The chemistries within phagosomes of APCs mediate microbial destruction as well as generate peptides for presentation on MHC class II. The antimicrobial effector NADPH oxidase (NOX2), which generates superoxide within maturing phagosomes, has also been shown to regulate activities of cysteine cathepsins through modulation of the lumenal redox potential. Using real-time analyses of lumenal microenvironmental parameters, in conjunction with hydrolysis pattern assessment of phagocytosed proteins, we demonstrated that NOX2 activity not only affects levels of phagosomal proteolysis as previously shown, but also the pattern of proteolytic digestion. Additionally, it was found that NOX2 deficiency adversely affected the ability of bone marrow–derived macrophages, but not dendritic cells, to process and present the I-Ab–immunodominant peptide of the autoantigen myelin oligodendrocyte glycoprotein (MOG). Computational and experimental analyses indicated that the I-Ab binding region of the immunodominant peptide of MOG is susceptible to cleavage by the NOX2-controlled cysteine cathepsins L and S in a redox-dependent manner. Consistent with these findings, I-Ab mice that were deficient in the p47phox or gp91phox subunits of NOX2 were partially protected from MOG-induced experimental autoimmune encephalomyelitis and displayed compromised reactivation of MOG-specific CD4+ T cells in the CNS, despite eliciting a normal primary CD4+ T cell response to the inoculated MOG Ag. Taken together, this study demonstrates that the redox microenvironment within the phagosomes of APCs is a determinant in MHC class II repertoire production in a cell-specific and Ag-specific manner, which can ultimately impact susceptibility to CD4+ T cell–driven autoimmune disease processes.

Clathrate hydrates are specific cage-like structures formed by water molecules around a guest molecule. Despite the many studies that have been performed on clathrate hydrates, the actual molecular mechanism of both their homogeneous and heterogeneous nucleation has yet to be fully clarified. Here, by means of molecular simulations, we demonstrate how the interface of hexagonal ice can facilitate the heterogeneous nucleation of methane clathrate hydrate from an aqueous methane solution. Our results indicate an initial accumulation of methane molecules, which promote induction of defective structures, particularly coupled 5-8 ring defects, at the ice surface. Structural fluctuations promoted by these defective motifs assist hydrate cage formation next to the interface. The cage-like structures formed then act as a sink for methane molecules in the solution and enhance the stability and growth of an amorphous nucleus, which can evolve into a hydrate crystal upon annealing. These results are illustrative of how a surface that is structurally incompatible can serve to facilitate heterogeneous nucleation of a new crystalline phase. They should also further our general understanding of the formation of gas hydrates and their critical roles in various industrial and environmental processes, including carbon capture and storage.

Despite dedicated efforts aimed at revealing possible molecular structures of the ice defects associated with stacking faults in ice (I), these molecular arrangements have remained a puzzle. Here we demonstrate how the reorganization of water molecules on different faces of ice (I) can facilitate formation of stacking faults within a crystal. We show that a pair of point defects can manifest a particular combination of coupled five- and eight-membered rings (5-8 rings). These structural motifs can facilitate a shift in layers within an ice (I) crystal, thereby inducing stacking faults. Furthermore, the presence of molecular solutes such as methane at the ice interface appears to trigger the formation of coupled 5-8 rings. The observation of such coupled 5-8 ring defects provides insights into the possible molecular mechanisms of stacking fault formation in ice (I) and has implications for ice crystal growth phenomenology and the consequent physical and chemical properties of ice.

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Hydrogen sulfide (H2S) can be a significant component of oil and gas upstream production, where H2S can be naturally generated in situ from reservoir biomass and from sulfate-containing minerals through microbial sulfate reduction and (or) thermochemical sulfate reduction. On the other hand, the technologies employed in oil and gas production, especially from unconventional resources, also can contribute to generation or delay of appearance of H2S. Steam-assisted gravity drainage and hydraulic fracturing used in production of oil sands and shale oil/gas, respectively, can potentially convert the sulfur content of the petroleum into H2S or contribute excess amounts of H2S during production. A brief overview of the different classes of chemical reactions involved in the in situ generation and release of H2S is provided in this work. Speciation calculations and reaction mechanisms are presented to explain why thermochemical sulfate reduction progresses at faster rates under low pH. New studies regarding the degradation of a hydraulic fracture fluid additive (sodium dodecly sulfate) are reported for T = 200 °C, p = 17 MPa, and high ionic strengths. The absence of an ionic strength effect on the reaction rate suggests that the rate-limiting step involves the reaction of neutral species, such as elemental sulfur. This is not the case with other thermochemical sulfate reduction studies at T > 300 °C. These two different kinetic regimes complicate the goal of extrapolating laboratory results for field-specific models for H2S production.