Developing methods for the direct functionalization of quinones for assembly of highly functionalized quinones or bioactive natural products is an essential topic in the field of direct C–H ...functionalization. Quinone units are key motifs in many bioactive compounds and materials, and many innovative methods have been elaborated for the generation of these units. A major part of the established synthetic strategies combines installation of substituents on hydroquinones, phenols, or phenyl ethers through different coupling reactions with oxidation to produce the desired quinones. Most of these above‐mentioned methods introduce multiple chemical steps; however, the synthesis of quinoid compounds through the direct C–H functionalization of simple quinones remains challenging. This minireview summarizes the recently developed achievements for assembly of functionalized quinones through direct functionalization of simple quinones. Our focus will be on the methods and mechanism of these reactions that have appeared in the last two decades.
We focus on the recent advances, mainly in the past twenty years, in the synthesis of quinoid compounds through the direct functionalization of simple quinones. These reactions are classified by reaction types, including alkylation, arylation, amination/phosphination, sulfenylation, and others, in which the scope and limits, as well as the mechanisms of these reactions, are highlighted.
Smart luminescent metal–organic frameworks (MOFs) demonstrate promising performance in the detection of toxic gases. The incorporation of twisted or rotary organic ligands with aggregation‐induced ...emission (AIE) characteristics can provide further opportunities in designing such smart MOFs with new topologies and stimuli‐responsive behaviors. Herein, novel AIE MOFs are reported with reversible luminescence or a magnetic switch for HCl vapor detection. The twisted conformation of tetrakis(4‐carboxyphenyl)ethylene (TCPE) ligand leads to the unique M+–L–M−–L–M∞ (M = metal clusters, L = ligand) configuration for ZnMOF and CoMOF. Different from conventional MOFs with M–L∞ topology, ZnMOF and CoMOF exhibit a blue‐to‐yellow greenish fluorescence transition and a ferrimagnetic‐to‐antiferromagnetic switch behavior, respectively, upon recognition of HCl vapor. The adsorbed HCl molecules rather than coordinated ones are determined to be the main reason, and such luminescence and magnetic switch can be induced in a reversible manner via HCl vapor adsorption/desorption processes with high reliability. This work of AIE MOFs with twisted and rotary ligands shall pave new avenue in design of smart MOFs with new topologies and stimuli‐responsive behavior for real‐time sensing and detection applications.
With twisted AIE ligands, smart MOFs with M+–L–M––L–M∞ configuration are synthesized. Such unique topology renders these MOFs the specific responsiveness for HCl vapor detection. Upon recognition of HCl vapor, ZnMOF shows a fast blue‐to‐yellow greenish emission transition, while CoMOF exhibits a ferrimagnetic to antiferromagnetic switch behaviour.
While the presence of microplastics (MPs) in marine environments has been detected worldwide, the importance of MPs pollution in freshwater environments has also been emphasized in recent years. ...However, the body of knowledge regarding the biological effects of MPs on freshwater organisms is still much more limited than on marine organisms. The aim of the present study was to evaluate the accumulation and tissue distribution of MPs in the freshwater fish red tilapia (Oreochromis niloticus), as well as the biochemical effects of MPs on O. niloticus. During 14 days of exposure to 0.1 μm polystyrene-MPs at concentrations of 1, 10, and 100 μg L−1, the MPs concentrations in various tissues of O. niloticus generally increased over time following the order gut > gills > liver ≈ brain. Moreover, the acetylcholinesterase (AChE) activity in the fish brain was inhibited by MPs exposure, with a maximum inhibition rate of 37.7%, suggesting the potential neurotoxicity of MPs to freshwater fish. The activities of cytochrome P450 (CYP) enzymes 7-ethoxyresorufin O-deethylase (EROD) and 7-benzyloxy-4-trifluoromethyl-coumarin O-dibenzyloxylase (BFCOD) in the fish liver exhibited clear temporal variabilities, with significant decreases followed by elevations compared to the control. The alterations of the EROD and BFCOD activities indicate the potential involvement of CYP enzymes for the metabolism of MPs. The activity of antioxidative enzyme superoxide dismutase (SOD) in the liver was significantly induced throughout the exposure period, while the malondialdehyde (MDA) content did not vary with MPs exposure, suggesting that the antioxidative enzymatic system in O. niloticus could prevent oxidative damage. These results highlight the ingestion and accumulation of MPs in different tissues of freshwater fish, which lead to perturbations in fish biological systems and should be considered in environmental risk assessment.
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•The accumulation level of PS-MPs followed the order gut > gills > liver ≈ brain.•Exposure to PS-MPs inhibited AChE activity in the brain of red tilapia.•Exposure to PS-MPs disturbed metabolism in the liver of red tilapia.•Antioxidant systems in red tilapia can cope with oxidative stress from PS-MPs.
Exposure to polystyrene-microplastics can result in obvious accumulation in red tilapia and provoke alterations in various biochemical endpoints.
There are hundreds of thousands metric tons of microplastics (MPs) present in aquatic environments. The MPs coexist with other pollutants in water bodies, such as pharmaceuticals, and may carry and ...transfer them into aquatic organisms, consequently causing unpredictable ecological risks. The purpose of the present study was to evaluate the effect of the presence of polystyrene microplastics (PS-MPs) on the distribution and bioaccumulation of roxithromycin (ROX) in freshwater fish red tilapia (Oreochromis niloticus) as well as their interactive biochemical effects in red tilapia. PS-MPs were found to enhance the bioaccumulation of ROX in fish tissues compared to ROX-alone exposure. In the treatment of PS-MPs (100 μg L−1) combined with ROX (50 μg L−1), the highest concentrations of ROX reached 39,672.9 ± 6311.4, 1767.9 ± 277.8, 2907.5 ± 225.0, and 4307.1 ± 186.5 μg kg−1 in gut, gills, brain, and liver, respectively. Furthermore, compared to the ROX alone, the neurotoxicity caused by ROX was alleviated due to the presence of MPs after 14 d of exposure. The activities of cytochrome P450 (CYP) enzymes 7-ethoxyresorufin O-deethylase (EROD) and 7-benzyloxy-4-trifluoromethyl-coumarin O-dibenzyloxylase (BFCOD) in fish livers exposed to all co-exposure treatments exhibited great variability compared to ROX alone after 14 d of exposure, suggesting that the presence of MPs may affect the metabolism of ROX in tilapia. Compared with ROX alone, the superoxide dismutase (SOD) activity increased significantly, and malondialdehyde (MDA) contents decreased in the co-exposure treatments, showing that oxidative damage in situations of co-exposure to MPs and ROX was mitigated in fish livers after 14 d of exposure. Collectively, the presence of MPs could affect the fate and toxicity of other organic pollutants in fish. The results emphasize the importance to study the interactions between MPs and other organic pollutants in aquatic environments.
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•Interactive effects of microplastics and roxithromycin on fish were studied.•PS-MPs could enhance ROX bioaccumulation in red tilapia.•PS-MPs could mitigate the neurotoxicity and oxidative damage caused by ROX.•The presence of PS-MPs could affect the metabolism of ROX.
Background and Aim
Remimazolam tosilate (RT) is a new short‐acting GABA(A) receptor agonist, having potential to be an effective option for procedural sedation. Here, we aimed to compare the efficacy ...and safety of RT with propofol in patients undergoing upper gastrointestinal endoscopy.
Methods
This positive‐controlled, non‐inferiority, phase III trial recruited patients at 17 centers, between September 2017 and November 2017. A total of 384 patients scheduled to undergo upper gastrointestinal endoscopy were randomly assigned to receive RT or propofol. Primary endpoint was the success rate of sedation. Adverse events (AEs) were recorded to evaluate safety.
Results
The success rate of sedation in the RT group was non‐inferior to that in the propofol group (97.34% vs 100.00%; difference in rate −2.66%, 95% CI −4.96 to −0.36, meeting criteria for non‐inferiority). Patients in the RT group had longer time to adequate sedation (P < 0.0001) but shorter time to fully alert (P < 0.0001) than that in the propofol group. The incidences of hypotension (13.04% vs 42.86%, P < 0.0001), treatment‐related hypotension (0.54% vs 5.82%, P < 0.0001), and respiratory depression (1.09% vs 6.88%, P = 0.0064) were significantly lower in the RT group. AEs were reported in 74 (39.15%) patients in the RT group and 114 (60.32%) patients in the propofol group, with significant difference (P < 0.0001).
Conclusion
This trial established non‐inferior sedation success rate of RT compared with propofol. RT allows faster recovery from sedation compared with propofol. The safety profile is favorable and appears to be superior to propofol, indicating that it was feasible and well tolerated for patients.
Identification of new nasopharyngeal carcinoma (NPC) biomarkers is of great clinical value for the diagnosis and treatment of NPC. HOTAIR, a cancer‐related long non‐coding RNA, was tested and its ...prognostic value for NPC was evaluated. As determined using in situ hybridization (ISH), 91 of 160 (56.87%) paraffin‐embedded NPC biopsies showed high expression levels of HOTAIR (staining index score ≥ 6). HOTAIR was upregulated in tumors with a large size (P = 0.021), more advanced clinical stage (P = 0.012) and increased lymph node tumor burden (P = 0.005). Quantified using real‐time PCR, HOTAIR expression levels in fresh tissue and paraffin‐embedded samples were 5.2 ~ 48.4‐fold higher compared with non‐cancer tissue samples. Moreover, HOTAIR expression levels increased with clinical stage progression, which was consistent with ISH findings in the paraffin‐embedded tissue. Most importantly, NPC patients with higher HOTAIR levels had a poor prognosis for overall survival using univariate and multivariate analysis. In addition, HOTAIR mediated the migration, invasion and proliferation of NPC cells in vitro. HOTAIR is a potential biomarker for the prognosis of NPC, and dysregulation of HOTAIR might play an important role in NPC progression.
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•Effects of nano- and micro-plastics (N/MPs) with three sizes on tilapia were studied.•MPs with the size of 70 − 90 μm could be accumulated and were hazardous in tilapia.•5 μm MPs ...caused stronger toxicity than 70 − 90 MPs or 0.3 μm NPs in tilapia.•Toxicity of N/MPs may not be simply negatively correlated with their sizes.
Nanoplastics (NPs) and microplastics (MPs) are a heterogeneous class of pollutants with diverse sizes in aquatic environments. To evaluate the hazardous effects of N/MPs with different sizes, the accumulation, oxidative stress, cytochrome P450 (CYP) enzymes, neurotoxicity, and metabolomics changes were investigated in the red tilapia exposed to three sizes of polystyrene (PS) N/MPs (0.3, 5, and 70 − 90 μm). After 14-d exposures, the largest particles (70 − 90 μm) showed the highest accumulation levels in most cases. Exposures to PS-MPs (5 and 70 − 90 μm) caused a more severe oxidative stress in red tilapia than PS-NPs. The activity of CYP3A-related enzyme was obviously inhibited by PS-NPs, whereas the CYP enzymes in the liver may not be sensitive to MP exposures. In the brain, only 5 μm PS-MPs significantly inhibited the acetylcholinesterase activity. After exposures, the treatments with 0.3, 5, and 70 − 90 μm N/MPs resulted in 31, 40, and 23 significantly differentially expressed metabolites, respectively, in which the pathway of tyrosine metabolism was significantly affected by all the three PS-N/MP exposures. Overall, the PS particles within the μm size posed more severe stress to red tilapia. Our results suggest that the toxicity of N/MPs may not show a simply monotonic negative correlation with their sizes.
An efficient cobalt(III)‐catalyzed C‐2‐selective indole C–H hydroarylation of acrolein, enones, and glyoxylates was achieved under mild reaction conditions. The versatile cobalt(III) catalyst ...displayed excellent positional selectivity with the assistance of pyrimidinyl, pyridyl, and pyrazolyl directing groups, thus overcoming the inherent C‐3 selectivity of an electrophilic indole derivatization. This approach provides an expedient route to indolyl‐substituted aldehydes, ketones, and esters with wide functional group tolerance. In addition, it also features high step‐ and atom‐economy.
The development of digital technology and the sharing economy has extended corporations' innovative activities beyond the corporation's boundaries, so it has become more urgent to govern the lack of ...social responsibility and alienation of platform corporations from the perspective of social agents. First, the platform's CSR classification and social responsibility governance's main content are analyzed in this research. Then, this study uses government agencies, platform corporations, users, and the public as governance subjects and compares governance decisions with and without public and user oversight. Finally, the optimal balance strategy for each governing subject, the optimal trajectory of governance volume, and the trajectory of total revenue are obtained. The study found that: 1) Public and user supervision can improve the governance volume while encourage the governance motivation of government agencies and platform corporations. 2) The level of user supervision effort has a greater impact on the total governance revenue than public supervision. 3) The revenue of the system and the governance volume are greater in a centralized decision-making process, indicating that those involved should co-operate in governance based on the principle of mutual benefit. 4) The platform corporation has an incompatible but unified relationship between its social duty and financial success.
The present study used red tilapia (Oreochromis niloticusas) as the model fish to compare the interactive effects between aged and virgin microplastics (MPs) with the antibiotic sulfamethoxazole ...(SMX) and the β-blocker propranolol (PRP). To this end, the ultraviolet irradiation was used to simulate the MP aging in the environment. The accumulations of MPs and pharmaceuticals, and changes in enzyme activities and genes expressions in tilapia were also evaluated. Some physical properties of MPs changed during the aging process, reflected by 0.27- and 0.16-fold increases in the specific surface area and average pore volume, respectively. And more carbonyl formation was observed on the surface of aged MPs. Compared to the 14-d coexposure with virgin MPs, the MP aging increased the accumulation of PRP by 82.3% in the brain, whereas decreased the concentration of SMX by 46.1% in the gills. The stress on tilapia caused by the MPs and PRP was alleviated by the aging process, largely related to the lower neurotoxicity and reduced lipid peroxidation damages. However, the coexposure to aged MPs and SMX would result in higher inhibitions of cytochrome P450 enzymes activities. The results of the transcriptomics showed that the MP aging mainly influenced the expression of genes related to the metabolic process, immune system process, and the genetic information process in tilapia under the coexposure to MPs and pharmaceuticals. Collectively, our results suggest that the MP aging could induce complex changes in the interactive effects between MPs and pharmaceuticals on aquatic organisms.
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•Microplastic (MP) aging changed the accumulations of two pharmaceuticals.•MP aging alleviated the neural and oxidative damages of MPs and propranolol (PRP).•MP aging increased the CYP enzymes disorders by MPs and sulfamethoxazole (SMX).•MP aging influenced the expression of genes related to metabolic and immune system.•PRP and SMX influenced the expression of genes related to pathological processes.
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