Interfacial Enrichment of Lauric Acid Assisted by Long-Chain Fatty Acids, Acidity and Salinity at Sea Spray Aerosol Surfaces.

Surfactant monolayers at sea spray aerosol (SSA) surfaces regulate various atmospheric processes including gas transfer, cloud interactions, and radiative properties. Most experimental studies of SSA employ a simplified surfactant mixture of long-chain fatty acids (LCFAs) as a proxy for the sea surface microlayer or SSA surface. However, medium-chain fatty acids (MCFAs) make up nearly 30% of the FA fraction in nascent SSA. Given that LCFA monolayers are easily disrupted upon the introduction of chemical heterogeneity (such as mixed chain lengths), simple FA proxies are unlikely to represent realistic SSA interfaces. Integrating experimental and computational techniques, we characterize the impact that partially soluble MCFAs have on the properties of atmospherically relevant LCFA mixtures. We explore the extent to which the MCFA lauric acid (LA) is surface stabilized by varying acidity, salinity, and monolayer composition. We also discuss the impacts of pH on LCFA-assisted LA retention, where the presence of LCFAs may shift the surface-adsorption equilibria of laurate─the conjugate base─toward higher surface activities. Molecular dynamic simulations suggest a mechanism for the enhanced surface retention of laurate. We conclude that increased FA heterogeneity at SSA surfaces promotes surface activity of soluble FA species, altering monolayer phase behavior and impacting climate-relevant atmospheric processes

#COVIDisAirborne: AI-enabled multiscale computational microscopy of delta SARS-CoV-2 in a respiratory aerosol

We seek to completely revise current models of airborne transmission of respiratory viruses by providing never-before-seen atomic-level views of the SARS-CoV-2 virus within a respiratory aerosol. Our work dramatically extends the capabilities of multiscale computational microscopy to address the significant gaps that exist in current experimental methods, which are limited in their ability to interrogate aerosols at the atomic/molecular level and thus obscure our understanding of airborne transmission. We demonstrate how our integrated data-driven platform provides a new way of exploring the composition, structure, and dynamics of aerosols and aerosolized viruses, while driving simulation method development along several important axes. We present a series of initial scientific discoveries for the SARS-CoV-2 Delta variant, noting that the full scientific impact of this work has yet to be realized

Revealing the Impacts of Chemical Complexity on Submicron Sea Spray Aerosol Morphology

Sea spray aerosol (SSA) ejected through bursting bubbles at the ocean surface are complex mixtures of salts and organic species. Composition affects their ability to form marine clouds which cover nearly three-quarters of the Earth and play a critical role in the climate system. Submicron SSA particles have long lifetimes in the atmosphere and impact the Earths climate, yet their cloud-forming potential is difficult to study at the single-particle level using conventional experimental techniques due to their small size. Here, we use large-scale molecular dynamics (MD) simulations as a computational microscope to provide never-before-seen, dynamical views of 40-nm model aerosol particles and their detailed molecular morphologies. We investigate how increasing chemical complexity impacts the distribution and partitioning of organic material throughout individual particles for a range of organic constituents with varying chemical properties. Our simulations show that organic surfactants commonly found in SSA readily partition between both the surface and interior of the aerosol, indicating that nascent SSA may be more heterogeneous than traditional morphological models suggest. We support our computational observations of heterogeneity at the SSA surface with Brewster angle microscopy on model interfaces. Ultimately, our work establishes large-scale MD simulations as a novel technique for interrogating aerosols at the single-particle level, and shows the morphological mechanisms underlying why submicron SSA readily absorb waterand thus have a higher cloud forming potentialthan would otherwise be predicted for organic-rich aerosols

Derlin rhomboid pseudoproteases employ substrate engagement and lipid distortion to enable the retrotranslocation of ERAD membrane substrates.

Nearly one-third of proteins are initially targeted to the endoplasmic reticulum (ER) membrane, where they are correctly folded and then delivered to their final cellular destinations. To prevent the accumulation of misfolded membrane proteins, ER-associated degradation (ERAD) moves these clients from the ER membrane to the cytosol, a process known as retrotranslocation. Our recent work in Saccharomyces cerevisiae reveals a derlin rhomboid pseudoprotease, Dfm1, is involved in the retrotranslocation of ubiquitinated ERAD membrane substrates. In this study, we identify conserved residues of Dfm1 that are critical for retrotranslocation. We find several retrotranslocation-deficient Loop 1 mutants that display impaired binding to membrane substrates. Furthermore, Dfm1 possesses lipid thinning function to facilitate in the removal of ER membrane substrates, and this feature is conserved in its human homolog, Derlin-1, further implicating that derlin-mediated retrotranslocation is a well-conserved process

Insights into the behavior of nonanoic acid and its conjugate base at the air/water interface through a combined experimental and theoretical approach.

The partitioning of medium-chain fatty acid surfactants such as nonanoic acid (NA) between the bulk phase and the air/water interface is of interest to a number of fields including marine and atmospheric chemistry. However, questions remain about the behavior of these molecules, the contributions of various relevant chemical equilibria, and the impact of pH, salt and bulk surfactant concentrations. In this study, the surface adsorption of nonanoic acid and its conjugate base is quantitatively investigated at various pH values, surfactant concentrations and the presence of salts. Surface concentrations of protonated and deprotonated species are dictated by surface-bulk equilibria which can be calculated from thermodynamic considerations. Notably we conclude that the surface dissociation constant of soluble surfactants cannot be directly obtained from these experimental measurements, however, we show that molecular dynamics (MD) simulation methods, such as free energy perturbation (FEP), can be used to calculate the surface acid dissociation constant relative to that in the bulk. These simulations show that nonanoic acid is less acidic at the surface compared to in the bulk solution with a pK a shift of 1.1 ± 0.6, yielding a predicted surface pK a of 5.9 ± 0.6. A thermodynamic cycle for nonanoic acid and its conjugate base between the air/water interface and the bulk phase can therefore be established. Furthermore, the effect of salts, namely NaCl, on the surface activity of protonated and deprotonated forms of nonanoic acid is also examined. Interestingly, salts cause both a decrease in the bulk pK a of nonanoic acid and a stabilization of both the protonated and deprotonated forms at the surface. Overall, these results suggest that the deprotonated medium-chain fatty acids under ocean conditions can also be present within the sea surface microlayer (SSML) present at the ocean/atmosphere interface due to the stabilization effect of the salts in the ocean. This allows the transfer of these species into sea spray aerosols (SSAs). More generally, we present a framework with which the behavior of partially soluble species at the air/water interface can be predicted from surface adsorption models and the surface pK a can be predicted from MD simulations

Insights into the behavior of nonanoic acid and its conjugate base at the air/water interface through a combined experimental and theoretical approach.

The partitioning of medium-chain fatty acid surfactants such as nonanoic acid (NA) between the bulk phase and the air/water interface is of interest to a number of fields including marine and atmospheric chemistry. However, questions remain about the behavior of these molecules, the contributions of various relevant chemical equilibria, and the impact of pH, salt and bulk surfactant concentrations. In this study, the surface adsorption of nonanoic acid and its conjugate base is quantitatively investigated at various pH values, surfactant concentrations and the presence of salts. Surface concentrations of protonated and deprotonated species are dictated by surface-bulk equilibria which can be calculated from thermodynamic considerations. Notably we conclude that the surface dissociation constant of soluble surfactants cannot be directly obtained from these experimental measurements, however, we show that molecular dynamics (MD) simulation methods, such as free energy perturbation (FEP), can be used to calculate the surface acid dissociation constant relative to that in the bulk. These simulations show that nonanoic acid is less acidic at the surface compared to in the bulk solution with a pK a shift of 1.1 ± 0.6, yielding a predicted surface pK a of 5.9 ± 0.6. A thermodynamic cycle for nonanoic acid and its conjugate base between the air/water interface and the bulk phase can therefore be established. Furthermore, the effect of salts, namely NaCl, on the surface activity of protonated and deprotonated forms of nonanoic acid is also examined. Interestingly, salts cause both a decrease in the bulk pK a of nonanoic acid and a stabilization of both the protonated and deprotonated forms at the surface. Overall, these results suggest that the deprotonated medium-chain fatty acids under ocean conditions can also be present within the sea surface microlayer (SSML) present at the ocean/atmosphere interface due to the stabilization effect of the salts in the ocean. This allows the transfer of these species into sea spray aerosols (SSAs). More generally, we present a framework with which the behavior of partially soluble species at the air/water interface can be predicted from surface adsorption models and the surface pK a can be predicted from MD simulations

Revealing the Impacts of Chemical Complexity on Submicrometer Sea Spray Aerosol Morphology

Sea spray aerosol (SSA) ejected through bursting bubbles at the ocean surface is a complex mixture of salts and organic species. Submicrometer SSA particles have long atmospheric lifetimes and play a critical role in the climate system. Composition impacts their ability to form marine clouds, yet their cloud-forming potential is difficult to study due to their small size. Here, we use large-scale molecular dynamics (MD) simulations as a "computational microscope" to provide never-before-seen views of 40 nm model aerosol particles and their molecular morphologies. We investigate how increasing chemical complexity impacts the distribution of organic material throughout individual particles for a range of organic constituents with varying chemical properties. Our simulations show that common organic marine surfactants readily partition between both the surface and interior of the aerosol, indicating that nascent SSA may be more heterogeneous than traditional morphological models suggest. We support our computational observations of SSA surface heterogeneity with Brewster angle microscopy on model interfaces. These observations indicate that increased chemical complexity in submicrometer SSA leads to a reduced surface coverage by marine organics, which may facilitate water uptake in the atmosphere. Our work thus establishes large-scale MD simulations as a novel technique for interrogating aerosols at the single-particle level

#COVIDisAirborne:AI-Enabled Multiscale Computational Microscopy of Delta SARS-CoV-2 in a Respiratory Aerosol

We seek to completely revise current models of airborne transmission of respiratory viruses by providing never-before-seen atomic-level views of the SARS-CoV-2 virus within a respiratory aerosol. Our work dramatically extends the capabilities of multiscale computational microscopy to address the significant gaps that exist in current experimental methods, which are limited in their ability to interrogate aerosols at the atomic/molecular level and thus obscure our understanding of airborne transmission. We demonstrate how our integrated data-driven platform provides a new way of exploring the composition, structure, and dynamics of aerosols and aerosolized viruses, while driving simulation method development along several important axes. We present a series of initial scientific discoveries for the SARS-CoV-2 Delta variant, noting that the full scientific impact of this work has yet to be realized