N-Iodosuccinimide-Mediated Synthesis of Benzo-Fused Bisimidazoles Enabled by a One-Pot Tandem Reaction of Fluorinated Propargyl Amidines.

A N-iodosuccinimide (NIS)-mediated divergent and efficient tandem reaction between fluorinated propargyl amidines and aromatic o-diamines without any metal catalyst and additive under mild reaction conditions was developed for the synthesis of benzo-fused bisimidazoles in moderate to excellent yields. Preliminary mechanistic studies suggested that this reaction proceeded by an intermediate of secondary amine derived from 5-iodomethyl imidazole, and NIS played another role of oxidation reagent to promote the formation of a benzimidazole motif.

Synthesis of Tetrahydro-5H-indolo[2,3-b]quinolines through Copper-Catalyzed Cascade Reactions of Aza-o-quinone Methides with Indoles.

A variety of tetrahydro-5H-indolo[2,3-b]quinolines were prepared in 40-97% yields through a copper(II)-catalyzed cascade reaction of aza-o-quinone methides generated in situ from 2-(chloromethyl)anilines and indoles. Experimental results showed that the reaction underwent double 1,4-additions and sequential intramolecular cyclization. The present method features broad substrate scope, good functional group tolerance, and easy gram scalable preparation of indolo[2,3-b]quinolines.

Significant Reductions in Secondary Aerosols after the Three-Year Action Plan in Beijing Summer.

Air quality in China has continuously improved during the Three-Year Action Plan (2018-2020); however, the changes in aerosol composition, properties, and sources in Beijing summer remain poorly understood. Here, we conducted real-time measurements of aerosol composition in five summers from 2018 to 2022 along with WRF-Community Multiscale Air Quality simulations to characterize the changes in aerosol chemistry and the roles of meteorology and emission reductions. Largely different from winter, secondary inorganic aerosol and photochemical-related secondary organic aerosol (SOA) showed significant decreases by 55-67% in summer, and the most decreases occurred in 2021. Comparatively, the decreases in the primary aerosol species and gaseous precursors were comparably small. While decreased atmospheric oxidation capacity as indicated by ozone changes played an important role in changing SOA composition, the large decrease in aerosol liquid water and small increase in particle acidity were critical for nitrate changes by decreasing gas-particle partitioning substantially (∼28%). Analysis of meteorological influences demonstrated clear and similar transitions in aerosol composition and formation mechanisms at a relative humidity of 50-60% in five summers. Model simulations revealed that emission controls played the decisive role in reducing sulfate, primary OA, and anthropogenic SOA during the Three-Year Action Plan, while meteorology affected more nitrate and biogenic SOA.

Refractory black carbon aerosols in rainwater in the summer of 2019 in Beijing: Mass concentration, size distribution and wet scavenging ratio.

Black carbon (BC) aerosols in the atmosphere play a significant role in climate systems due to their strong ability to absorb solar radiation. The lifetime of BC depends on atmospheric transport, aging and consequently on wet scavenging processes (in-cloud and below-cloud scavenging). In this study, sequential rainwater samples in eight rainfall events collected in 2 mm interval were measured by a tandem system including a single particle soot photometer (SP2) and a nebulizer. The results showed that the volume-weighted average (VWA) mass concentrations of refractory black carbon (rBC) in each rainfall event varied, ranging from 10.8 to 78.9 µg/L. The highest rBC concentrations in the rainwater samples typically occurred in the first fraction from individual rainfall events. The geometric mean median mass-equivalent diameter (MMD) decreased under precipitation, indicating that rBC with larger sizes was relatively aged and preferentially removed by wet scavenging. A positive correlation (R2 = 0.73) between the VWA mass concentrations of rBC in rainwater and that in ambient air suggested the important contribution of scavenging process. Additionally, the contributions of in-cloud and below-cloud scavenging were distinguished and accounted for 74% and 26% to wet scavenging, respectively. The scavenging ratio of rBC particles was estimated to be 0.06 on average. This study provides helpful information for better understanding the mechanism of rBC wet scavenging and reducing the uncertainty of numerical simulations of the climate effects of rBC.

Vertically Resolved Aerosol Chemistry in the Low Boundary Layer of Beijing in Summer.

Air quality in Beijing has been improved significantly in recent years; however, our knowledge of the vertically resolved aerosol chemistry in summer remains poor. Here, we carried out comprehensive measurements of aerosol composition, gaseous species, and aerosol optical properties on a meteorological tower in Beijing in summer and compared with those measured in winter. Our results showed that aerosol liquid water (ALW) contributing approximately 50% of the total mass with higher values aloft played a crucial role in aerosol formation. Particularly, the higher nitrate concentration in city aloft than at the ground level during daytime was mainly due to the enhanced gas-particle partitioning driven by ALW and particle acidity. The vertical profiles of organic aerosol (OA) factors varied more differently in the urban boundary layer. Although the ubiquitous decreases in primary OA with the increase in height were mainly due to the influences of local emissions and vertical convection, the vertical differences in oxygenated OA between summer and winter may be related to the photochemical processing of different biogenic and anthropogenic volatile organic compounds. The single-scattering albedo, brown carbon, and absorption Ångstrom exponent of aerosol particles also presented different vertical profiles between day and night due to the vertical changes in aerosol chemistry.

Comparative genomic and secretomic characterisation of endophytic Bacillus velezensis LC1 producing bioethanol from bamboo lignocellulose.

Bacillus is an excellent organic matter degrader, and it has exhibited various abilities required for lignocellulose degradation. Several B. velezensis strains encode lignocellulosases, however their ability to efficiently transform biomass has not been appreciated. In the present study, through the comparative genomic analysis of the whole genome sequences of 21 B. velezensis strains, CAZyome related to lignocellulose degradation was identified and their similarities and differences were compared. Subsequently, the secretome of B. velezensis LC1 by liquid chromatography-tandem mass spectrometry (LC-MS/MS) were identified and confirmed that a considerable number of proteins were involved in lignocellulose degradation. Moreover, after 6-day treatment, the degradation efficiency of the B. velezensis LC1 toward cellulose, hemicellulose and lignin were 59.90%, 75.44% and 23.41%, respectively, the hydrolysate was subjected to ethanol fermentation with Saccharomyces cerevisiae and Escherichia coli KO11, yielded 10.44 g/L ethanol after 96 h. These results indicate that B. velezensis LC1 has the ability to effectively degrade bamboo lignocellulose and has the potential to be used in bioethanol production.

Copper(I)-catalyzed [4 + 2] cycloaddition of aza-ortho-quinone methides with bicyclic alkenes.

A variety of tetrahydroquinoline-fused bicycles bearing multiple stereocenters are prepared in good yields with high diastereoselectivity through Cu2O-catalyzed [4 + 2] cycloaddition of aza-ortho-quinone methides (ao-QMs) with bicyclic alkenes. Mechanistic studies reveal that the Cu(i) catalyst not only promotes the formation of ao-QMs through a radical process by single electron transfer but also accelerates [4 + 2] cycloaddition. The reaction was easily performed on gram scale and the obtained tetrahydroquinoline-fused bicycles can be converted to diverse tetrahydroquinoline scaffolds.

Vertical Distributions of Primary and Secondary Aerosols in Urban Boundary Layer: Insights into Sources, Chemistry, and Interaction with Meteorology.

Vertical measurements are essential for the characterization of aerosol and boundary layer interactions; yet, our knowledge of vertical profiles of primary and secondary aerosol species in megacities is limited. Here, we conducted comprehensive vertical measurements of aerosol particle composition on a 325 m meteorological tower with two aerosol chemical speciation monitors in winter in urban Beijing. The simultaneous measurements at ground level, 140, and 240 m illustrated similar aerosol bulk composition at these three heights. However, the vertical ratios varied significantly among different aerosol species. Particularly, the vertical ratios of the aqueous phase and photochemical-related secondary organic aerosol (SOA) (aqOOA/OOA) decreased significantly, accompanied by the increases in ratios of secondary to primary OA, highlighting different chemical properties of OA between ground level and aloft, and the large impacts of vertical changes in meteorology and gaseous precursors on SOA formation. The vertical changes in NO3/SO4 ratios, however, were mostly insignificant, likely due to the low relative humidity and aerosol water content that inhibited nocturnal heterogeneous reactions in the residual layer. Considerable increases in the ratios of 240 m to ground level in the early morning were also observed for most aerosol species, demonstrating impact of residual layer on the air pollution of 2nd day.

Real-time characterization of aerosol particle composition, sources and influences of increased ventilation and humidity in an office.

Most of human exposure to atmospheric pollutants occurs indoors, and the components of outdoor aerosols may have been changed in the way before reaching indoor spaces. Here we conducted real-time online measurements of mass concentrations and chemical composition of black carbon and the non-refractory species in PM2.5 in an occupied office for approximately one month. The open-close windows and controlled dampness experiments were also performed. Our results show that indoor aerosol species primarily originate from outdoors with indoor/outdoor ratio of these species typically less than unity except for certain organic aerosol (OA) factors. All aerosol species went through filtration upon transport indoors. Ammonium nitrate and fossil fuel OA underwent evaporation or particle-to-gas partitioning, while less oxidized secondary OA (SOA) underwent secondary formation and cooking OA might have indoor sources. With higher particulate matter (PM) mass concentration outdoors than in the office, elevated natural ventilation increased PM exposure indoors and this increased exposure was prolonged when outdoor PM was scavenged. We found that increasing humidity in the office led to higher indoor PM mass concentration particularly more oxidized SOA. Overall, our results highlight that indoor exposure of occupants is substantially different from outdoor in terms of mass concentrations and chemical species.

Major Facilitator Superfamily Transporter Gene FgMFS1 Is Essential for Fusarium graminearum to Deal with Salicylic Acid Stress and for Its Pathogenicity towards Wheat.

Wheat is a major staple food crop worldwide, due to its total yield and unique processing quality. Its grain yield and quality are threatened by Fusarium head blight (FHB), which is mainly caused by Fusarium graminearum. Salicylic acid (SA) has a strong and toxic effect on F. graminearum and is a hopeful target for sustainable control of FHB. F. graminearum is capable of efficientdealing with SA stress. However, the underlying mechanisms remain unclear. Here, we characterized FgMFS1 (FGSG_03725), a major facilitator superfamily (MFS) transporter gene in F. graminearum. FgMFS1 was highly expressed during infection and was upregulated by SA. The predicted three-dimensional structure of the FgMFS1 protein was consistent with the schematic for the antiporter. The subcellular localization experiment indicated that FgMFS1 was usually expressed in the vacuole of hyphae, but was alternatively distributed in the cell membrane under SA treatment, indicating an element of F. graminearum in response to SA. ΔFgMFS1 (loss of function mutant of FgMFS1) showed enhanced sensitivity to SA, less pathogenicity towards wheat, and reduced DON production under SA stress. Re-introduction of a functional FgMFS1 gene into ∆FgMFS1 recovered the mutant phenotypes. Wheat spikes inoculated with ΔFgMFS1 accumulated more SA when compared to those inoculated with the wild-type strain. Ecotopic expression of FgMFS1 in yeast enhanced its tolerance to SA as expected, further demonstrating that FgMFS1 functions as an SA exporter. In conclusion, FgMFS1 encodes an SA exporter in F. graminearum, which is critical for its response to wheat endogenous SA and pathogenicity towards wheat.

Aerosol characterization in a city in central China plain and implications for emission control.

Extensive studies on aerosol chemistry have been carried out in megacities in China, however, aerosol characterization in Central China Plain (CCP) is limited. Here we conducted real-time measurements of fine particle composition with a time-of-flight aerosol chemical speciation monitor in Kaifeng, Henan province in October 2019. Our results showed that nitrate and organics constituted the major fraction of non-refractory PM2.5 for the entire study, on average accounting for 34% and 33%, respectively. However, aerosol composition was substantially different among four periods due to different meteorological conditions and chemical processing. For instance, nitrate presented the lowest contribution during the first period due to evaporative loss associated with high temperature (T), and then rapidly increased during polluted periods as a function of relative humidity (RH). Positive matrix factorization analysis showed the dominance of secondary organic aerosol (SOA) in OA, and also the changes in OA composition under different T and RH levels. In addition, this study is unique with two periods of local emission controls. Back trajectory and coefficient of divergence analysis showed that air pollution in CCP was overall homogeneously distributed. As a result, the effectiveness of local emission controls in this region was strongly affected by meteorological conditions and regional transport. We found that one of the periods with emission control even showed the highest concentrations for the entire study. Our results point towards the limited effect of local emission controls in mitigating air pollution in CCP, and highlight the importance of joint emission controls under unfavorable meteorological conditions.

The interactions between gut microbiota and bioactive ingredients of traditional Chinese medicines: A review.

In recent years, the interaction between the bioactive ingredients of traditional Chinese medicine (TCM) and gut microbiota has been a focus of many studies. When TCM enters the digestive tract, some bioactive ingredients are not absorbed into the gut well thus leading to low bioavailability. Ingredients of TCM are metabolised, or biotransformed by gut microbiota, thereby producing new bioactive molecules, and promote medicine absorption into the circulation. At the same time, the ingredients of TCM effect the composition and structure of gut microbiota, thereby influencing the remote function of diseased organs / tissues through the systemic action of the gut microbiota. In this review, we summarise the gut microbiota-mediated metabolism of flavonoids, alkaloids, terpenoids, saponins, polysaccharides, phenylpropanoids, and organic acids, along with a discussion on the metabolites formed and the biotransformation pathways involving various enzymes. We also highlight the importance of bioactive ingredients of TCM in regulating gut microbiota.

Synthesis of Furo[3,2-b]quinolines and Furo[2,3-b:4,5-b']diquinolines through [4 + 2] Cycloaddition of Aza-o-Quinone Methides and Furans.

An approach for the construction of furo[3,2-b]quinolines and furo[2,3-b:4,5-b']diquinolines is developed through a metal-free [4 + 2] cycloaddition of easily available in situ generated aza-o-quinone methides and furans. The reaction tolerates a wide range of aza-o-quinone methides and substituted furans to afford the corresponding dihydro- or tetrahydrofuroquinolines in good to excellent yields. Mechanistic studies reveal that the reaction involves a concerted [4 + 2] cycloaddition pathway and shows a high regioselectivity of cycloaddition for a furan ring. The present method features mild reaction conditions, dearomatization of furans, high regio- and diastereoselectivity, gram-scalable preparations, and diversity of furoquinolines.

The Role of CTGF in Inflammatory Responses Induced by Silica Particles in Human Bronchial Epithelial Cells.

BACKGROUND: Prolonged exposure to crystalline silica leads to persistent pulmonary inflammation and progressive fibrosis. Connective tissue growth factor (CTGF) has emerged as a potent proinflammatory and profibrotic regulator to participate in a variety of chronic inflammatory diseases. However, the role of CTGF in silica-induced pulmonary inflammation remains poorly understood. METHODS: To explore the effect of CTGF on inflammatory responses caused by silica particles, human bronchial epithelial cells (16HBE) were transfected with CTGF siRNA and exposed to silica particles at concentrations of 0, 12.5, 25, 50, 100 µg/ml for 48 h. Intracellular CTGF mRNA and protein expressions were determined by RT-PCR and Western blotting, respectively. The levels of inflammatory cytokines including IL-8, TNF-α, IL-6, IL-1ß, IL-17A and TGF-ß1 were measured by ELISA kits. RESULTS: Silica particles induce significantly elevated intracellular CTGF mRNA expression in 16HBE cells in a dose-dependent manner when compared with blank control group (P < 0.05). The secretions of IL-8, TNF-α, IL-6 and IL-17A were also significantly increased by silica particles (P < 0.05). After exposure to 25 or 50 µg/ml silica particles, the expression of intracellular CTGF mRNA was significantly inhibited in 16HBE cells when transfected with CTGF siRNA (P < 0.05). The secreted levels of IL-8, TNF-α, IL-6 and IL-17A induced by silica particles were also significantly lower from CTGF siRNA-transfected cells than that from normal 16HBE cells (P < 0.05). CONCLUSION: Inhibition of CTGF gene attenuates silica-induced inflammatory responses in bronchial epithelial cells, suggesting that CTGF could be a pivotal regulator in the development of silica-induced inflammation.

High signal-intensity abnormalities in susceptibility-weighted imaging for primary intracerebral hemorrhage.

Purpose: To identify the regularity of signal evolution of intracerebral hemorrhage on susceptibility-weighted imaging (SWI) at different stages compared with T1-weighted imaging (T1WI) and T2-weighted imaging (T2WI). Methods: We retrospectively evaluated a series of 365 patients who underwent T1WI, T2WI, and SWI examination simultaneously or sequentially in our hospital from January 2015 to May 2017. Two neuroradiologists assessed the images and discrepancies between their interpretations were resolved by consensus. Statistical analysis was performed using Chi-squared and Kappa tests. Results: Of the 365 patients on SWI sequence, 94 were enrolled. SWI detected the cases at different stages; T1WI detected 89 cases and T2WI detected 91 cases. The signal intensity of intracerebral hemorrhage on SWI was significantly associated with T1WI imaging and T2WI (χ2 = 4.651; p < 0.05; χ2 = 26.396; p < 0.01, respectively), especially at the late subacute stage. There was moderate consistency between the signal intensity of intracerebral hemorrhage on T2WI and SWI (Kappa coefficient = 0.530). Conclusion: Intracerebral hemorrhage has a varied appearance on SWI, and the evolution of signal of intracerebral hemorrhage on SWI sequence is influenced by T1WI and T2WI. Hematoma detection should be closely combined with clinical manifestation.

Plasma Sfrp5 levels correlate with determinants of the metabolic syndrome in Chinese adults.

BACKGROUND: Secreted frizzled-related protein-5 (Sfrp5) is a novel adipokine, and it has been found to link insulin resistance with diabetes. Animal studies have revealed the role of Sfrp5 in regulating lipid and glucose metabolism. The objective of this study was to investigate the relationship between Sfrp5 and the metabolic syndrome (MetS) in a cross-sectional study. METHODS: We conducted a series of cross-sectional studies of Chinese population including 194 control participants and 90 MetS patients. Circulating Sfrp5 concentrations were determined by ELISA. The relationships between circulating Sfrp5 levels and MetS components were assessed. RESULTS: Circulating Sfrp5 was significantly lower in newly examined MetS patients than in control participants (49.1 ± 17.2 vs 61.6 ± 23.2 µg/L, P < .01). Circulating Sfrp5 correlated negatively with markers of adiposity (waist-to-hip ratio, body mass index, and free fatty acids, P < .001 or P < .05). Furthermore, Sfrp5 levels correlated with fasting insulin, 2 h-ins, fasting blood glucose, 2 h post-glucose load blood glucose, HbA1c , and homeostasis model assessment of insulin resistance. In addition, circulating Sfrp5 levels were closely associated with blood pressure, high-density lipoprotein cholesterol, triglycerides, and atherosclerotic index. Circulating concentrations of Sfrp5 decreased progressively with continued increases in the numbers of MetS components. The analysis of receiver operating characteristic curves revealed that the best cutoff value for circulating Sfrp5 to predict MetS was 46.8 µg/L (sensitivity 70.1 %, specificity 47.8 %, and AUC 0.66). CONCLUSIONS: We conclude that Sfrp5 may be an adipokine that is associated with the pathogenesis of MetS in humans.

[Variety systematization and research progress of Mongolian medicine "Bashaga"].

Mongolian medicine is the traditional drug with the theory of Mongolian medicine and pharmacy as a guide, which made a great contribution to the survival and development of the Mongolian people. Mongolian medicine "Bashaga" faced the situations of origin is unclear, and clinical therapy is confused and so on. This paper summarizes the original plants and studies the species textual research and ethnopharmacology of Mongolian medicine "Bashaga". This paper intends to ensure authentic plant and provide comprehensive insight into the chemical constituents, pharmacology and application status of Mongolian medicine "Bashaga" to discuss the rationality of the confirmation in "Bashaga" authentic plant.

Seasonal characterization of chemical and optical properties of water-soluble organic aerosol in Beijing.

Water-soluble organic aerosol (WSOA) plays a crucial role in altering radiative forcing and impacting human health. However, our understanding of the seasonal variations of WSOA in Chinese megacities after the three-year clean air action plan is limited. In this study, we analyzed PM2.5 filter samples collected over one year (2020-2021) in Beijing to characterize the seasonal changes in the chemical and optical properties of WSOA using an offline aerosol mass spectrometer along with spectroscopy techniques. The mean mass concentration of WSOA during the observation period was 8.84 ± 7.12 µg m-3, constituting approximately 64-67 % of OA. Our results indicate the contribution of secondary OA (SOA) increased by 13-28 % due to a substantial reduction in primary emissions after the clean air action plan. The composition of WSOA exhibited pronounced seasonal variations, with a predominant contribution from less oxidized SOA in summer (61 %) and primary OA originating from coal combustion and biomass burning during the heating season (34 %). The mass absorption efficiency of WSOA at 365 nm in winter was nearly twice that in summer, suggesting that WSOA from primary emissions possesses a stronger light-absorbing capability than SOA. On average, water-soluble brown carbon accounted for 33-48 % of total brown carbon absorption. Fluorescence analysis revealed humic-like substances as the most significant fluorescence component of WSOA, constituting 82 %. Furthermore, both absorption and fluorescence chromophores were associated with nitrogen-containing compounds, highlighting the role of nitrogen-containing species in influencing the optical properties of WSOA. The results are important for chemical transport models to accurately simulate the WSOA and its climate effects.

Clinical effect of limited posterior decompression and 13-mm titanium mesh implantation on severe thoracolumbar burst fractures: A case series.

Background: Posterior incision with 270° spinal canal decompression and reconstruction surgery is a treatment option for thoracolumbar burst fractures (TLBF), but the large diameter titanium mesh placement is difficult. This study evaluated the characteristics and clinical effects of limited posterior decompression and 13-mm titanium mesh implantation to treat TLBF. Hypothesis: 13-mm titanium meshes could be used to fix thoracolumbar burst fractures. Patients and methods: This case series included patients who underwent limited posterior decompression and 13-mm titanium mesh implantation at China Medical University Shaoxing Hospital (01/2015-12/2019). The Cobb angle, injury vertebral anterior edge height loss percentage, and spinal canal occupancy rate were analyzed. The degree of spinal cord injury was evaluated according to the ASIA grade. Results: Fifteen patients were included (eight males and seven females). The patients were 32.2 ± 4.6 years of age. The American Association of Spinal Injury improved after surgery (A/B/C/D/E: from 2/6/5/2/0 to 0/0/2/8/5, P < 0.001). The Cobb angle decreased after surgery (from 20.1 ± 4.8° to 7.1 ± 1.4°, P < 0.001) but increased to 8.2 ± 0.9° at 1 year (P = 0.003). The percentage of loss of the anterior edge height of the injured vertebrae decreased after surgery (from 40.9% ± 6.1% to 7.5% ± 1.8%, P < 0.001) and decreased at 1 year (7.0% ± 1.5%, P = 0.044). The spinal canal occupancy rate decreased after surgery (from 64.8% ± 7.8% to 20.1% ± 4.2%, P < 0.001) but did not decrease further at 1 year (19.4% ± 3.4%, P = 0.166). Discussion: Spinal canal limited posterior decompression, and 13-mm titanium mesh implantation in the treatment of TLBF can achieve one-stage spinal canal decompression and three-column reconstruction. The curative effect was satisfying. Level of evidence: Level IV; case series.

Palladacycle-Catalyzed Regioselective Heck Reaction Using Diaryliodonium Triflates and Aryl Iodides.

We describe a P-containing palladacycle-catalyzed regioselective Heck reaction of 2,3-dihydrofuran with diaryliodonium salts and aryl iodides to afford 2-aryl-2,5-dihydrofurans and 2-aryl-2,3-dihydrofurans, respectively, in good yields. Mechanistic studies revealed that the oxidative addition of diaryliodonium salts to palladacycles to form Pd(IV) species showed high chemoselectivity and that electron-rich aryl moieties were preferentially transferred to the Heck product. DFT calculations indicated that the regioselectivity-determining step is the reductive elimination reaction rather than the isomerization and reinsertion of Pd(IV)-hydride intermediates into the double bond.