Theoretical Investigation on Water-Free, Water- and Self-Assisted H-Abstraction Reactions from Dimethylamine by Hydroxy Radicals.

Accurate branching ratios of the H-abstraction reactions from dimethylamine (DMA) by OH radicals are important in understanding the atmospheric fate of DMA. In this work, the reaction kinetics of the water-free, water-assisted, and self-assisted H-abstraction reactions between DMA and OH radicals are accurately determined using the multipath canonical variational theory with the small-curvature tunneling correction, to explore the catalytic effects of the reactant (DMA) and product (water). To choose a suitable method that well describes the current reaction systems, various combinations with seven DFT methods and six basis sets are first evaluated, and the M08-HX/ma-TZVP method is identified as the most appropriate, with a mean unsigned deviation of 0.9 kcal mol-1 against the gold-standard CCSD(T)/CBS(T-Q) method. Based on the determined potential energy surfaces with the considerations of ground-state structures and specific-reaction parameters of zero-point energies, rate constants and branching ratios are calculated in a wide temperature range. The calculations show that the participation of water and DMA can lead to three-body complexes with a lower energy and influence the energy barriers, but neither of them shows the catalytic effect on the H-abstraction reactions in terms of kinetics. Additionally, the branching ratio analysis demonstrates that the product distribution is significantly altered in the presence of DMA and water.

Mycobacterial CpsA activates type I IFN signaling in macrophages via cGAS-mediated pathway.

Type I interferon (IFN) production is crucial in tuberculosis pathogenesis, yet the bacterial factors initiating this process are incompletely understood. CpsA, protein of Mycobacterium marinum and Mycobacterium tuberculosis, plays a key role in maintaining bacterial virulence and inhibiting host cell LC3-associated phagocytosis. By utilizing CpsA full deletion mutant studies, we re-verified its essential role in infection-induced pathology and revealed its new role in type I IFN expression. CpsA deficiency hindered IFN production in infected macrophages in vitro as well as zebrafish and mice in vivo. This effect was linked to the cGAS-TBK1-IRF3 pathway, as evidenced by decreased TBK1 and IRF3 phosphorylation in CpsA-deficient bacterial strain-infected macrophages. Moreover, we further show that CpsA deficiency cause decreased cytosolic DNA levels, correlating with impaired phagosomal membrane rupture. Our findings reveal a new function of mycobacterial CpsA in type I IFN production and offer insight into the molecular mechanisms underlying mycobacterial infection pathology.

Experimental study of microwave-catalytic oxidative degradation of COD in livestock farming effluent by copper-loaded activated carbon.

The problem of massive discharge of livestock wastewater is becoming more and more severe, causing irreversible damage to the ecological environment, and how to treat livestock wastewater efficiently and rapidly deserves to be studied in depth. In this work, CuO/granular activated carbon (GAC) loaded catalysts were prepared and characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), nitrogen adsorption/desorption techniques, and X-ray energy spectroscopy (EDS). The results showed that CuO was successfully attached to the GAC surface with good adsorption performance. The effects of catalyst dosage, H2O2 dosage, initial pH, microwave power and microwave irradiation time in different reaction systems on the degradation efficiency of chemical oxygen demand (COD) in wastewater were investigated, and the orthogonal experiments were used to explore the importance ranking of these factors. The highest degradation rate of COD was found to be enhanced by 12.1% in the reaction system of CuO/GAC, and the initial pH had the greatest effect on the COD removal rate. The combined MW/catalyst/H2O2 method used in this work provided a rapid and effective degradation of COD in wastewater, which can be helpful for reference in other microwave catalytic oxidation studies.

The continuum disordered pinning model.

Any renewal processes on [Formula: see text] with a polynomial tail, with exponent [Formula: see text], has a non-trivial scaling limit, known as the [Formula: see text]-stable regenerative set. In this paper we consider Gibbs transformations of such renewal processes in an i.i.d. random environment, called disordered pinning models. We show that for [Formula: see text] these models have a universal scaling limit, which we call the continuum disordered pinning model (CDPM). This is a random closed subset of [Formula: see text] in a white noise random environment, with subtle features:Any fixed a.s. property of the [Formula: see text]-stable regenerative set (e.g., its Hausdorff dimension) is also an a.s. property of the CDPM, for almost every realization of the environment.Nonetheless, the law of the CDPM is singular with respect to the law of the [Formula: see text]-stable regenerative set, for almost every realization of the environment. The existence of a disordered continuum model, such as the CDPM, is a manifestation of disorder relevance for pinning models with [Formula: see text].