Wildfires emit O3 precursors but there are large variations in emissions, plume heights, and photochemical processing. These factors make it challenging to model O3 production from wildfires using ...Eulerian models. Here we describe a statistical approach to characterize the maximum daily 8-h average O3 (MDA8) for 8 cities in the U.S. for typical, nonfire, conditions. The statistical model represents between 35% and 81% of the variance in MDA8 for each city. We then examine the residual from the model under conditions with elevated particulate matter (PM) and satellite observed smoke (“smoke days”). For these days, the residuals are elevated by an average of 3–8 ppb (MDA8) compared to nonsmoke days. We found that while smoke days are only 4.1% of all days (May–Sept) they are 19% of days with an MDA8 greater than 75 ppb. We also show that a published method that does not account for transport patterns gives rise to large overestimates in the amount of O3 from fires, particularly for coastal cities. Finally, we apply this method to a case study from August 2015, and show that the method gives results that are directly applicable to the EPA guidance on excluding data due to an uncontrollable source.
Insecticide susceptibility is mainly determined by the insect host, but symbiotic bacteria are also an important affecting factor. In this study, we investigate the relationship between the structure ...of gut bacterial symbionts and insecticide susceptibility in Diaphorina citri, the important carrier of Candidatus Liberibacter asiaticus (CLas), the causal agent of Huanglongbing (HLB). Our results indicated that antibiotic treatment significantly increased the susceptibility of D. citri to bifenthrin and thiamethoxam, and significantly decreased the relative abundance of Wolbachia and Profftella, enzyme activities of CarEs, and expression level of multiple CarE genes. The relative loads of Wolbachia and Profftella were positively correlated with DcitCCE13, DcitCCE14, DcitCCE15, and DcitCCE16. RNAi and prokaryotic expression revealed that DcitCCE15 is associated with bifenthrin metabolism. These results revealed that bacterial symbionts might regulate DcitCCE15 expression, which is involved in the susceptibility of D. citri to bifenthrin.
Fusarium head blight caused by Fusarium graminearum is a devastating disease in wheat that seriously endangers food security and human health. Previous studies have found that the secondary ...metabolite phenazine-1-carboxamide produced by biocontrol bacteria inhibited F. graminearum by binding to and inhibiting the activity of histone acetyltransferase Gcn5 (FgGcn5). However, the detailed mechanism of this inhibition remains unknown. Our structural and biochemical studies revealed that phenazine-1-carboxamide (PCN) binds to the histone acetyltransferase (HAT) domain of FgGcn5 at its cosubstrate acetyl-CoA binding site, thus competitively inhibiting the histone acetylation function of the enzyme. Alanine substitution of the residues in the binding site shared by PCN and acetyl-CoA not only decreased the histone acetylation level of the enzyme but also dramatically impacted the development, mycotoxin synthesis, and virulence of the strain. Taken together, our study elucidated a competitive inhibition mechanism of Fusarium fungus by PCN and provided a structural template for designing more potent phenazine-based fungicides.
The post-harvest fumigant, sulfuryl fluoride (SO2F2), is a >1000-fold more potent greenhouse gas than carbon dioxide and methane. Pilot studies have shown that SO2F2 fumes vented from fumigation ...chambers can be captured and hydrolyzed by hydroxide (OH–) and hydrogen peroxide (H2O2) at pH ∼ 12 in a scrubber, producing SO4 2– and F– as waste salts. To reduce the costs and challenges associated with purchasing and mixing these reagents onsite, this study evaluates the electrochemical generation of OH– and H2O2 within spent scrubbing solution, taking advantage of the waste SO4 2– and F– as free sources of electrolyte. The study used a gas diffusion electrode constructed from carbon paper coated with carbon black as a catalyst selective for the reduction of O2 to H2O2. Under galvanostatic conditions, the study evaluated the effect of electrochemical conditions, including applied cathodic current density and electrolyte strength. Within an electrolyte containing 200 mM SO4 2– and 400 mM F–, comparable to the waste salts generated by a SO2F2 scrubbing event, the system produced 250 mM H2O2 at pH 12.6 within 4 h with a Faradaic efficiency of 98.8% for O2 reduction to H2O2. In a scrubbing-water sample from lab-scale fumigation, the system generated ∼200 mM H2O2 at pH 13.5 within 4 h with a Faradaic efficiency of 75.6%. A comparison of the costs to purchase NaOH and H2O2 against the electricity costs for electrochemical treatment indicated that the electrochemical approach could be 38–71% lower, depending on the local cost of electricity.
Celangulin V is a novel botanical insecticide with significant bioactivity and a unique molecular target, but its complex polyol ester structure hinders its broader application in agriculture. To ...discover new analogues of celangulin V with a simpler structure and enhanced biological activities, we initiated a research project aimed at simplifying its structure and assessing insecticidal efficacy. In this study, a series of novel 1-tetralone derivatives were designed via a structure-based rational design approach and synthesized by a facile method. The biological activities of the target compounds were determined against Mythimna separata (M. separata), Plutella xylostella, and Rhopalosiphum padi. The results revealed that most of the synthesized compounds exhibited superior activities compared to celangulin V. Remarkably, the insecticidal activity of compound 6.16 demonstrated 102-fold greater stomach toxicity than celangulin V against M. separata. In addition, certain compounds showed significant contact toxicity against M. separata, a finding not reported previously in the structural optimization studies of celangulin V. Molecular docking analysis illustrated that the binding pocket of compound 6.16 with the H subunit of V-ATPase was the same as celangulin V. This study presents novel insights into the structural optimization of botanical pesticides.
Flavescence dorée phytoplasma (FDp) is a phytopathogenic bacterium associated with Grapevine yellowS disease, which causes heavy damage to viticultural production. Epidemiological data revealed that ...some FDp strains appear to be more widespread and aggressive. However, there is no data on mechanisms underlying the variable pathogenicity among strains. In this research, we employed chromatographic and spectrophotometric techniques to assess how two strains of FDp influence the levels of grapevine phenolic compounds, which are frequently utilized as indicative markers of stress conditions. The results pointed to the upregulation of all branches of phenolic metabolism through the development of infection, correlating with the increase in antioxidative capacity. The more aggressive strain M54 induced stronger downregulation of phenolics’ accumulation at the beginning and higher upregulation by the end of the season than the less aggressive M38 strain. These findings reveal potential targets of FDp effectors and provide the first functional demonstration of variable pathogenicity between FDp strains, suggesting the need for future comparative genomic analyses of FDp strains as an important factor in exploring the management possibilities of FDp.
The various grass-induced epichloëcyclins of the Epichloë spp. are ribosomally synthesized and post-translationally modified peptides (RiPPs), produced as small, secreted cyclopeptides from a ...single gene, gigA. Here, four clustered and coregulated genes (gigA, gigB, gigC, and kexB) with predicted roles in epichloëcyclin production in Epichloë festucae were evaluated through gene disruption. Subsequent chemical analysis indicates that GigB is a DUF3328 domain-containing protein associated with cyclization of epichloëcyclins; GigC is a methyltransferase enzyme responsible for N-methylation of desmethylepichloëcyclins; and KexB is a subtilisin-like enzyme, partly responsible for the propeptide cleavage of epichloëcyclin intermediates. Symbiotic effects on the host phenotype were not observed for gigA, gigC, or kexB mutants, although ΔgigB infection correlated with increased host tiller height and biomass, while only ΔkexB exhibited an effect on endophyte morphology. Disrupting epichloëcyclin biosynthesis showed negligible influence on the biosynthesis of E. festucae-associated alkaloids. Epichloëcyclins may perform other secondary metabolism functions in Epichloë and other fungi.
The imbalance between osteogenesis and osteoclastogenesis is a feature of bone metabolic disease. Cadmium (Cd) exposure causes human bone loss and osteoporosis (OP) through bioaccumulation of the ...food chain. However, the impact of Cd on bone tissues and the underlying molecular mechanisms are not well-characterized. In the current study, we found that the Cd concentration in bone tissues of OP patients was higher than normal subjects; meanwhile, the nuclear silent information regulator of transcription 1 (SIRT1) protein expression level was significantly decreased, which is a new star molecule to treat OP. It is further revealed that SIRT1 activation markedly reprograms bone metabolic and stress-response pathways that incline with osteoblast (OB) apoptosis. Suppressing reactive oxygen species (ROS) release with N-acetyl-l-cysteine (NAC) abolished Cd-induced reduction of SIRT1 protein, deacetylation of P53, OB apoptosis, and attenuated OP. Conversely, overexpression of SIRT1 suppressed Cd-induced ROS release. SIRT1 overexpression in vivo and in vitro dampened PGC-1α protein, acetylation of P53 at lysine 382, and caspase-dependent apoptosis. These results reveal that ROS/SIRT1 controls P53 acetylation and coordinates OB apoptosis involved in the onset of OP.
Di-(2-Ethylhexyl) phthalate (DEHP) and microplastics (MPs) have released widespread residues to the environment and possess the ability to cause damage to humans and animals. However, there are still ...gaps in the study of damage to neurons caused by DEHP and MPs in mice cerebra and whether they have combined toxic effects. To investigate the underlying mechanism of action, mice were fed 200 mg/kg DEHP and 10 mg/L MPs in vivo. In vitro, NS20Y (CBNumber: CB15474825) cells were treated with 25 μM DEHP and 775 mg/L MPs. Next, qRT-PCR and western blot analysis were performed to evaluate PI3K/AKT pathway genes, mitochondrial dynamics-related genes, apoptosis-related genes, and GSK-3β and its associated genes, mRNA, and protein expression. To determine pathological changes in the mice cerebra, hematoxylin and eosin (H&E) staining, transmission electron microscopy, and TUNEL staining were employed. To determine the levels of reactive oxygen species (ROS) and apoptosis cells in vitro, ROS staining, acridine orange/ethidium bromide (AO/EB) staining, and flow cytometry were performed. Our results demonstrated that DEHP and MPs caused changes in mitochondrial function, and GSK-3β and its associated gene expression in mice through the PI3K/AKT pathway, which eventually led to apoptosis of neurons. Moreover, our findings showed that DEHP and MPs have a combined toxic effect on mice cerebra. Our findings facilitate the understanding of the neurotoxic effects of DEHP and MPs on neurons in the cerebra of mice and help identify the important role of maintaining normal mitochondrial function in protecting cerebrum health.
Efficient preconcentration is critical for sensitive and selective electrochemical detection of metal ions, but rapid specific enrichment with depressed absorption of interfering ions at the ...electrode is challenging. Here, we proposed an electric field-induced specific preconcentration to boost the analytical performance of DNA-based electrochemical sensors for Hg2+ detection. As for such preconcentration, a positive external electric field was first used to enrich Hg2+ at an electrode assembled with T-rich DNA, thus boosting T–Hg2+–T recognitions. The following applied inverse electric field strips the nonspecifically absorbed Hg2+ and other interfering ions, thus depressing matrix interferences via self-cleaning. Based on this principle, we designed a portable device to realize programmable control of electric fields; a T–Hg2+–T recognition-based electrochemical sensor was thus fabricated as a model platform to assess the feasibility of electric field-induced preconcentration. The experimental results revealed that such a strategy decreased the time of T–Hg2+–T-based recognition from 60 to 20 min and led to detection with better reproducibility by depressing the influence of free Hg2+ as well as interfering ions. This strategy offered Hg2+ detection limits of 0.01 pMthree-fold better than that without preconcentrationwithin 22 min. The proposed preconcentration strategy offers a new way to enhance the analytical performance of sensing at the solid–liquid interface.
