Photooxidation-Initiated Aqueous-Phase Formation of Organic Peroxides: Delving into Formation Mechanisms.

Formation of highly oxygenated molecules (HOMs) such as organic peroxides (ROOR, ROOH, and H2O2) is known to degrade food and organic matter. Gas-phase unimolecular autoxidation and bimolecular RO2 + HO2/RO2 reactions are prominently renowned mechanisms associated with the formation of peroxides. However, the reaction pathways and conditions favoring the generation of peroxides in the aqueous phase need to be evaluated. Here, we identified bulk aqueous-phase ROOHs in varying organic precursors, including a laboratory model compound and monoterpene oxidation products. Our results show that formation of ROOHs is suppressed at enhanced oxidant concentrations but exhibits complex trends at elevated precursor concentrations. Furthermore, we observed an exponential increase in the yield of ROOHs when UV light with longer wavelengths was used in the experiment, comparing UVA, UVB, and UVC. Water-soluble organic compounds represent a significant fraction of ambient cloud-water components (up to 500 µM). Thus, the reaction pathways facilitating the formation of HOMs (i.e., ROOHs) during the aqueous-phase oxidation of water-soluble species add to the climate and health burden of atmospheric particulate matter.

Field evidence of brown carbon absorption enhancement linked to organic nitrogen formation in Indo-Gangetic Plain.

Atmospheric brown carbon (BrC), a short-lived climate forcer, absorbs solar radiation and is a substantial contributor to the warming of the Earth's atmosphere. BrC composition, its absorption properties, and their evolution are poorly represented in climate models, especially during atmospheric aqueous events such as fog and clouds. These aqueous events, especially fog, are quite prevalent during wintertime in Indo-Gangetic Plain (IGP) and involve several stages (e.g., activation, formation, and dissipation, etc.), resulting in a large variation of relative humidity (RH) in the atmosphere. The huge RH variability allowed us to examine the evolution of water-soluble brown carbon (WS-BrC) diurnally and as a function of aerosol liquid water content (ALWC) and RH in this study. We explored links between the evolution of WS-BrC mass absorption efficiency at 365 nm (MAEWS-BrC-365) and chemical characteristics, viz., low-volatility organics and water-soluble organic nitrogen (WSON) to water-soluble organic carbon (WSOC) ratio (org-N/C), in the field (at Kanpur in central IGP) for the first time worldwide. We observed that WSON formation governed enhancement in MAEWS-BrC-365 diurnally (except during the afternoon) in the IGP. During the afternoon, the WS-BrC photochemical bleaching dwarfed the absorption enhancement caused by WSON formation. Further, both MAEWS-BrC-365 and org-N/C ratio increased with a decrease in ALWC and RH in this study, signifying that evaporation of fog droplets or bulk aerosol particles accelerated the formation of nitrogen-containing organic chromophores, resulting in the enhancement of WS-BrC absorptivity. The direct radiative forcing of WS-BrC relative to that of elemental carbon (EC) was ∼19 % during wintertime in Kanpur, and âˆ¼ 40 % of this contribution was in the UV-region. These findings highlight the importance of further examining the links between the evolution of BrC absorption behavior and chemical composition in the field and incorporating it in the BrC framework of climate models to constrain the predictions.

Comprehensive analysis of emissions from wood and cow dung burning using chemometrics and two-dimensional gas chromatography.

Biomass burning is a global source of climate- and health-affecting emissions. The impacts of biomass burning emissions (BBE) are tied to their complex and variable chemical makeup. For instance, the nitrogen content of BBE influences their capacity to absorb light, and therefore affect the Earth's radiative budget. Factors such as temperature, biomass type, or air flow rate during the combustion all modify the composition of BBE, making accurate characterization challenging. Herein, for the first time, principal component analysis (PCA) was applied to emissions gathered during laboratory-based combustion of wood and cow dung biomass in a tube furnace. A thermal desorption two dimensional time-of-flight gas chromatography mass spectrometry (TD-GC × GC-ToF-MS) setup was employed to separate and identify chemical species. By combining these techniques with a feature selection algorithm, we determined that low temperature and air flow rate lead to greater feature separation on PCA scores plots. Of the 729 variables used to construct the plots, 61 were identified as significant. These species - including sugars such as d-Allose and melezitose, as well as tracers such as levoglucosan and guaiacol - significantly differentiated emissions from wood versus cow dung biomass, especially at lower temperatures. In particular, combustion of either fuel at 0.2 slpm and 500 °C, lead to 20 times the variability in levoglucosan peak area over more efficient furnace parameters. Chemical species evolved only from dung burning contained on average 0.595 nitrogen atoms versus 0.515 for wood, indicating that a higher nitrogen content of the base fuel may not necessarily translate into emission of unique nitrogen containing species, potentially causing the underestimation of dung burning impacts. Overall, TD-GC × GC-ToF-MS coupled to PCA reliably separated emissions from wood and dung biomass while simultaneously identifying significant chemical features, displaying the suitability of this combination of techniques towards characterizing complex BBE matrices in the future.

Light absorption potential of water-soluble organic aerosols in the two polluted urban locations in the central Indo-Gangetic Plain.

PM2.5 (particulate matter having aerodynamic diameter ≤2.5 µm) samples were collected during wintertime from two polluted urban sites (Allahabad and Kanpur) in the central Indo-Gangetic Plain (IGP) to comprehend the sources and atmospheric transformations of light-absorbing water-soluble organic aerosol (WSOA). The aqueous extract of each filter was atomized and analyzed in a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). Water-soluble organic carbon (WSOC) and WSOA concentrations at Kanpur were ∼1.2 and ∼1.5 times higher than that at Allahabad. The fractions of WSOC and secondary organic carbon (SOC) to total organic carbon (OC) were also significantly higher ∼53% and 38%, respectively at Kanpur compared to Allahabad. This indicates a higher abundance of oxidized WSOA at Kanpur. The absorption coefficient (babs-365) of light-absorbing WSOA measured at 365 nm was 46.5 ± 15.5 Mm-1 and 73.2 ± 21.6 Mm-1 in Allahabad and Kanpur, respectively, indicating the dominance of more light-absorbing fractions in WSOC at Kanpur. The absorption properties such as mass absorption efficiency (MAE365) and imaginary component of refractive index (kabs-365) at 365 nm at Kanpur were also comparatively higher than Allahabad. The absorption forcing efficiency (Abs SFE; indicates warming effect) of WSOA at Kanpur was ∼1.4 times higher than Allahabad. Enhancement in light absorption capacity was observed with the increase in f44/f43 (fraction of m/z 44 (f44) to 43 (f43) in organic mass spectra) and O/C (oxygen to carbon) ratio of WSOA at Kanpur while no such trend was observed for the Allahabad site. Moreover, the correlation between carbon fractions and light absorption properties suggested the influence of low-volatile organic compounds (OC3 + OC4 fraction obtained from thermal/optical carbon analyzer) in increasing the light absorption capacity of WSOA in Kanpur.

Absorption properties and forcing efficiency of light-absorbing water-soluble organic aerosols: Seasonal and spatial variability.

Light-absorbing organic aerosols, also known as brown carbon (BrC), enhance the warming effect of the Earth's atmosphere. The seasonal and spatial variability of BrC absorption properties is poorly constrained and accounted for in the climate models resulting in a substantial underestimation of their radiative forcing estimates. This study reports seasonal and spatial variability of absorption properties and simple forcing efficiency of light-absorbing water-soluble organic carbon (WSOC, SFEWSOC) by utilizing current and previous field-based measurements reported mostly from Asia along with a few observations from Europe, the USA, and the Amazon rainforest. The absorption coefficient of WSOC at 365 nm (babs-365) and the concentrations of carbonaceous species at Kanpur were about an order of magnitude higher during winter than in the monsoon season owing to differences in the boundary layer height, active sources and their strengths, and amount of seasonal wet precipitation. The WSOC aerosols during winter exhibited ∼1.6 times higher light absorption capacity than in the monsoon season at Kanpur site. The assessment of spatial variability of the imaginary component of the refractive index spectrum (kλ) across South Asia has revealed that it varies from ∼1 to 2 orders of magnitude and light absorption capacity of WSOC ranges from 3 to 21 W/g. The light absorption capacity of WSOC aerosols exhibited less spatial variability across East Asia (5-13 W/g) when compared to that in the South Asia. The photochemical aging of WSOC aerosols, indicated by the enhancement in WSOC/OC ratio, was linked to degradation in their light absorption capacity, whereas the absorption Ångström exponent (AAE) remained unaffected. This study recommends the adoption of refined climate models where sampling regime specific absorption properties are calculated separately, such that these inputs can better constrain the model estimates of the global effects of BrC.

Therapeutically effective covalent spike protein inhibitors in treatment of SARS-CoV-2.

COVID-19 [coronavirus disease 2019] has resulted in over 204,644,849 confirmed cases and over 4,323,139 deaths throughout the world as of 12 August 2021, a total of 4,428,168,759 vaccine doses have been administered. The lack of potentially effective drugs against the virus is making the situation worse and dangerous. Numerous forces are working on finding an effective treatment against the virus but it is believed that a de novo drug would take several months even if huge financial support is provided. The only solution left with is drug repurposing that would not only provide effective therapy with the already used clinical drugs, but also save time and cost of the de novo drug discovery. The initiation of the COVID-19 infection starts with the attachment of spike glycoprotein of SARS-CoV-2 to the host receptor. Hence, the inhibition of the binding of the virus to the host membrane and the entry of the viral particle into the host cell are one of the main therapeutic targets. This paper not only summarizes the structure and the mechanism of spike protein, but the main focus is on the potential covalent spike protein inhibitors.

Understanding the origin of carbonaceous aerosols during periods of extensive biomass burning in northern India.

Post-harvest crop residue burning is extensively practiced in North India, which results in enhanced particulate matter (PM) concentrations. This study explores the PM2.5 (particulate matter with aerodynamic diameter ≤ 2.5 µm) emissions during various time periods (pre-monsoon, monsoon, and post-monsoon) over the biomass burning source region in Beas, Punjab. The PM2.5 concentrations during the pre-monsoon period (106-458 µg m-3) and the post-monsoon period (184-342 µg m-3) were similar but much higher than concentrations during the monsoon season (23-95 µg m-3) due to enhanced wet deposition. However, the carbonaceous aerosol fraction in PM2.5 was nearly double in the post-monsoon season (∼27%) than the pre-monsoon period (∼15%). A higher contribution of secondary organic carbon (SOC) observed during the pre-monsoon season can be attributed to enhanced photochemical activity in dry conditions. Stable carbon isotope ratio (δ13C value) of ambient PM allowed elucidation of contributing sources. δ13CTC correlation with SOC during post-monsoon and pre-monsoon periods suggests significant influence of secondary formation processes during both time periods. The concentrations of carbon fractions in sampled sources and aerosols suggests contribution of biofuels, resulting in enhanced PM concentration at this location. δ13CTC values of pre- and post-monsoon samples show dominance of freshly emitted aerosols from local sources. Impact of biomass and biofuel combustion was also confirmed by biomass burning K+BB tracer, indicating that major agriculture residue burning occurred primarily during nighttime. C3 plant derived aerosols dominated at the sampling location during the entire sampling duration and contributed significantly during the pre-monsoon season. Whereas, both fossil fuel and C3 plant combustion contributed to the total mass of carbonaceous aerosols during the post-monsoon and monsoon seasons.