Insights into the antineoplastic activity and mechanisms of action of coumarin-coordinated 8-hydroxyquinoline ruthenium(II/III) compounds.

Ruthenium(II/III) coordination compounds have gained widespread attention as chemotherapy drugs, photosensitizers, and photodynamic therapy reagents. Herein, a family of 11 novel coumarin-coordinated 8-hydroxyquinoline ruthenium(II/III) compounds, i.e., [RuII2(µ2-Cl)2(QL1a)2(DMSO)4] (YNU-4a = Yulin Normal University-4a), [RuII2(µ2-Cl)2(QL1b)2(DMSO)4] (YNU-4b), [RuII2(µ2-Cl)2(QL1c)2(DMSO)4] (YNU-4c), [RuII2(µ2-Cl)2(QL1d)2(DMSO)4]⋅2CH3OH (YNU-4d), [RuII(QL1e)2(DMSO)2] (YNU-4e), [RuIII(QL1e)2(QL3a)] (YNU-4f), [RuIII(QL1e)2(QL3b)] (YNU-4g), [RuIII(QL1e)2(QL3c)] (YNU-4h), [RuIICl2(H-QL3a)2(DMSO)2] (YNU-4i), [RuIICl2(H-QL3b)2(DMSO)2] (YNU-4j), and [RuIICl2(H-QL3c)2(DMSO)2] (YNU-4k), featuring the coligands 5,7-diiodo-8-hydroxyquinoline (H-QL1a), 5,7-dichloro-8-quinolinol (H-QL1b), 5-chloro-7-iodo-8-hydroxyquinolin (H-QL1c), 5,7-dibromo-8-hydroxyquinoline (H-QL1d), and 5,7-dichloro-8-hydroxy-2-methylquinoline (H-QL1e) and the main ligands 6,7-dichloro-3-pyridin-2-yl-chromen-2-one (H-QL3a), 6-bromo-3-pyridin-2-yl-chromen-2-one (H-QL3b), and 6-chloro-3-pyridin-2-yl-chromen-2-one (H-QL3c), respectively. The structure of compounds YNU-4a-YNU-4k was fully confirmed by conducting various spectroscopic analyses. The anticancer activity of YNU-4a-YNU-4k was evaluated in cisplatin-resistant A549/DDP lung cancer cells (LC549) versus normal embryonic kidney (HEK293) cells. Notably, compound YNU-4f bearing QL1e and QL3a ligands showed a more pronounced antiproliferative effect against LC549 cells (IC50 = 1.75 ± 0.09 µM) with high intrinsic selectivity toward LC549 cancer cells than YNU-4a-YNU-4e, H-QL1a-H-QL1e, cisplatin (PDD), YNU-4g-YNU-4k, and H-QL3a-H-QL3c. Additionally, a colocalization assay analysis of YNU-4e and YNU-4f showed that these two ruthenium(II/III) compounds were subcellularly accumulated in the mitochondria and other regions of the cytoplasm, where they induce mitophagy, adenosine triphosphate (ATP) reduction, mitochondrial respiratory chain complex I/IV(RC1/RC4) inhibition, and mitochondrial dysfunction. Accordingly, compounds YNU-4a-YNU-4k can be regarded as mitophagy inductors for the eradication of cisplatin-resistant LC549 cancer cells.

Investigating the molecular mechanisms of Pseudalteromonas sp. LD-B1's algicidal effects on the harmful alga Heterosigma akashiwo.

Heterosigma akashiwo is a harmful algal bloom species that causes significant detrimental effects on marine ecosystems worldwide. The algicidal bacterium Pseudalteromonas sp. LD-B1 has demonstrated potential effectiveness in mitigating these blooms. However, the molecular mechanisms underlying LD-B1's inhibitory effects on H. akashiwo remain poorly understood. In this study, we employed the comprehensive methodology, including morphological observation, assessment of photosynthetic efficiency (Fv/Fm), and transcriptomic analysis, to investigate the response of H. akashiwo to LD-B1. Exposure to LD-B1 resulted in a rapid decline of H. akashiwo's Fv/Fm ratio, with cells transitioning to a rounded shape within 2 hours, subsequently undergoing structural collapse and cytoplasmic leakage. Transcriptomic data revealed sustained downregulation of photosynthetic genes, indicating impaired functionality of the photosynthetic system. Additionally, genes related to the respiratory electron transfer chain and antioxidant defenses were consistently downregulated, suggesting prolonged oxidative stress beyond the cellular antioxidative capacity. Notably, upregulation of autophagy-related genes was observed, indicating autophagic responses in the algal cells. This study elucidates the molecular basis of LD-B1's algicidal effects on H. akashiwo, advancing our understanding of algicidal mechanisms and contributing to the development of effective strategies for controlling harmful algal blooms.

Integration of nonlinear two-photon excited fluorescence and photocatalysis boosts overall water splitting performance.

A nonlinear two-photon excited fluorescence photocatalytic system was constructed for the first time by integrating (ZnO)1-x(GaN)x photocatalyst and a fluorescence solution of phenanthridine derivatives. This work offers a strategy for increasing the photocatalytic solar spectral utilization rate and boosting the expectation for photocatalytic solar-to-hydrogen efficiencies.

Chinese Herbal Formula, Modified Guilu Erxian Glue, Alleviates Apoptosis of Hematopoietic Stem Cells by Regulating SLAM-SAP Signal Pathway in Aplastic Anemia Mice Model.

ETHNOPHARMACOLOGICAL RELEVANCE: Guilu Erxian Glue (GEG) and Danggui Buxue Tang (DBT) are traditional Chinese herbal formulas. According to the theory of traditional Chinese medicine, the combination of those two formulas (Modified Guilu Erxian Glue, MGEG) has the effects of tonifying the kidney and producing blood, was usually used to treat bone marrow failure diseases, including aplastic anemia (AA). AIM OF THE STUDY: T lymphocytes play a crucial role in the disease pathogenesis and progression of AA. Our preliminary results confirmed that GEG can improve the damage of hematopoietic stem cells in mice, while DBT can reduce the proliferation and differentiation of T lymphocytes and inhibit the production of IFN-γ. We hypothesized that the combination of those two herbal formulas could inhibit immune attack and restore hematopoietic function through multiple mechanisms. In this study, we aim to study the curative effect of MGEG on regulating the expression of Signal lymphocyte activating molecule (SLAM), an activation-related molecule in T lymphocytes, thereby suppressing the immune function of T cells and decelerating the damage to hematopoietic stem cells. MATERIALS AND METHODS: High-performance liquid chromatography-electrospray ionization/mass spectrometry system was used to identify the components of the MGEG formulation. Induction of aplastic anemia mouse model by injecting allogeneic lymphocyte suspension into BABL/c mice after ionizing radiation. Cyclosporine A (CsA) was used as a positive control drug. Flow cytometry was used to detect the number and apoptosis rate of hematopoietic stem cells in the bone marrow. Enzyme-linked immunosorbent assay was performed to measure the levels of IFN-γ and TNF-α. Immunofluorescence staining was used to assess the expression of T-bet and SLAM-SAP. Western Blot was conducted to examine the expression of activation-related molecules in T lymphocytes and proteins related to the Fas signal pathway. Hematoxylin-eosin staining was performed to observe pathological changes in the bone marrow tissue. Wright-Giemsa staining was utilized to evaluate alterations in the cellular composition and basic structure of the bone marrow cells (BMCs). Transmission electron microscopy was employed to observe changes in the structure and morphology of hematopoietic stem cells. The hematology analyzer was used to detect peripheral blood parameters. RESULTS: Twenty-three different components were identified in MGEG. After MGEG treatment, the expression levels of Fyn and SLAM-SAP binding were increased in AA mice, while the expression levels of T-bet were decreased and the secretion of IFN-γ was reduced significantly. Additionally, MGEG also could downregulate the protein levels of Fas, caspase-3, and cleaved caspase-3 in AA mice. CONCLUSION: MGEG could attenuate the production of IFN-γ by promoting the SLAM-SAP signal pathway to regulate the generation and distribution of T-bet in T cells. Additionally, it suppresses apoptosis of HSCs through intervention in the Fas-dependent pathway, thereby mitigating immune-mediated damage to HSCs.

Visible-Light-Promoted Cascade Carboxylation/Arylation of Unactivated Alkenes with CO2 for the Synthesis of Carboxylated Indole-Fused Heterocycles.

Described here is a visible-light-promoted cascade carboxylation/arylation of indole-tethered unactivated alkenes with CO2 to access various carboxylated indole-fused heterocycles. This reaction is initiated by the addition of a CO2 radical anion to the alkene motif toward an alkyl carbon radical, followed by its addition to the aromatic ring, and then rearomatization to afford the final products. This reaction provides a facile and sustainable protocol for the construction of carboxylated indole-fused heterocycles using CO2 as the carboxylic source.

Trophic effects of jellyfish blooms on fish populations in ecosystems of the coastal waters of China.

Jellyfish play an important role in the material cycling and energy flow of food webs, and massive aggregations may have deleterious consequences for local fisheries; yet a theoretical framework of the trophic effects of jellyfish blooms on coastal fisheries is unclear. To address this knowledge gap, we assessed the trophic interactions between cooccurring bloom jellyfish and dominant fish groups (omnivorous fish and piscivorous fish) in the coastal waters of China (CWC) via stable isotope analysis; we subsequently discussed how jellyfish blooms may affect energy flow through coastal ecosystems. Our results indicate a considerable degree of trophic overlap (mean ratio > 65 %) between jellyfish and small omnivorous fish (< 10 cm), highlighting a similarity in feeding habits, while the overlap ratio decreased to <55 % of the large omnivorous fish group (> 10 cm). Relatively higher trophic levels and smaller overlaps of large omnivorous fish were found in the ecosystem with high jellyfish biomass, which suggested that they may reinforce the ontogenetic trophic shift pattern to alleviate the potential for resource competition with jellyfish under conditions of jellyfish explosion. The smallest trophic overlap (< 20 %) highlighted the strong trophic differentiation between jellyfish and piscivorous fish. Additionally, our study suggested that a massive aggregation of jellyfish can negatively influence zooplankton but may not transfer energy further up efficiently, implying a weak trophic coupling between jellyfish and upper-trophic levels in CWC ecosystems. Thus, we speculate that jellyfish play an important role in shaping pathways involved in the energy transfer of food webs and that large blooms may negatively affect fisheries through bottom-up control affecting prey availability. In general, these results hold strong potential to further improve the understanding of the trophic interactions between jellyfish and fish populations. Furthermore, this study provides valuable data for predicting the consequences of jellyfish blooms on ecosystems, and is crucial for ecosystem-based management of coastal fisheries.

Isotopic evidence for the dietary difference between Rhizostomeae Nemopilema nomurai and Semaeostomeae Cyanea nozakii.

Blooms of the Rhizostomeae Nemopilema nomurai and the Semaeostomeae Cyanea nozakii have become more prominent in the coastal waters of China since the end of the 20th century. However, the trophic ecology of these jellyfish species remain incompletely understood. In this study, the trophic characterizations of N. nomurai and C. nozakii populations were assessed using stable isotope analysis (SIA), with a focus on the important bloom area offshore of the Yangtze Estuary. Our results indicated obvious trophic differences between two scyphomedusae. The higher trophic position of the C. nozakii population in the coastal planktonic food web was reflected by its relatively large δ15N value compared to that of N. nomurai. The MixSIAR model indicated that small copepods (<1000 µm) and seston were important food sources for N. nomurai, and showed a stable dietary, irrespective of N. nomurai size. Conversely, C. nozakii exhibited a more diverse diet composition, and gelatinous organisms also were an important part of the diet of C. nozakii. Moreover, a pronounced ontogenetic shift in the diet of C. nozakii was observed, consisting of an increase in the proportion of zooplanktonic prey (excluding seston) in the C. nozakii diet with diameter. This study provides isotopic evidence of the substantial difference in trophic ecology between N. nomurai and C. nozakii, which resulted from the variations in SI values and diet compositions. Inconsistent size-based variation patterns were observed in trophic ontogenetic shifts within the N. nomurai and C. nozakii groups, highlighting a need for further investigation. These results will give insights into the characteristics of trophic ecology and functional roles of Rhizostomeae and Semaeostomeae, and indicate the need for a more careful consideration of the representations of Rhizostomeae and Semaeostomeae in coastal ecosystems, so as not to underestimate the knowledge of taxon-specific ecological effects on energy flow.

A Bayesian network for simultaneous keyframe and landmark detection in ultrasonic cine.

Accurate landmark detection in medical imaging is essential for quantifying various anatomical structures and assisting in diagnosis and treatment planning. In ultrasound cine, landmark detection is often associated with identifying keyframes, which represent the occurrence of specific events, such as measuring target dimensions at specific temporal phases. Existing methods predominantly treat landmark and keyframe detection as separate tasks without harnessing their underlying correlations. Additionally, owing to the intrinsic characteristics of ultrasound imaging, both tasks are constrained by inter-observer variability, leading to potentially higher levels of uncertainty. In this paper, we propose a Bayesian network to achieve simultaneous keyframe and landmark detection in ultrasonic cine, especially under highly sparse training data conditions. We follow a coarse-to-fine landmark detection architecture and propose an adaptive Bayesian hypergraph for coordinate refinement on the results of heatmap-based regression. In addition, we propose Order Loss for training bi-directional Gated Recurrent Unit to identify keyframes based on the relative likelihoods within the sequence. Furthermore, to exploit the underlying correlation between the two tasks, we use a shared encoder to extract features for both tasks and enhance the detection accuracy through the interaction of temporal and motion information. Experiments on two in-house datasets (multi-view transesophageal and transthoracic echocardiography) and one public dataset (transthoracic echocardiography) demonstrate that our method outperforms state-of-the-art approaches. The mean absolute errors for dimension measurements of the left atrial appendage, aortic annulus, and left ventricle are 2.40 mm, 0.83 mm, and 1.63 mm, respectively. The source code is available at github.com/warmestwind/ABHG.

A potential early-atheroprotective target: Irgm1 mediates lymphangiogenesis through LEC autophagy by Tfeb translocation.

Lymphatic dysfunction is a pivotal pathological mechanism underlying the development of early atherosclerotic plaques. Potential targets of lymphatic function must be identified to realize the early prevention and treatment of atherosclerosis (AS). The immunity-related GTPase Irgm1 is involved in orchestrating cellular autophagy and apoptosis. However, the effect of Irgm1 on early AS progression, particularly through alterations in lymphatic function, remains unclear. In this study, we confirmed the protective effect of lymphangiogenesis on early-AS in vivo. Subsequently, an in vivo model of early AS mice with Irgm1 knockdown shows that Irgm1 reduces early atherosclerotic plaque burden by promoting lymphangiogenesis. Given that lymphatic endothelial cell (LEC) autophagy significantly contributes to lymphangiogenesis, Irgm1 may enhance lymphatic circulation by promoting LEC autophagy. Moreover, Irgm1 orchestrates autophagy in LECs by inhibiting mTOR and facilitating nuclear translocation of Tfeb. Collectively, these processes lead to lymphangiogenesis. Thus, this study establishes a link between Irgm1 and early AS, thus revealing a novel mechanism by which Irgm1 exerts an early protective influence on AS within the context of lymphatic circulation. The insights gained from this study have the potential to revolutionize the approach and management of AS onset.

Photo-thermal Catalytic Hydrogenation of Halogenated Nitrobenzenes over Ni/P25 Catalyst.

As haloanilines (HANs) are important organic intermediates and fine chemicals, their preparation over non-noble-metal-based catalysts by catalytic hydrogenation has attracted wide attention. However, the reaction suffers from relatively harsh conditions. Herein, we found that a 3.5%Ni/P25 catalyst exhibited superior photo-thermal catalytic activity with a TOFs of 5207 h-1 for hydrogenation of p-chloronitrobenzene (p-CNB) to p-chloroaniline under a 300 W full spectrum, which was much higher than that of photo- and thermal catalysis alone. Moreover, the 3.5%Ni/P25 catalyst could be recycled 4 times and was effective for the hydrogenation of various halonitrobenzenes (HNBs) with superior selectivity. Furthermore, the kinetic research showed that the excellent catalytic performance could be attributed to the better activation and dissociation of H2 by photo-thermal catalysis and the hydrogenation of p-CNB obeyed the condensation routine by ionic hydrogenation over 3.5%Ni/P25.

Visible Light Photoredox-Catalyzed Formyl/Carboxylation of Activated Alkenes with Glyoxylic Acid Acetals and CO2.

A photoredox-catalyzed sequential α-formyl/carboxylation of alkenes with glyoxylic acid acetals and CO2 has been developed to afford a range of masked γ-formyl esters in good yields, which could be readily transformed into diverse compounds, such as γ-formyl ester, hemiacetal, and 1,4-diol. This reaction features mild conditions, readily available starting materials, and operational simplicity.

Identification of signaling pathways that specify a subset of migrating enteric neural crest cells at the wavefront in mouse embryos.

During enteric nervous system (ENS) development, pioneering wavefront enteric neural crest cells (ENCCs) initiate gut colonization. However, the molecular mechanisms guiding their specification and niche interaction are not fully understood. We used single-cell RNA sequencing and spatial transcriptomics to map the spatiotemporal dynamics and molecular landscape of wavefront ENCCs in mouse embryos. Our analysis shows a progressive decline in wavefront ENCC potency during migration and identifies transcription factors governing their specification and differentiation. We further delineate key signaling pathways (ephrin-Eph, Wnt-Frizzled, and Sema3a-Nrp1) utilized by wavefront ENCCs to interact with their surrounding cells. Disruptions in these pathways are observed in human Hirschsprung's disease gut tissue, linking them to ENS malformations. Additionally, we observed region-specific and cell-type-specific transcriptional changes in surrounding gut tissues upon wavefront ENCC arrival, suggesting their role in shaping the gut microenvironment. This work offers a roadmap of ENS development, with implications for understanding ENS disorders.

Progress in Biomarkers Related to Biliary Atresia.

Biliary atresia (BA) is a congenital cholestatic disease that can seriously damage children's liver function. It is one of the main reasons for liver transplantation in children. Early diagnosis of BA is crucial to the prognosis of patients, but there is still a lack of reliable non-invasive diagnostic methods. Additionally, as some children are in urgent need of liver transplantation, evaluating the stage of liver fibrosis and postoperative native liver survival in children with BA using a straightforward, efficient, and less traumatic method is a major focus of doctors. In recent years, an increasing number of BA-related biomarkers have been identified and have shown great potential in the following three aspects of clinical practice: diagnosis, evaluation of the stage of liver fibrosis, and prediction of native liver survival. This review focuses on the pathophysiological function and clinical application of three novel BA-related biomarkers, namely MMP-7, FGF-19, and M2BPGi. Furthermore, progress in well-known biomarkers of BA such as gamma-glutamyltransferase, circulating cytokines, and other potential biomarkers is discussed, aiming to provide a reference for clinical practice.

A New Automated Prognostic Prediction Method Based on Multi-Sequence Magnetic Resonance Imaging for Hepatic Resection of Colorectal Cancer Liver Metastases.

Colorectal cancer is a prevalent and life-threatening disease, where colorectal cancer liver metastasis (CRLM) exhibits the highest mortality rate. Currently, surgery stands as the most effective curative option for eligible patients. However, due to the insufficient performance of traditional methods and the lack of multi-modality MRI feature complementarity in existing deep learning methods, the prognosis of CRLM surgical resection has not been fully explored. This paper proposes a new method, multi-modal guided complementary network (MGCNet), which employs multi-sequence MRI to predict 1-year recurrence and recurrence-free survival in patients after CRLM resection. In light of the complexity and redundancy of features in the liver region, we designed the multi-modal guided local feature fusion module to utilize the tumor features to guide the dynamic fusion of prognostically relevant local features within the liver. On the other hand, to solve the loss of spatial information during multi-sequence MRI fusion, the cross-modal complementary external attention module designed an external mask branch to establish inter-layer correlation. The results show that the model has accuracy (ACC) of 0.79, the area under the curve (AUC) of 0.84, C-Index of 0.73, and hazard ratio (HR) of 4.0, which is a significant improvement over state-of-the-art methods. Additionally, MGCNet exhibits good interpretability.

Clinical application of endoscopic diaphragmotomy and dilation in a congenital duodenal diaphragm.

Background: A congenital duodenal diaphragm (CDD) is a rare cause of duodenal obstruction in infants and children. The traditional approach to treatment has been surgical intervention either with excision and duodenoplasty or with bypass through a duodenoduodenostomy, which is invasive and carries the risk of anastomotic leakage. Aims: To summarize the key points of differential diagnosis and treatment of a CDD under gastroscopy and to evaluate its efficacy and safety. Methods: The clinical data of patients with a duodenal obstruction diagnosed and treated by gastroscopy in our hospital between January 2019 and December 2022 were retrospectively analyzed. The gastroscopic features of the CDD were summarized. The clinical outcomes of patients with CDD treated by gastroscopy were collected and investigated. Results: A total of 13 children with a duodenal obstruction underwent a gastroscopic examination and/or treatment, and of these, 10 were diagnosed as having a CDD and 3 were finally diagnosed as having an annular pancreas. A dome-shaped structure during inspiration (9/10) and a guidewire that could be inserted through the opening into the distal lumen (6/10) were the gastroscopic features of the CDD, while the annular pancreas had none of these features. The 10 patients, 4 men and 6 women with the CDD, were treated through endoscopic diaphragmotomy and dilation. The age and weight at operation was 15 days to 7 years (M: 2.25 years) and 2.85-22 kg (M: 13.6 kg), respectively. A total of 11 endoscopic operations were performed in the 10 patients. The time of single operation was 15-55 min (M: 38 min). The patients did not experience complications such as bleeding, pneumoperitoneum, and duodenal papilla injury during the operation. Feeding was started 12-24 h after surgery, and the patients were discharged 2-10 days (M: 7 days) postoperatively. The patients were followed up for 3-36 months (M: 17 months), and none of them had a recurrence of vomiting. However, three showed a recurrence of stenosis in upper gastrointestinal imaging, one of whom underwent a partial diaphragm resection again 2 months after the primary treatment. Conclusions: A CDD can be confirmed by endoscopy based on its characteristic features. Endoscopic diaphragmotomy and balloon dilation are safe and effective, which can be a new option for minimally invasive treatment of a CDD.

Transcriptome analysis of the harmful alga Heterosigma akashiwo under a 24-hour light-dark cycle.

The photoperiod, which is defined as the period of time within a 24-hour time frame that light is available, is an important environmental regulator of several physiological processes in phytoplankton, including harmful bloom-forming phytoplankton. The ichthyotoxic raphidophyte Heterosigma akashiwo is a globally distributed bloom-forming phytoplankton. Despite extensive studies on the ecological impact of H. akashiwo, the influence of the photoperiod on crucial biological processes of this species remains unclear. In this study, gene expression in H. akashiwo was analyzed over a 24-hour light-dark (14:10) treatment period. Approximately 36 % of unigenes in H. akashiwo were differentially expressed during this 24-hour treatment period, which is indicative of their involvement in the response to light-dark variation. Notably, the number of differentially expressed genes exhibited an initial increase followed by a subsequent decrease as the sampling time progressed (T0 vs. other time points). Unigenes associated with photosynthesis and photoprotection reached their peak expression levels after 2-4 h of illumination (T12-T14). In contrast, the expression of unigenes associated with DNA replication peaked at the starting point of the dark period (T0). Furthermore, although several unigenes annotated to photoreceptors displayed potential diel periodicity, genes from various photoreceptor families (such as phytochrome and cryptochrome) showed unique expression patterns. Collectively, our findings offer novel perspectives on the response of H. akashiwo to the light-dark cycle, serving as a valuable resource for investigating the physiology and ecology of this species.

Synchrotron Radiation Based X-ray Absorption Spectroscopy: Fundamentals and Applications in Photocatalysis.

Photocatalysis is one of the most promising green technologies to utilize solar energy for clean energy achievement and environmental governance. There is a knotty problem to rational designing high-performance photocatalyst, which largely depends on an in-depth insight into their structure-activity relationships and complex photocatalytic reaction mechanisms. Synchrotron radiation based X-ray absorption spectroscopy (XAS) is an important characterization method for photocatlayst to offer the element-specific key geometric and electronic structural information at the atomic level, on this basis, time-resolved XAS technique has a huge impact on mechanistic understanding of photochemical reaction owing to their powerful ability to probe, in real-time, the electronic and geometric structures evolution within photocatalysis reactions. This review will focus on the fundamentals of XAS and their applications in photocatalysis. The detailed applications obtained from XAS is described through the following aspects: 1) identifying local structure of photocatalyst; 2) uncovering in situ structure and chemical state evolution during photocatalysis; 3) revealing the photoexcited process. We will provide an in depth understanding on how the XAS method can guide the rational design of highly efficient photocatalyst. Finally, a systematic summary of XAS and related significance is made and the research perspectives are suggested.

Visible-Light Photoredox-Catalyzed Intermolecular α-Aminomethyl/Carboxylative Dearomatization of Indoles with CO2 and α-Aminoalkyl Radical Precursors.

Disclosed here is a visible-light photoredox-catalyzed intermolecular sequential α-aminomethyl/carboxylative dearomatization of indoles with CO2 and α-aminoalkyl radical precursors, affording a series of functionalized indoline-3-carboxylic acids and lactams in good yields with high regioselectivity. This multicomponent reaction provides a green and facile method for the synthesis of diverse functionalized indolines by using CO2 as the carboxylic and carbonyl source.

Arsenic trioxide alleviates atherosclerosis by inhibiting CD36-induced endocytosis and TLR4/NF-κB-induced inflammation in macrophage and ApoE-/- mice.

BACKGROUND: Inflammation and lipid accumulation are key events in atherosclerosis progression. Despite arsenic trioxide's (ATO) toxicity, at appropriate doses, it is a useful treatment for various diseases treatment. ATO prevents vascular restenosis; however, its effects on atherosclerotic plaque development and instability remain unclear. METHODS: ApoE-/- mice were fed high-fat diet for 4 months, and starting at the third month, ATO was intravenously administered every other day. Atherosclerotic lesion size, histological characteristics, and related protein and lipid profiles were assessed using samples from the aorta, carotid artery, and serum. The anti-inflammatory and anti-pyroptosis effects of ATO were investigated by stimulating RAW264.7 and THP-1 cell lines with oxidized low-density lipoprotein (ox-LDL) or lipopolysaccharide (LPS). RESULTS: ATO reduced atherosclerotic lesion formation and plasma lipid levels in ApoE-/- mice. In the serum and aortic plaques, ATO reduced the levels of pro-inflammatory factors, including interleukin (IL) 6 and tumor necrosis factor α, but increased IL-10 levels. Mechanistically, ATO promoted the CD36-mediated internalization of ox-LDL in a peroxisome proliferator-activated receptor γ-dependent manner. Furthermore, ATO downregulated Toll-like receptor 4 (TLR4) expression in plaques and macrophages and inhibited p65 nuclear translocation and IκBα degradation. ATO reduced macrophage pyroptosis by downregulating NLR family pyrin domain-containing 3 (NLRP3) expression and caspase 1 activation. CONCLUSION: ATO has potential atheroprotective effects, especially in macrophages. The mechanisms were inhibition of CD36-mediated foam cell formation and suppression of inflammatory responses and pyroptosis mediated by TLR4/nuclear factor κB and NLRP3 activation. Our findings provide evidence supporting the potential atheroprotective value of ATO.

Facet-Dependent Photocatalytic Behavior of Rutile TiO2 for the Degradation of Volatile Organic Compounds: In Situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy and Density Functional Theory Investigations.

In this study, a custom rutile titanium dioxide (TiO2) photocatalyst with a single exposed surface was utilized to investigate the facet-dependent photocatalytic mechanism of toluene. The degradation of toluene was dynamically monitored using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) technology coupled with theoretical calculations. The findings demonstrated that the photocatalytic degradation rate on the TiO2 (001) surface was nearly double that observed on the TiO2 (110) surface. This remarkable enhancement can be attributed to the heightened stability in the adsorption of toluene molecules and the concurrent reduction in the energy requirement for the ring-opening process of benzoic acid on the TiO2 (001) surface. Moreover, the TiO2 (001) surface generated a greater number of reactive oxygen species (ROS), thereby promoting the separation of photogenerated charge carriers and concurrently diminishing their recombination rates, amplifying the efficiency of photocatalysis. This research provides an innovative perspective for a more comprehensive understanding of the photocatalytic degradation mechanism of TiO2 and presents promising prospects for significant applications in environmental purification and energy fields.