peroxy−acetyl peroxy system, measurements of the lifetimes based on a phenomenological model are shown to correlate well with available experimental data for recombination reactions of peroxy radicals in cases where the rate-limiting transition state lies below the reactants in energy. Further, we predict reaction rates for larger α-pinene-derived peroxy radicals, and we interpret our results in tandem with available experimental data on these systems, which are of great relevance to improve our understanding of atmospheric aerosol formation.Peer reviewe

Isomer-Resolved Mobility-Mass Analysis of alpha-Pinene Ozonolysis Products

Highly oxygenated organic molecules (HOMs) are important sources of atmospheric aerosols. Resolving the molecular-level formation mechanisms of these HOMs from freshly emitted hydrocarbons improves the understanding of aerosol properties and their influence on the climate. In this study, we measure the electrical mobility and mass-to-charge ratio of alpha-pinene oxidation products using a secondary electrospray-differential mobility analyzer-mass spectrometer (SESI-DMA-MS). The mass-mobility spectrum of the oxidation products is measured with seven different reagent ions generated by the electrospray. We analyzed the mobility-mass spectra of the oxidation products C9-10H14-18O2-6. Our results show that acetate and chloride yield the highest charging efficiencies. Analysis of the mobility spectra suggests that the clusters have 1-5 isomeric structures (i.e., ion-molecule cluster structures with distinct mobilities), and the number is affected by the reagent ion. Most of the isomers are likely cluster isomers originating from binding of the reagent ion to different sites of the molecule. By comparing the number of observed isomers and measured mobilities and collision cross sections between standard pinanediol and pinonic acid to the values observed for C10H18O2 and C10H16O3 produced from oxidation of alpha-pinene, we confirm that pinanediol and pinonic acid are the only isomers for these elemental compositions in our experimental conditions. Our study shows that the SESI-DMA-MS produces new information from the first steps of oxidation of alpha-pinene.Peer reviewe

Nitrogen fixation and denitrification activity differ between coral- and algae-dominated Red Sea reefs

Coral reefs experience phase shifts from coral- to algae-dominated benthic communities, which could affect the interplay between processes introducing and removing bioavailable nitrogen. However, the magnitude of such processes, i.e., dinitrogen (N-2) fixation and denitrification levels, and their responses to phase shifts remain unknown in coral reefs. We assessed both processes for the dominant species of six benthic categories (hard corals, soft corals, turf algae, coral rubble, biogenic rock, and reef sands) accounting for>98% of the benthic cover of a central Red Sea coral reef. Rates were extrapolated to the relative benthic cover of the studied organisms in co-occurring coral- and algae-dominated areas of the same reef. In general, benthic categories with high N-2 fixation exhibited low denitrification activity. Extrapolated to the respective reef area, turf algae and coral rubble accounted for>90% of overall N-2 fixation, whereas corals contributed to more than half of reef denitrification. Total N-2 fixation was twice as high in algae- compared to coral-dominated areas, whereas denitrification levels were similar. We conclude that algae-dominated reefs promote new nitrogen input through enhanced N-2 fixation and comparatively low denitrification. The subsequent increased nitrogen availability could support net productivity, resulting in a positive feedback loop that increases the competitive advantage of algae over corals in reefs that experienced a phase shift.Peer reviewe

Large methane releases lead to strong aerosol forcing and reduced cloudiness

The release of vast quantities of methane into the atmosphere as a result of clathrate destabilization is a potential mechanism for rapid amplification of global warming. Previous studies have calculated the enhanced warming based mainly on the radiative effect of the methane itself, with smaller contributions from the associated carbon dioxide or ozone increases. Here, we study the effect of strongly elevated methane (CH4) levels on oxidant and aerosol particle concentrations using a combination of chemistry-transport and general circulation models. A 10-fold increase in methane concentrations is predicted to significantly decrease hydroxyl radical (OH) concentrations, while moderately increasing ozone (O3). These changes lead to a 70 % increase in the atmospheric lifetime of methane, and an 18 % decrease in global mean cloud droplet number concentrations (CDNC). The CDNC change causes a radiative forcing that is comparable in magnitude to the longwave radiative forcing ("enhanced greenhouse effect") of the added methane. Together, the indirect CH4-O3 and CH4-OH-aerosol forcings could more than double the warming effect of large methane increases. Our findings may help explain the anomalously large temperature changes associated with historic methane releases

High rates of carbon and dinitrogen fixation suggest a critical role of benthic pioneer communities in the energy and nutrient dynamics of coral reefs

Following coral mortality in tropical reefs, pioneer communities dominated by filamentous and crustose algae efficiently colonize substrates previously occupied by coral tissue. This phenomenon is particularly common after mass coral mortality following prolonged bleaching events associated with marine heatwaves. Pioneer communities play an important role for the biological succession and reorganization of reefs after disturbance. However, their significance for critical ecosystem functions previously mediated by corals, such as the efficient cycling of carbon (C) and nitrogen (N) within the reef, remains uncertain. We used 96 carbonate tiles to simulate the occurrence of bare substrates after disturbance in a coral reef of the central Red Sea. We measured rates of C and dinitrogen (N-2) fixation of pioneer communities on these tiles monthly over an entire year. Coupled with elemental and stable isotope analyses, these measurements provide insights into macronutrient acquisition, export and the influence of seasonality. Pioneer communities exhibited high rates of C and N(2)fixation within 4-8 weeks after the introduction of experimental bare substrates. Ranging from 13 to 25 mu mol C cm(-2) day(-1)and 8 to 54 nmol N cm(-2) day(-1), respectively, C and N(2)fixation rates were comparable to reported values for established Red Sea coral reefs. This similarity indicates that pioneer communities may quickly compensate for the loss of benthic productivity by corals. Notably, between 40% and 85% of fixed organic C was exported into the environment, constituting a vital source of energy for the coral reef food web. Our findings suggest that benthic pioneer communities may play a crucial, yet overlooked role in the C and N dynamics of oligotrophic coral reefs by contributing to the input of new C and N after coral mortality. While not substituting other critical ecosystem functions provided by corals (e.g. structural habitat complexity and coastal protection), pioneer communities likely contribute to maintaining coral reef nutrient cycling through the accumulation of biomass and import of macronutrients following coral loss. A freePlain Language Summarycan be found within the Supporting Information of this article.Peer reviewe