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A photoinduced three-component radical addition-aminalization cascade was accomplished, enabling rapid assembly of a wide range of densely functionalized γ-lactams. Key to this transformation is the electron-donor-acceptor (EDA) generation of enamine and in situ trapping of an iminium intermediate with bromodifluoroacetamide. This rationally designed protocol fully takes advantage of the polarity crossover (enamine-iminium) in the process, providing the modular assembly of previously inaccessible scaffolds. The reaction proceeds under mild reaction conditions with excellent regio- and diastereoselectivity, which is amenable to structurally varied substrates and pharmaceuticals.

Herein, a photoinduced, Pd-catalyzed direct 1,2-carboamination of conjugated 1,3-dienes has been successfully achieved. Sequential regioselective C-C bond and enantioselective C-N bond formation allows rapid assembly of a wide range of value-added chiral allylic amines from readily available N -hydroxyphthalimide (NHP) esters and 1,3-dienes under mild conditions. This developed protocol further demonstrates the versatility and potency of the photoexcited Pd catalytic system with a bifunctional reagent in the streamlined difunctionalization of C═C bonds.

Herein, we report a photoinduced 1,7-hydrosulfonylation of allylic ethers and amides via a sequential Pd-mediated 1,5-HAT process and Pd-catalyzed allylic nucleophilic attack of arylsulfonates. This rationally designed synthetic protocol allows for facile construction of a series of structurally novel allylic sulfonated scaffolds, and features mild conditions, cheap and readily available raw materials and functional group compatibility.

Stable and easy-to-handle sodium salts of sulfonyl oximes were first identified to proceed via visible-light-driven phophine-mediated successive deoxygenation to realize the anti -Markovnikov hydrothiolation of alkenes, which could serve as an odorless sulfur source. Mechanistic studies revealed that the key thiyl radical intermediate could be generated in situ from the sulfonyl oxime anion via a phosphine-mediated fragmentation and a sequential deoxygenation process. Notably, a wide range of alkenes, including acrylamides, acrylates, vinyl ketones, vinyl sulfones, and acrylonitriles, are competent substrates for this protocol, which is highly beneficial for the construction of structurally diversified organosulfur compounds.

Nickel/photoredox catalysis has emerged as a powerful platform for exploring nontraditional and challenging cross-couplings. Herein, a metallaphotoredox catalytic protocol has been developed on the basis of a tertiary amine-ligated boryl radical-induced halogen atom transfer process under blue-light irradiation. A wide variety of aryl and heteroaryl bromides featuring different functional groups and pharmaceutical moieties were facilely coupled to rapidly install C(sp 3 )-enriched aromatic scaffolds. The compatibility of Lewis base-ligated borane with nickel catalysis was well exemplified to extend the chemical space for Ni-catalyzed cross-electrophile coupling.

Ten C-geranylated flavonoids, along with three known analogues, were isolated from the leaves of Artocarpus communis. The chemical structures of these compounds were unambiguously determined via comprehensive spectroscopic analysis, single-crystal X-ray diffraction experiments, and quantum chemical electronic circular dichroism calculations. Structurally, artocarones A-I (1-9) represent a group of unusual, highly modified C-geranylated flavonoids, in which the geranyl chain is cyclised with the ortho-hydroxy group of flavonoids to form various heterocyclic scaffolds. Notably, artocarones E and G-I (5 and 7-9) feature a 6H-benzo[c]chromene core that is hitherto undescribed in C-geranylated flavonoids. Artocarone J (10) is the first example of C-9-C-16 connected C-geranylated aurone. Meanwhile, the plausible biosynthetic pathways for these rare C-geranylated flavonoids were also proposed. Notably, compounds 1, 2, 4, 8, 11, and 12 exhibited promising in vitro inhibitory activities against respiratory syncytial virus and herpes simplex virus type 1., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Reproductive toxicity is one of the important issues in chemical safety. Traditional laboratory testing methods are costly and time-consuming with raised ethical issues. Only a few in silico models have been reported to predict human reproductive toxicity, but none of them make full use of the topological information of compounds. In addition, most existing atom-based graph neural network methods focus on attributing model predictions to individual nodes or edges rather than chemically meaningful fragments or substructures. In current studies, we develop a novel fragment-based graph transformer network (FGTN) approach to generate the QSAR model of human reproductive toxicity by considering internal topological structure information of compounds. In the FGTN model, the compound is represented by a graph architecture using fragments to be nodes and bonds linking two fragments to be edges. A super molecule-level node is further proposed to connect all fragment nodes by undirected edges, obtaining global molecular features from fragment embeddings. The FGTN model achieved an accuracy (ACC) of 0.861 and an area under the receiver operating characteristic curve (AUC) value of 0.914 on nonredundant blind tests, outperforming traditional fingerprint-based machine learning models and atom-based GCN model. The FGTN model can attribute toxic predictions to fragments, generating specific structural alerts for the positive compound. Moreover, FGTN may also have the capability to distinguish various chemical isomers. We believe that FGTN can be used as a reliable and effective tool for human reproductive toxicity prediction in contribution to the advancement of chemical safety assessment., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Background: Chemicals may lead to acute liver injuries, posing a serious threat to human health. Achieving the precise safety profile of a compound is challenging due to the complex and expensive testing procedures. In silico approaches will aid in identifying the potential risk of drug candidates in the initial stage of drug development and thus mitigating the developmental cost., Methods: In current studies, QSAR models were developed for hepatotoxicity predictions using the ensemble strategy to integrate machine learning (ML) and deep learning (DL) algorithms using various molecular features. A large dataset of 2588 chemicals and drugs was randomly divided into training (80%) and test (20%) sets, followed by the training of individual base models using diverse machine learning or deep learning based on three different kinds of descriptors and fingerprints. Feature selection approaches were employed to proceed with model optimizations based on the model performance. Hybrid ensemble approaches were further utilized to determine the method with the best performance., Results: The voting ensemble classifier emerged as the optimal model, achieving an excellent prediction accuracy of 80.26%, AUC of 82.84%, and recall of over 93% followed by bagging and stacking ensemble classifiers method. The model was further verified by an external test set, internal 10-fold cross-validation, and rigorous benchmark training, exhibiting much better reliability than the published models., Conclusion: The proposed ensemble model offers a dependable assessment with a good performance for the prediction regarding the risk of chemicals and drugs to induce liver damage., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2024 Khan, Ren, Cao, Ye, Wang, Guo, Yang and Chen.)

Herein, a transition-metal-free phosphorylation of benzyl fluorides with P(O)-H compounds is disclosed. In the presence of t BuOK, various benzyl fluorides react with P(O)-H compounds to produce the corresponding benzyl phosphine oxides, phosphinates, and phosphonates in good to high yields. This base-promoted phosphorylation reaction offers a facile and general strategy for the construction of a C(sp 3 )-P bond.

Herein, visible light-induced, nickel-catalyzed direct functionalization of the Hantzsch esters (HEs) with readily accessible alkyl bromides has been successfully achieved by taking advantage of HE as the reductant and substrate through an aromatization-dearomatization process. In this strategy, the single electron reduction of alkyl bromides by reactive Ni(I) species is essential for the success of this late-stage transformation. A wide range of 4-alkyl-1,4-dihydropyridines were rapidly assembled in moderate to good yields under mild conditions, rendering this photoinduced approach attractive for synthetic and medicinal chemistry.

Ethylene response factors have been shown to be involved in the effects of plant developmental processes and to regulate stress tolerance. The aim of this study was to recognize the regulatory mechanisms of ethylene response factors on tobacco plant height. In this study, a gene-edited mutant (ERF10-KO) and wild type (WT) were utilized as experimental materials. Transcriptome and metabolome analyses were used to investigate the regulatory mechanism of NtERF10 gene editing on plant height in tobacco. Here, through the analysis of differentially expressed genes (DEGs), 2051 genes were upregulated and 1965 genes were downregulated. We characterized the different ERF10-KO and WT plant heights and identified key genes for photosynthesis, the plant hormone signal transduction pathway and the terpene biosynthesis pathway. NtERF10 was found to affect the growth and development of tobacco by regulating the expression levels of the PSAA, PSBA, GLY17 and GGP3 genes. Amino acid metabolism was analyzed by combining analyses of differentially expressed genes (DEGs) and differentially accumulated metabolites (DAMs). In addition, we found that members of the bHLH, NAC, MYB, and WRKY transcription factor families have vital roles in regulating plant height. This study not only provides important insights into the positive regulation of the ethylene response factor NtERF10 on plant height during plant growth and development but also provides new research ideas for tobacco molecular breeding., (© 2024. The Author(s).)

Porcine reproductive and respiratory syndrome (PRRS) is a globally prevalent contagious disease caused by the positive-strand RNA PRRS virus (PRRSV), resulting in substantial economic losses in the swine industry. Modifying the CD163 SRCR5 domain, either through deletion or substitution, can eff1ectively confer resistance to PRRSV infection in pigs. However, large fragment modifications in pigs inevitably raise concerns about potential adverse effects on growth performance. Reducing the impact of genetic modifications on normal physiological functions is a promising direction for developing PRRSV-resistant pigs. In the current study, we identified a specific functional amino acid in CD163 that influences PRRSV proliferation. Viral infection experiments conducted on Marc145 and PK-15 CD163 cells illustrated that the mE535G or corresponding pE529G mutations markedly inhibited highly pathogenic PRRSV (HP-PRRSV) proliferation by preventing viral binding and entry. Furthermore, individual viral challenge tests revealed that pigs with the E529G mutation had viral loads two orders of magnitude lower than wild-type (WT) pigs, confirming effective resistance to HP-PRRSV. Examination of the physiological indicators and scavenger function of CD163 verified no significant differences between the WT and E529G pigs. These findings suggest that E529G pigs can be used for breeding PRRSV-resistant pigs, providing novel insights into controlling future PRRSV outbreaks.

A novel strategy for incorporating a trifluoroacetyl functionality into a range of structurally varied unsaturated bonds was developed by using PhI(OCOMe) 2 as an oxidant with a masked trifluoroacyl reagent as a trifluoroacetyl radical precursor. The oxidative decarboxylation of the masked trifluoroacyl precursor followed by a tandem radical process provides versatile access to 5- exo - trig cyclization of N -arylacrylamides, direct C(sp 2 )-H trifluoroacetylation of quinolines, isoquinoline, 2 H -indazole, and quinoxalin-2(1 H )-ones, and C(sp)-H trifluoroacetylation of alkynes. This protocol is characterized by mild reaction conditions, operational simplicity, and broad functional group compatibility.

Background: Neurodegenerative diseases are increasingly recognized for their association with oxidative stress, which leads to progressive dysfunction and loss of neurons, manifesting in cognitive and motor impairments. This study aimed to elucidate the neuroprotective role of peroxiredoxin II (Prx II) in counteracting oxidative stress-induced mitochondrial damage, a key pathological feature of neurodegeneration., Methods: We investigated the impact of Prx II deficiency on endoplasmic reticulum stress and mitochondrial dysfunction using HT22 cell models with knocked down and overexpressed Prx II. We observed alcohol-treated HT22 cells using transmission electron microscopy and monitored changes in the length of mitochondria-associated endoplasmic reticulum membranes and their contact with endoplasmic reticulum mitochondria contact sites (EMCSs). Additionally, RNA sequencing and bioinformatic analysis were conducted to identify the role of Prx II in regulating mitochondrial transport and the formation of EMCSs., Results: Our results indicated that Prx II preserves mitochondrial integrity by facilitating the formation of EMCSs, which are essential for maintaining mitochondrial Ca 2+ homeostasis and preventing mitochondria-dependent apoptosis. Further, we identified a novel regulatory axis involving Prx II, the transcription factor ATF3, and miR-181b-5p, which collectively modulate the expression of Armcx3, a protein implicated in mitochondrial transport. Our findings underscore the significance of Prx II in protecting neuronal cells from alcohol-induced oxidative damage and suggest that modulating the Prx II-ATF3-miR-181b-5p pathway may offer a promising therapeutic strategy against neurodegenerative diseases., Conclusions: This study not only expands our understanding of the cytoprotective mechanisms of Prx II but also offers necessary data for developing targeted interventions to bolster mitochondrial resilience in neurodegenerative conditions., (© 2024. The Author(s).)

A metal-free photosensitized 1,2-imino-sulfamoylation of olefins by employing a tailor-made sulfamoyl carbamate as the difunctionalization reagent has been established. This protocol exhibits versatility across a broad substrate scope, including aryl and aliphatic alkenes, leading to the synthesis of diverse β-imino sulfonamides in moderate to good yields. This method is characterized by its metal-free reaction system, mild reaction conditions, excellent regioselectivity, and high atom economy, serving as a promising platform for the preparation of β-amino sulfonamide-containing molecules, particularly in the context of drug discovery.

Herein, a dual photoredox/nickel catalyzed formylation of aryl bromide with commercially available 2,2-dimethoxy- N , N -dimethylethan-1-amine as an effective CO source has been successfully achieved, delivering a series of aromatic aldehydes in moderate to good yields. Compared with the traditional reductive carbonylation process, this newly designed synthetic protocol provides a straightforward toolbox to access aromatic aldehydes, obviating the use of carbon monoxide and stoichiometric reductants. Finally, the utility of this direct formylation reaction was demonstrated in the pharmaceutical analogue synthesis.

Seeking novel high-performance elastocaloric materials with low critical stress plays a crucial role in advancing the development of elastocaloric refrigeration technology. Here, as a first attempt, the elastocaloric effect of TiZrNbAl shape memory alloy at both room temperature and finite temperatures ranging from 245 K to 405 K, is studied systematically. Composition optimization shows that Ti-19Zr-14Nb-1Al (at.%), possessing excellent room-temperature superelasticity with a critical stress of around 100 MPa and a small stress hysteresis of around 70 MPa and outstanding fracture resistance with a compressive strain of 20% and stress of 1.7 GPa, demonstrates a substantial advantage as an elastocaloric refrigerant. At room temperature, a large adiabatic temperature change (ΔTad) of -6.7 K is detected, which is comparable to the highest value reported in the Ti-based alloys. A high elastocaloric cyclic stability, with almost no degradation of ΔTad after 4000 cycles, is observed. Furthermore, the sizeable elastocaloric effect can be steadily expanded from 255 K to 395 K with a temperature window of as large as 140 K. A maximum ΔTad of -7.9 K appears at 355 K. The present work demonstrates a promising potential of TiZrNbAl as a low critical stress and low hysteresis elastocaloric refrigerant.

The National Health Commission of the People's Republic of China has formulated the Quality Control Indexes for Oncology (2023 edition) , with the objective of improving medical quality scientifically, refined and standardized. Among these indexes, the rate of pretreatment clinical TNM staging and the coincidence rate of evaluation of pretreatment TNM staging lay national standards for patients to formulate rational and targeted treatment strategies. This article reviewed the literature and referred to Chinese Medical Association Clinical Practice Guide for Breast Surgery , and presented recommendations for the hot topics of breast surgery, such as pathological sampling of the breast specimen, sentinel lymph node biopsy for early-stage breast cancer, breast conserving surgery, axillary lymph node dissection, breast reconstruction surgery, endoscopic-assisted breast surgery, the principles of surgical treatment for metastatic breast cancer, neoadjuvant treatment for advanced disease, and surgical grade of breast surgery, which have been widely concerned in recent years, to help improve homogenization of breast cancer treatment in China.

Photoinduced generation of phosphoranyl radicals offers a versatile strategy to access a variety of synthetically valuable radicals. A long-standing challenge remains in the regulation of phosphoranyl radical to undergo α-scission pathway, although the β-scission mode has been intensively studied. We herein developed an unprecedented protocol for selective α-scission of the P(OH)R 3 radical intermediate under photocatalytic conditions. This efficient P-C bond cleavage via α-scission of the P(OH)R 3 radicals has been successfully utilized in the alkylation/fluoroalkylation of alkenes.

Herein, a visible-light-induced nickel-catalyzed cross-coupling of aryl bromide with nitrile has been reported. By utilization of readily available nitriles as carbonyl precursors, a range of structurally diverse aryl ketones were facilely constructed. The synthetic simplicity, mild reaction conditions, and acidic functional group tolerance would broaden the synthetic utilities of this developed protocol as an expedient alternative to Grignard/organolithium protocols.

This study aimed to investigate the differential expression of serum microRNAs in cognitive normal subjects (NC), patients with mild cognitive impairment (MCI), and patients with Alzheimer's disease (AD), with the objective of identifying potential diagnostic biomarkers. A total of 320 clinical samples, including 32 MCI patients, 288 AD patients, and 288 healthy controls, were collected following international standards. The expression of microRNAs in serum was analyzed using the Agilent human microRNA oligonucleotide microarray, and bioinformatics methods were employed to predict target genes and their involvement in AD-related pathways. Among the 122 microRNAs screened, five microRNAs (hsa-miR-208a-5p, hsa-miR-125b-1-3p, hsa-miR-3194-3p, hsa-miR-4652-5p, and hsa-miR-4419a) exhibited differential expression and met quality control standards. Bioinformatics analysis revealed that the target genes of these microRNAs were involved in multiple AD-related pathways, which changed with disease progression. These findings demonstrate significant differences in serum microRNA expression between NC, MCI, and AD patients. Three microRNAs were identified as potential candidates for the development of diagnostic models for MCI and AD. The results highlight the crucial role of microRNAs in the pathogenesis of AD and provide a foundation for the development of novel therapeutic strategies and personalized treatment approaches for AD. This study contributes to the understanding of AD at the molecular level and offers potential avenues for early diagnosis and intervention in AD patients.

Purpose: Different arch structures may cause different foot function injuries. In the past, the arch structure and flexibility of the foot were often defined by the height of the arch, and there was no three-dimensional (3D) structure classification method. In order to form a more complete 3D description, we propose a new classification system of arch volume flexibility (AVF), and then use this new classification system to investigate the relationship between the AVF and arch index (AI), and the arch height flexibility (AHF) and AI, respectively., Methods: It is proposed to recruit 180 young male adults for the test. We obtained arch volume and AI through 3D scanning and obtained the navicular height through manual measurement. Based on these data, we calculated the AHF and the AVF. Using the quintile method, these arches are divided into very stiff, stiff, neutral, flexible, and very flexible. According to AI value, all arches were divided into cavus, rectus, and planus. The distribution of AVF was compared using χ 2 goodness of fit test. The spearman correlation test was used to compare the AHF and AVF. A p < 0.05 indicates that the difference is statistically significant., Results: All participants' plantar data was obtained through 3D scanning, but only 159 of them were complete, so only 318 feet had valid data. The left AHF is (21.23 ± 12.91) mm/kN, and the right AHF is (21.71 ± 12.69) mm/kN. The AVF of the left foot arch is (207.35 ± 118.28) mm 3 /kg, while the right one is (203.00 ± 117.92) mm 3 /kg, and the total AVF of the arch was (205.17 ± 117.94) mm 3 /kg. There was no statistical difference in the AVF between the left and right feet for the same participant (n = 159, p = 0.654). In cavus, the percentage of arch with AVF is 21.4% (very stiff), 21.4% (stiff), 14.3% (neutral), 7.1% (flexible), and 35.7% (very flexible). In rectus, the percentage of arch with AVF is 23.9% (very stiff), 19.6% (stiff), 14.7% (neutral), 24.5% (flexible), and 17.2% (very flexible). In planus, the percentage of arch with AVF is 14.9% (very stiff), 20.6% (stiff), 27.0% (neutral), 16.3% (flexible), and 21.3% (very flexible). Moreover, the correlation between AHF and AVF is not significant (p = 0.060)., Conclusion: In cavus, rectus, and planus, different AVF accounts different percentage, but the difference is not statistically significant. AVF is evenly distributed in the arches of the feet at different heights. We further found the relationship between AHF and AVF is not significant. As a 3D index, AVF may be able to describe the flexibility of the arch more comprehensively than AHF., (Copyright © 2023 Chinese Medical Association. Production and hosting by Elsevier B.V. All rights reserved.)

Herein, a direct cross-dehydrogenative C-H amination of indoles has been successfully achieved, enabled by the merger of photocatalysis with nickel catalysis. This developed process does not require stoichiometric oxidants and prefunctionalization of amine partners, providing a concise platform for C-N bond formation. Moreover, the synthetic practicality of this transformation was well revealed by its high step- and atom-economy, high reaction efficiency, and broad functional group tolerance.

Background: Antinuclear antibodies (ANAs) are crucial in diagnosing autoimmune diseases, mainly systemic lupus erythematosus (SLE). This study aimed to compare the performance of chemiluminescence assay (CLIA) and line immunoassay (LIA) in detecting ANAs in patients with autoimmune diseases, evaluate their diagnostic accuracy for SLE, and develop a novel diagnostic model using CLIA-detected antibodies for SLE. Specimens from patients with autoimmune diseases and physical examination specimens were collected to parallel detect specific antibodies. Individual antibodies' diagnostic performance and a model combining multiple antibodies were assessed. The findings provide valuable insights into improving the diagnosis of SLE through innovative approaches., Aim: To compare the performance of CLIA and LIA in detecting ANAs in patients with autoimmune diseases, assess their accuracy for SLE, and develop a novel diagnostic model using CLIA-detected antibodies for SLE., Methods: Specimens have been obtained from 270 patients with clinically diagnosed autoimmune disorders, as well as 130 physical examination specimens. After that, parallel detection of anti-double-stranded DNA (dsDNA) antibody, anti-histone (Histone) antibody, anti-nucleosome (Nuc) antibody, anti-Smith (Sm) antibody, anti-ribosomal P protein (Rib-P) antibody, anti-sicca syndrome A (Ro60) antibody, anti-sicca syndrome A (Ro52) antibody, anti-sicca syndrome (SSB) antibody, anti-centromere protein B (Cenp-B) antibody, anti-DNA topoisomerase 1 (Scl-70) antibody, anti-histidyl tRNA synthetase (Jo-1) antibody, and anti-mitochondrial M2 (AMA-M2) antibody was performed using CLIA and LIA. The detection rates, compliance rates, and diagnostic performance for SLE were compared between the two methodologies, followed by developing a novel diagnostic model for SLE., Results: CLIA and LIA exhibited essentially comparable detection rates for anti-dsDNA antibody, anti-Histone antibody, anti-Nuc antibody, anti-Sm antibody, anti-Rib-P antibody, anti-Ro60 antibody, anti-Ro52 antibody, anti-SSB antibody, anti-Cenp-B antibody, anti-DNAScl-70 antibody, anti-Jo-1 antibody and anti-AMA-M2 antibody ( P > 0.05). The two methods displayed identical results for the detection of anti-dsDNA antibody, anti-Histone antibody, anti-Nuc antibody, anti-Sm antibody, anti-Ro60 antibody, anti-Ro52 antibody, anti-SSB antibody, anti-Cenp-B antibody, anti-Scl-70 antibody, and anti-AMA-M2 antibody (Kappa > 0.7, P < 0.05), but showed a moderate agreement for the detection of anti-Rib-P antibody and anti-Jo-1 antibody (Kappa = 0.671 and 0.665; P < 0.05). In addition, the diagnostic performance of these antibodies detected by both methods was similar for SLE. The diagnostic model's area under the curve values, sensitivity, and specificity, including an anti-dsDNA antibody and an anti-Ro60 antibody detected by CLIA, were 0.997, 0.962, and 0.978, respectively. These values were higher than the diagnostic performance of individual antibodies., Conclusion: CLIA and LIA demonstrated excellent overall consistency in detecting ANA profiles. A diagnostic model based on CLIA-detected antibodies can successfully contribute to developing a novel technique for detecting SLE., Competing Interests: Conflict-of-interest statement: All authors declare that there are no conflicts of interest., (©The Author(s) 2023. Published by Baishideng Publishing Group Inc. All rights reserved.)

A visible-light-induced radical relay strategy to access heterocycles bearing a monofluoromethylsufonyl moiety is reported, with PhI(OCOCH 2 F) 2 as the CH 2 F radical precursor and DABSO as the SO 2 source. A range of oxindoles, containing a CH 2 FSO 2 CH 2 - group at the C3 position, were synthesized from N -arylacrylamides in up to 97% yields. The protocol features catalyst-free photochemical tandem, mild reaction conditions, broad functional group compatibility, and good to excellent yields.

Development of a new catalytic and straightforward strategy to construct C-N bonds is playing a pivotal role in synthetic chemistry. Here, we report a photocatalysed protocol to access direct C-H amidation of indoles, enabled by a rationally designed tert -butyl alkyl((perfluoropyridin-4-yl)oxy)carbamate. A series of biologically important aminoindoles were prepared under mild conditions with excellent regioselectivity and broad substrate scope.

Herein, we report a visible-light-induced, palladium-catalyzed desaturation/sulfonation cascade, offering a concise route to a series of highly valuable 4-sulfonyltetrahydropyridine scaffolds from inexpensive and readily available piperidine derivatives with sodium sulfinates. The key to the success of this transformation is the well-designed sequence of palladium-mediated 1,5-hydrogen atom transfer/β-hydride elimination/allylic sulfonation process, which demonstrates the synthetic potentials for orchestrating synthetic events by rationally taking advantage of varied catalytic modes.

Reported herein is the design and development of a new photo-induced amidation protocol with the readily available N -chlorosulfonyl carbamate as an effective amidyl-radical precursor, which could be readily prepared from commercial low-cost chlorosulfonyl isocyanate (CSI) and alcohol feedstocks. The synthetic potency of this developed protocol was well demonstrated by direct amidation of various quinoxalin-2(1 H )-ones. The protocol could be further streamlined by implementing a one-pot/two-step/three-component process of CSI, alcohol, and quinoxalin-2(1 H )-one, with significantly improved reaction efficiency. This methodology offers an intriguing opportunity for rapid expansion of nitrogen-containing molecular complexity, thus inspiring comprehensive exploration of a new reaction mode of CSI reagent.

Background: Simian immunodeficiency virus (SIV) infection in rhesus macaques (Macaca mulatta) can lead to the development of SIV encephalitis (SIVE), which is closely related to human immunodeficiency virus (HIV)-induced dementia., Methods: This was done by analyzing SIV and SIVE encephalitis in infected M. mulatta hippocampus samples from two microarray data sets, identifying two groups of common differentially expressed genes and predicting associated protein interactions., Results: We found that eight genes-MX1, B2M, IFIT1, TYMP, STAT1, IFI44, ISG15, and IFI27-affected the negative regulation of biological processes, hepatitis C and Epstein-Barr viral infection, and the toll-like receptor signaling pathway, which mediate the development of encephalitis after SIV infection. In particular, STAT1 played a central role in the process by regulating biopathological changes during the development of SIVE., Conclusion: These findings provide a new theoretical basis for the treatment of encephalopathy after HIV infection by targeting STAT1., (© 2023 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.)

A Giese reaction of aryl bromides with electron-deficient alkenes was developed, enabled by a dual catalyst system containing Ni II complex and Ir III photocatalyst. This protocol could accommodate a variety of aryl bromides and electron-deficient alkenes, delivering the conjugate adducts in up to 97% yield. The utilization of photoexcited (dtbbpy)Ni II (aryl)Br intermediate as an aryl radical source allows this novel transformation of aryl halides, thus expanding the chemical space of excited nickel catalysis.

Direct oxidation of organosilanes is one of the most straightforward ways to access silanols. Herein, we describe a novel photo-induced strategy for oxidation of organosilanes to access silanols, promoted by a photoactive charge-transfer complex (CTC) between sodium benzenesulfinate and molecular O 2 . A streamlined sequence transformation of organosilanes to silyl ethers was also readily achieved. This developed protocol represents the first example of CTC-based oxidation of organosilanes, offering a facile approach to access a series of silanol and silyl ether products.

A visible-light-induced defluorinative dichloromethylation of α-CF 3 alkenes was developed with cheap and readily accessible chloroform simultaneously as a dichloromethylation reagent and reaction medium, leading to the facile preparation of new polyhalogenated scaffolds. Notably, the change from CHCl 3 to CDCl 3 offers a straightforward pathway for accessing the deuterated analogues with excellent degrees of D incorporation. Mechanistic studies suggested the reaction underwent a radical addition of the dichloromethyl radical with alkenes, followed by sequential single-electron transfer and defluorination. This protocol features mild conditions, easy operation, facile scalability, and high efficiency, allowing convenient access to dichloronated gem -difluoroalkenes.

A metal-free photosensitized three-component reaction of oxime esters, alkenes, and DABCO·(SO 2 ) 2 was developed. This protocol could accommodate a wide substrate scope, including activated and unactivated alkenes and aryl and aliphatic carboxylic acid oxime esters, delivering a broad range of β-amino sulfones in moderate to high yields. The insertion of SO 2 as a linker moiety allows the manipulation of the functionality in the reaction process, expanding the utility of oxime esters as bifunctional reagents.

An unprecedented photoredox-catalyzed phosphine-mediated deoxygenation of hexafluoroacetone hydrate was established to accomplish the hydroxylpolyfluoroalkylation of electron-deficient alkenes. A range of bis(trifluoromethyl)carbinols were facilely accessed by using readily available hexafluoroacetone hydrate, instead of toxic gaseous hexafluoroacetone. A range of electron-deficient alkenes are tolerated, giving the corresponding hydro-hydroxylpolyfluoroalkylated products in moderate to high yields. Remarkable features of this synthetic strategy include operational simplicity, mild reaction conditions, excellent regioselectivity, and broad functional group tolerance. The success of this strategy relies on the delicate utilization of aldehyde/ketone-gem-diol intrinsic equilibrium, which offers an innovated open-shell pathway for the assembly of synthetically challenging polyfluoroalkylated scaffolds., (© 2022 Wiley-VCH GmbH.)

A metal-free photosensitized protocol for regioselective diamination of alkene feedstocks over a single step was developed based on the rationally designed bifunctional diamination reagent, thus affording a range of differentially protected 1,2-diamines in moderate to high yields. Mechanistic studies reveal that the reaction is initiated with a triplet-triplet energy transfer between thioxanthone catalyst and diamination reagent, followed by fragmentation to simultaneously generate long-lived iminyl radical and transient amidyl radical. The excellent regioselectivity presumably stems from the large reactivity difference between two different N-centered radical species. This protocol is characterized by excellent regioselectivity, broad functional group tolerance, and mild reaction conditions, which would enrich the diversity and versatility of facilitate the diversity-oriented synthesis of 1,2-diamine-containing complex molecule scaffolds., (© 2022 Wiley-VCH GmbH.)

The purpose of this study was to evaluate how a person's view of life and death might influence various aspects of well-being. Similar studies have been conducted with adolescents in different cultures, but not with Chinese Tujia ethnic adolescents. Tujia adolescents ( N  = 309) completed the Meaning in Life Questionnaire (MLQ), the Death Attitude Profile (DAP), the Satisfaction with Life Scale (SWLS) and the Happiness Inventory (HI). Results indicated that Chinese Tujia ethnic adolescents maintain a relatively positive life-and-death view and overall well-being. Meaning in life and death attitude both corresponded with overall well-being. A dominance analysis indicated that meaning in life can predict the well-being of a person better than a death attitude. Limitations and future directions are discussed.

A photoredox-catalysed chlorination of quinoxalin-2(1 H )-ones was developed by using CHCl 3 as a chlorine source, thus affording various 3-chloroquinoxalin-2(1 H )-ones in moderate to high yields. This protocol is characterized by mild reaction conditions, excellent regioselectivity, and readily available chlorination agent. Considering the operational simplicity and low cost of this chlorination approach, this developed method offers an innovative pathway for rapid incorporation of chlorine functionality into heteroarenes, and will inspire broader exploitation of new chlorination strategies.

Herein, readily available and inexpensive CDCl 3 was first identified as a new trideuteromethylation reagent under photoredox-catalyzed conditions. Thus, a facile photocatalytic protocol for the C-H trideuteromethylation of quinoxalin-2(1 H )-one was achieved. This operationally straightforward transformation displays a broad scope and provides a new route to introduce the trideuteromethyl group (CD 3 ) with excellent levels of deuterium content.

A photoinduced, photocatalyst-free cyanoalkylation of nitrostyenes was explored, affording a series of cyanoalkylated alkenes in moderate to good yields. Mechanistic studies reveal that an electron donor-acceptor complex formed between O -aryl oximes and DIPEA is presumably involved in this process. The excellent functional group compatibility of this newly designed synthetic protocol allows for cyanoalkylation of structurally varied substrates, which offers an eco-friendly pathway for the assembly of cyanoalkylated alkenes.

Background: There is significant heterogeneity between gastroesophageal varices (GOV2) and isolated gastric varices (IGV1). The data on the difference between GOV2 and IGV1 are limited., Aim: To determine the etiology, clinical profiles, endoscopic findings, imaging signs, portosystemic collaterals in patients with GOV2 and IGV1., Methods: Medical records of 252 patients with gastric fundal varices were retrospectively collected, and computed tomography images were analyzed., Results: Significant differences in routine blood examination, Child-Pugh classification and MELD scores were found between GOV2 and IGV1. The incidence of peptic ulcers in patients with IGV1 (26.55%) was higher than that of GOV2 (11.01%), while portal hypertensive gastropathy was more commonly found in patients with GOV2 (22.02%) than in those with IGV1 (3.54%). Typical radiological signs of cirrhotic liver were more commonly observed in patients with GOV2 than in those with IGV1. In patients with GOV2, the main afferent vessels were via the left gastric vein (LGV) (97.94%) and short gastric vein (SGV) (39.18%). In patients with IGV1, the main afferent vessels were via the LGV (75.61%), SGV (63.41%) and posterior gastric vein (PGV) (43.90%). In IGV1 patients with pancreatic diseases, spleno-gastromental-superior mesenteric shunt (48.15%) was a major collateral vessel. In patients with fundic varices, the sizes of gastric/esophageal varices were positively correlated with afferent vessels (LGVs and PGVs) and efferent vessels (gastrorenal shunts). The size of the esophageal varices was negatively correlated with gastrorenal shunts in GOV2 patients., Conclusion: Significant heterogeneity in the etiology and vascular changes between GOV2 and IGV1 is useful in making therapeutic decisions., Competing Interests: Conflict-of-interest statement: All authors have nothing to disclose, (©The Author(s) 2022. Published by Baishideng Publishing Group Inc. All rights reserved.)

A novel visible-light-driven organocatalytic protocol to access aerobic oxidative cleavage of olefins, promoted by sodium benzene sulfinate, is described herein. An array of alkenes smoothly delivered the corresponding aldehydes and ketones under transition-metal-free conditions. Notably, α-halo-substituted styrenes proceeded with photoinduced oxidation to finally afford α-halo-acetophenones with halogen migration. Crucial to this oxidation was the formation of charge-transfer complexes between sodium benzene sulfinate with molecular O 2 to ultimately deliver the carbonyl products.

The mechanism of the phosphine-catalysed domino sequence of alkynoates and activated methylenes has been computationally studied. The computational results revealed that the [3 + 2] annulation sequence could be ruled out, due to a difficult Knoevenagel condensation of aromatic aldehydes and active methylenes. The reaction proceeds through a [4 + 1] annulation pathway, which involves a phosphine-catalysed MBH-type reaction followed by a [1,5]-proton shift and dehydration to afford vinyl phosphonium intermediates as four-carbon synthons in the annulation reaction. Then 1,3-dicarbonyls act as nucleophiles to attack vinyl phosphonium intermediates, subsequently leading to a stepwise [1,3]-proton shift and an intramolecular nucleophilic attack to close the five-member ring.

Reported herein is a visible-light-induced, catalyst-free intramolecular cyclization of 4-phenylsulfonyl-2,3,5,6-tetrachloropyridine, leading to rapid assembly of a series of unprecedented benzo[4,5]thieno[3,2- c ]pyridine 5,5-dioxide scaffolds under mild conditions. The rational introduction of a perchloropyridin-4-yl module significantly facilitated this photoinduced process and offers a versatile platform for broad structural variation. Mechanistic studies revealed that a newly identified charge-transfer complex with carbonate is crucial to this photoinduced process.

Herein, a tunable iodization/deuterolysis protocol for phosphonium ylides by employing D 2 O as the deuterium source was designed. Notably, this process could be manipulated by tuning the base, thus leading to two valuable deuterated building blocks - benzyl iodides and aromatic aldehydes with broad substrate scope, good functional group compatibility and excellent deuteration degree. Concise syntheses of a series of deuterated drug analogues have been achieved based on the developed deuteration reaction platform.

A highly modular 1,4-difunctionalization of 1,3-dienes with bromodifluoroacetamides and sulfinates/amines through a photoinduced palladium-catalyzed radical relay process is described herein. This developed protocol offers a facile and general route to access a variety of value-added CF 2 -incorporated alkenes in moderate to good yields. The versatility and flexibility of this approach have been well illustrated by readily accessible starting materials, synthetic convenience, and wide functional group compatibility.

A phosphine-mediated, well-designed Morita-Baylis-Hillman-type/Wittig cascade for the rapid assembly of a quinolinone framework from benzaldehyde derivatives is developed for the first time. By rationally combining I 2 /NIS-mediated cyclization, biologically relevant 3-(benzopyrrole/furan-2-yl) quinolinones were facilely synthesized in a one-pot process by starting from 3-styryl-quinolinones bearing an o -hydroxy/amino group, significantly expanding the chemical space of this privileged skeleton. Further utility of this protocol is illustrated by successfully performing this transformation in a catalytic manner through in situ reduction of phosphine oxide by phenylsilane.

Reported herein is a photoredox-catalyzed amination of o- hydroxyarylenaminones with tert -butyl ((perfluoropyridin-4-yl)oxy)carbamate, a versatile amidyl-radical precursor developed in our laboratory. This work establishes a new cascade pathway for the assembly of a range of 3-aminochromones under mild conditions. Downstream transformations of the obtained 3-aminochromones to construct diverse amino pyrimidines greatly broaden the applications of this photocatalyzed protocol.

A catalyst-free strategy for regioselective hydroxydifluoroalkylation of alkenes with alkyl bromides was developed, affording a series of difluoroalkylated tertiary alcohols in moderate to good yields. This photocatalyst-free protocol shows broad substrate scope under mild conditions. Moreover, mechanistic studies revealed that a newly identified electron donor-acceptor complex is crucial to this transformation.