A visible-light-catalyzed sulfonylation reaction of an aryl selenonium salt via an electron donor-acceptor complex.

An efficient synthesis of sulfone structures through selenonium salts and sodium sulfinates was developed. Under the irradiation of a blue LED lamp, the two substrates generate aryl and sulfonyl radicals through the activation of the intermediate electron donor acceptor (EDA) complex, thereby synthesizing aromatic, heteroaromatic and aliphatic sulfones in medium to good yields. The advantages of this strategy are metal-free, mild conditions and the leaving group is recycled to construct new selenonium salts.

SIRT6 alleviates senescence induced by Porphyromonas gingivalis in human gingival fibroblasts.

OBJECTIVE: Bidirectional influences between senescence and inflammation are newly discovered. This study aimed to clarify the roles and mechanism of Porphyromonas gingivalis (P. gingivalis) in exacerbating senescence in human gingival fibroblasts (HGFs). DESIGN: Subgingival plaque and gingivae were collected from twenty-four periodontitis patients and eighteen periodontally healthy subjects. Quantities of P. gingivalis in subgingival plaque were explored using real-time PCR and the expressions of p53, p21 and SIRT6 in gingivae were detected by IHC. Moreover, senescence in HGFs was induced by P. gingivalis lipopolysaccharide (LPS) and the expressions of senescence-related ß-galactosidase (SA-ß-gal), p53, p21 and senescence-associated secretory phenotype (IL-6 and IL-8) with or without treatment by SIRT6 activator UBCS039 were explored by IHC, western blot and ELISA, respectively. In addition, the levels of SIRT6, Nrf2, HO-1 and reactive oxygen species (ROS) were examined by western blot and flow cytometry. RESULTS: Quantities of P. gingivalis in subgingival plaque and semi-quantitative scores of p53 and p21 in gingivae of periodontitis patients were increased compared with healthy controls (p < 0.05), while SIRT6 score in periodontitis patients was decreased (p < 0.001). Quantities of P. gingivalis were positively correlated with p53 and p21 scores (0.6 < r < 0.9, p < 0.01), and negatively correlated with SIRT6 score (-0.9 < r<-0.6, p < 0.01). Moreover, P. gingivalis LPS increased the levels of SA-ß-gal, p53, p21, IL-6, IL-8 and ROS and decreased the levels of SIRT6, Nrf2 and HO-1 in HGFs, which was rescued by UBCS039 (p < 0.05). CONCLUSIONS: P. gingivalis LPS could induce senescence of HGFs, which could be reversed by SIRT6 via Nrf2-HO-1 signaling pathway.

A Zn(II) Coordination Polymer for Fluorescent Turn-Off Selective Sensing of Heavy Metal Cation and Toxic Inorganic Anions.

A novel coordination polymer [Zn(atyha)2]n (1) (Hatyha = 2-(2-aminothiazole-4-yl)-2- hydroxyiminoacetic acid) was constructed by hydrothermal reaction of Zn2+ with Hatyha ligand. CP 1 exhibits a 2D (4,4)-connected topological framework with Schläfli symbol of {44·62}, where atyha- anions serve as tridentate ligands, bridging with Zn2+ through carboxylate, thiazole and oxime groups. CP 1 displays a strong ligand-based photoluminescence at 390 nm in the solid state, and remains significantly structurally stable in water. Interestingly, it can be utilized as a fluorescent probe for selective and sensitive sensing of Fe3+, Cr2O72- and MnO4- through the fluorescent turn-off effect with limit of detection (LOD) of 3.66 × 10-6, 2.38 × 10-5 and 2.94 × 10-6 M, respectively. Moreover, the efficient recyclability for detection of Fe3+ and Cr2O72- is better than that for MnO4-. The mechanisms of fluorescent quenching involve reversible overlap of UV-Vis absorption bands of the analytes (Fe3+, Cr2O72- and MnO4-) with fluorescence excitation and emission bands for CP 1, respectively.

Lattice Matching and Microstructure of the Aromatic Amide Fatty Acid Salts Nucleating Agent on the Crystallization Behavior of Recycled Polyethylene Terephthalate.

To solve the decrease in the crystallization, mechanical and thermal properties of recycled polyethylene terephthalate (rPET) during mechanical recycling, the aromatic amide fatty acid salt nucleating agents Na-4-ClBeAmBe, Na-4-ClBeAmGl and Na-4-ClAcAmBe were synthesized and the rPET/nucleating agent blend was prepared by melting blending. The molecular structure, the thermal stability, the microstructure and the crystal structure of the nucleating agent were characterized in detail. The differential scanning calorimetry (DSC) result indicated that the addition of the nucleating agent improved the crystallization temperature and accelerated the crystallization rate of the rPET. The nucleation efficiencies (NE) of the Na-4-ClBeAmBe, Na-4-ClBeAmGl and Na-4-ClAcAmBe were increased by 87.2%, 87.3% and 41.7% compared with rPET which indicated that Na-4-ClBeAmBe and Na-4-ClBeAmGl, with their long-strip microstructures, were more conducive to promoting the nucleation of rPET. The equilibrium melting points (Tm0) of rPET/Na-4-ClBeAmBe, rPET/Na-4-ClBeAmGl and rPET/Na-4-ClAcAmBe were increased by 11.7 °C, 18.6 °C and 1.9 °C compared with rPET, which illustrated that the lower mismatch rate between rPET and Na-4-ClBeAmGl (0.8% in b-axis) caused Na-4-ClBeAmGl to be the most capable in inducing the epitaxial crystallization and orient growth along the b-axis direction of the rPET. The small angle X-ray diffraction (SAXS) result proved this conclusion. Meanwhile, the addition of Na-4-ClBeAmGl caused the clearest increase in the rPET of its flexural strength and heat-distortion temperature (HDT) at 20.4% and 46.7%.

Preoperative Frailty Assessment Predicts Postoperative Mortality, Delirium and Pneumonia in Elderly Lung Cancer Patients: A Retrospective Cohort Study.

BACKGROUND: The purpose of this study was to investigate the predictive value of the 5-factor modified frailty index (mFI-5) for postoperative mortality, delirium and pneumonia in patients over 65 years of age undergoing elective lung cancer surgery. METHODS: Data were collected from a single-center retrospective cohort study conducted in a general tertiary hospital from January 2017 to August 2019. In total, the study included 1372 elderly patients aged over 65 who underwent elective lung cancer surgery. They were divided into frail group (mFI-5, 2-5), prefrail group (mFI-5, 1) and robust group (mFI-5, 0) on the basis of mFI-5 classification. The primary outcome was postoperative 1-year all-cause mortality. Secondary outcomes were postoperative pneumonia and postoperative delirium. RESULTS: Frailty group had the highest incidence of postoperative delirium (frailty 31.2% versus prefrailty 1.6% versus robust 1.5%, p < 0.001), postoperative pneumonia (frailty 23.5% versus prefrailty 7.2% versus robust 7.7%, p < 0.001), and postoperative 1-year mortality (frailty 7.0% versus prefrailty 2.2% versus robust 1.9%. p < 0.001). Frail patients have significantly longer length of hospitalization than those in the robust group and prefrail patients (p < 0.001). Multivariate analysis showed a clear link between frailty and increased risk of postoperative delirium (aOR 2.775, 95% CI 1.776-5.417, p < 0.001), postoperative pneumonia (aOR 3.291, 95% CI 2.169-4.993, p < 0.001) and postoperative 1-year mortality (aOR 3.364, 95% CI, 1.516-7.464, p = 0.003). CONCLUSIONS: mFI-5 has potential clinical utility in predicting postoperative death, delirium and pneumonia incidence in elderly patients undergoing radical lung cancer surgery. Frailty screening of patients (mFI-5) may provide benefits in risk stratification, targeted intervention efforts, and assist physicians in clinical decision-making.

Cane Molasses Derived N-Doped Graphene Quantum Dots: Dynamic Quenching Synergistically Photoinduced Electron Transfer for the Instant Detection of Nitrofuran Antibiotics.

The development of a highly selective, simple, and rapid detection method for nitrofuran antibiotics (NFs) is of great significance for food safety, environmental protection, and human health. To meet these needs, in this work, cyan-color highly fluorescent N-doped graphene quantum dots (N-GQDs) were synthesized using cane molasses as the carbon source and ethylenediamine as the nitrogen source. The synthesized N-GQDs have an average particle size of 6 nm, a high fluorescence intensity with 9 times that of undoped GQDs, and a high quantum yield (24.4%) which is more than 6 times that of GQDs (3.9%). A fluorescence sensor based on N-GQDs for the detection of NFs was established. The sensor shows advantages of fast detection, high selectivity, and sensitivity. The limit of detection for furazolidone (FRZ) was 0.29 µM, the limit of quantification (LOQ) was 0.97 µM, and the detection range was 5-130 µM. The fluorescence quenching mechanism of the sensor was explored by fluorescence spectroscopy, UV-vis absorption spectroscopy, Stern-Volmer quenching constant, Zeta potential, UV-vis diffuse reflectance spectroscopy, and cyclic voltammetry. A fluorescence quenching mechanism of dynamic quenching synergized with photoinduced electron transfer was revealed. The developed sensor was also successfully applied for detecting FRZ in various real samples, and the results were satisfactory.

Visible-light-mediated α-amino alkylation of ketimines and aldimines for the synthesis of 1,2-diamines.

A visible-light-mediated protocol to prepare 1,2-diamines has been successfully explored based on the photoredox/Brønsted acid co-catalyzed α-amino alkylations of imines with tertiary amines. Both ketimines and aldimines are applicable to this transformation. Various 1,2-diamines with different functional groups were produced in moderate to excellent yields. Moreover, this approach could be performed on a gram scale, showing its practicality.

Visible light-mediated three-component functionalization of olefins with sulfoxyimidoylsulfonium salt for the synthesis of ß-amino alcohols and amino ethers.

A new strategy involving three-component functionalization of olefins with sulfoxyimidoylsulfonium salt and a nucleophilic reagent for the synthesis of ß-amino alcohols and ß-amino ethers by photoredox catalysis was developed. The sulfoxyimidoylsulfonium salt is important and serves as the N-centred radical precursor. ß-Amino alcohols and ß-amino ethers bearing various functional groups are synthesized in good yields under mild conditions. Furthermore, the advantages of this strategy are greater safety, no additives, and easy to obtain raw materials.

A comprehensive content analysis of 104 Chinese electronic cigarette manufacturing enterprise official websites.

OBJECTIVE: The goal was to analyse website content of Chinese electronic (e) cigarette manufacturing enterprises and understand the marketing strategies to provide evidence for decision-makers to regulate manufacturers. METHODS: Through QCC.com, one of the largest enterprise information query platforms in China, we identified 104 official manufacturer websites in 2021. A codebook including 6 sections with 31 items was developed and all webpages were coded separately by two trained researchers. RESULTS: Over half of the websites (56.7%) did not have age verification for entry. Thirty-two (30.8%) websites had no restriction for minors to use or purchase e-cigarettes, and 79 (76.0%) had no health warning. Overall, 99 websites (95.2%) displayed their products, and 72 (69.2%) displayed e-flavours. The most frequently used descriptions of products included good taste (68.3%), positive mood (62.5%), leakage resistance (56.7%), enjoyment (47.1%), reduced harm (45.2%), alternatives to cigarettes (43.3%) and long battery life (42.3%). Additionally, 75 websites (72.1%) provided contact information on different channels, including WeChat (59.6%), Weibo (41.3%), Facebook (13.5%), Instagram (12.5%) and brand apps (2.9%). Manufacturers provided investment and franchise information (59.6%) and offline store information (17.3%). In addition, 41.3% websites included content regarding corporate social responsibility. CONCLUSIONS: Chinese e-cigarette manufacturers' official websites have become a platform for presenting product and brand information, establishing online and offline marketing loops, and displaying corporate social responsibility with weak age restrictions on access and a lack of health warnings. The Chinese government should implement strict regulatory measures on e-cigarette enterprises.

Antitumor effect of luteolin proven by patient-derived organoids of gastric cancer.

Luteolin (Lut) has been shown to inhibit gastric cancer (GC); however, its efficacy compared to other clinical drugs has not been examined in human samples. This study aimed to elucidate the antitumor activity of Lut in GC patient-derived organoids (PDOs). PDOs were established from GC cancer tissues, and the characterization of tissues and PDOs was performed using whole-exome sequencing. Drug sensitivity tests were performed by treating PDOs with Lut, norcantharidin (NCTD), and carboplatin (CP). RNA sequencing of PDOs was performed to elucidate the antitumor mechanism of Lut, which was further verified in three GC cell lines. Eleven PDOs were successfully constructed, and were highly consistent with the pathophysiology and genetic changes in the corresponding tumors. The IC50s of Lut, NCTD, and CP of PDOs were 27.19, 23.9, and 37.87 µM, respectively. Lut treatment upregulated FOXO3, DUSP1, and CDKN1A expression and downregulated IL1R1 and FGFR4 expression in GC cell lines, which was consistent with the results of PDOs. We demonstrate that Lut exerted stronger antitumor effects than CP, but a similar effect to that of NCTD, which was obtained in an in vitro PDO system. Additionally, Lut exerted varying degrees of antitumor effects against the PDOs, thereby indicating that PDO may be a useful preclinical drug screening tool for personalized treatment.

Symbiotic integration of waste disposal capability within a city cluster: The case of the Yangtze River Delta.

With the ongoing urbanization in developing regions, integrating regional waste disposal capability is challenging due to unbalanced economic development and rising environmental issues. This research proposed a multi-dimensional symbiotic integration of waste disposal capability. Applying data from the Yangtze River Delta (YRD) in China, we first explore the waste flows and interactions between cities to identify the possibility of inter-municipal collaboration based on the augmented gravity model. We then employ social network analysis to categorize the cities in the collaborative network of waste disposal into subgroups by functionalities. Finally, we proposed the top-down framework of symbiotic networks for waste disposal. Our findings indicate that YRD cities can be classified into four types according to their waste density and disposal efficiency: High-High, Low-High, Low-Low, and High-Low. We also identify three types of inter-municipal collaborative relationships: between high-density and high-efficiency cities, between high-density cities, and between high-efficiency cities. The city subgroups can be categorized into "high-efficiency clusters," "high-density clusters," and "hub clusters," which pave the way for a shared or complementary urban symbiosis in the waste recycling industry. The division of roles among subgroups enables symbiotic activities within the city cluster. This paper extends the spatial scope of industrial symbiosis literature and has practical implications for transitioning to a circular economy in waste management of developing countries.

Visible-light-catalyzed C-H arylation of (hetero)arenes via arylselenonium salts.

A novel photo-induced C-H arylation of (hetero)arenes has been developed. Aryl selenonium salts as an aryl source led to the arylation of aromatic (hetero)cyclic compounds via C-Se bond activation under blue LED irradiation. The method simply utilizes the safe and clean energy source and yields a range of site-selective biphenyl or bi-heterocyclic products in medium to good yields. Furthermore, the borylation and Sonogashira coupling of aryl selenonium salts proceed in good yields as well. From the results, it is shown that selenonium salts are more reactive than sulfonium salts.

Investigation of the Locked-Unlocked Mechanism in Living Anionic Polymerization Realized with 1-(Tri-isopropoxymethylsilylphenyl)-1-phenylethylene.

Reported is an intriguing advance in living anionic polymerization (LAP) by a "locked-unlocked" mechanism in which the living anionic species can be quantitatively locked by end-capping with 1-(tri-isopropoxymethylsilylphenyl)-1-phenylethylene (DPE-Si(O-iPr)3 ) and can be unlocked by adding the key, sodium 2,3-dimethylpentan-3-olate (NaODP). These new insights into this mechanism were carefully confirmed by designing reactions involving sequential feeding of quantitative DPE-Si(O-iPr)3 and traditional monomers mixed with NaODP, and subsequently characterizing the corresponding samples, taken during the feeding process, by GPC, NMR, and MALDI-TOF-MS techniques. The switch from the locked to unlocked state was clearly confirmed by these characterization techniques. The putative locked-unlocked mechanism in the LAP was simulated by the Gaussian method. This intriguing mechanistic finding of LAP reactions is expected to supplement the existing knowledge and facilitate the tailoring of specific structures for these polymerizations.

Efficient caproic acid production from lignocellulosic biomass by bio-augmented mixed microorganisms.

Producing caproic acid via carboxylate platform is an environmentally-friendly approach for treating lignocellulosic agricultural waste. However, its implementation is still challenged by low product yields and selectivity. A microbiome named cellulolytic acid-producing microbiome (DCB), proficient in producing cellulolytic acid, was successfully acquired and shows promise for producing high-level caproic acid. In this study, a bioaugmentation method utilizing Clostridium kluyveri is proposed to enhance caproic acid yield of DCB using rice straw. With exogenous ethanol, bioaugmentation with Clostridium kluyveri significantly improved the caproic acid concentration and selectivity by 7 times and 4.5 times, achieving 12.9 g/L and 55.1 %, respectively. The addition of Clostridium kluyveri introduced reverse ß-oxidation pathway, a more efficient caproic acid production pathway. Meanwhile, bioaugmentation enriched the bacteria proficient in degrading straw and producing short-chain fatty acids, providing more substrates for caproic acid production. This study provides potential bioaugmentation strategies for optimizing caproic acid yield from lignocellulosic biomass.

Large-Scale Bio-Inspired FPGA Models for Path Planning.

The hippocampus provides significant inspiration for spatial navigation and memory in both humans and animals. Constructing large-scale spiking neural network (SNN) models based on the biological neural systems is an important approach to comprehend the computational principles and cognitive function of the hippocampus. Such models are usually implemented on neuromorphic computing platforms, which often have limited computing resources that constrain the achievable scale of the network. This work introduces a series of digital design methods to realize a Field-Programmable Gate Array (FPGA) friendly SNN model. The methods include FPGA-friendly nonlinear calculation modules and a fixed-point design algorithm. A brain-inspired large-scale SNN of ∼21 k place cells for path planning is mapped on FPGA. The results show that the path planning tasks in different environments are finished in real-time and the firing activities of place cells are successfully reproduced. With these methods, the achievable network size on one FPGA chip is increased by 1595 times with higher resource usage efficiency and faster computation speed compared to the state-of-the-art.

Efficacy of non-pharmacological interventions for primary dysmenorrhoea: a systematic review and Bayesian network meta-analysis.

OBJECTIVES: To assess the relative benefits of various non-pharmacological interventions on treating primary dysmenorrhoea within a network meta-analysis. STUDY DESIGN: Systematic review and Bayesian network meta-analysis. INCLUSION CRITERIA: Randomised controlled trial involving patient with primary dysmenorrhoea and received non-pharmacological interventions. DATA SOURCES: Four databases (Medline, Embase, Cochrane Library and Web of Science) were searched from inception to October first, 2022. RISK-OF-BIAS ROB ASSESSMENT: RoB 2.0 assessment tools was used to assess the risk of bias in the included studies. SYNTHESIS OF RESULTS: Conventional meta-analysis was conducted by pairwise comparison between non-pharmacological therapy and control treatment. The Bayesian network meta-analysis was conducted by the Aggregate Data Drug Information System Software based on the consistency or inconsistency model, and rank probability was used to indicate the priority of non-pharmacological therapy. RESULTS: 33 studies involving eight non-pharmacological interventions were included. With regard to conventional meta-analysis, we selected Visual Analogue Scale (VAS) as primary outcome to evaluate the pain intensity. The result showed that eight interventions (Exercise, Herb, Acupuncture, Aromatherapy, Transcutaneous Electrical Nerve Stimulation, Topical heat, Acupressure, Yoga) displayed positive effect on reduction of menstrual pain compared with placebo or no treatment. A Bayesian network meta-analysis revealed that exercise -3.20 (95% CI -4.01 to -2.34), acupuncture -2.90 (95% CI -3.97 to -2.85) and topical heat -2.97 (95% CI -4.66 to -1.29) probably resulted in a reduction in pain intensity (VAS) . CONCLUSIONS: Non-pharmacological interventions may result in a reduction or slight reduction in pain intensity compared with no treatment or placebo. Specifically, exercise and acupuncture are considered as potentially effective non-pharmacological treatments in short-term treatment. Indeed, larger and better methodological quality research is needed. TRIAL REGISTRATION NUMBER: CRD42022351021.

Age-dependent coupling characteristics of bilateral frontal EEG during desflurane anesthesia.

Objectives.The purpose of this study is to investigate the age dependence of bilateral frontal electroencephalogram (EEG) coupling characteristics, and find potential age-independent depth of anesthesia monitoring indicators for the elderlies.Approach.We recorded bilateral forehead EEG data from 41 patients (ranged in 19-82 years old), and separated into three age groups: 18-40 years (n= 12); 40-65 years (n= 14), >65 years (n= 15). All these patients underwent desflurane maintained general anesthesia (GA). We analyzed the age-related EEG spectra, phase amplitude coupling (PAC), coherence and phase lag index (PLI) of EEG data in the states of awake, GA, and recovery.Main results.The frontal alpha power shows age dependence in the state of GA maintained by desflurane. Modulation index in slow oscillation-alpha and delta-alpha bands showed age dependence and state dependence in varying degrees, the PAC pattern also became less pronounced with increasing age. In the awake state, the coherence in delta, theta and alpha frequency bands were all significantly higher in the >65 years age group than in the 18-40 years age group (p< 0.05 for three frequency bands). The coherence in alpha-band was significantly enhanced in all age groups in GA (p< 0.01) and then decreased in recovery state. Notably, the PLI in the alpha band was able to significantly distinguish the three states of awake, GA and recovery (p< 0.01) and the results of PLI in delta and theta frequency bands had similar changes to those of coherence.Significance.We found the EEG coupling and synchronization between bilateral forehead are age-dependent. The PAC, coherence and PLI portray this age-dependence. The PLI and coherence based on bilateral frontal EEG functional connectivity measures and PAC based on frontal single-channel are closely associated with anesthesia-induced unconsciousness.

Sevoflurane exerts antidepressant-like effects via the BDNF-TrkB pathway.

Depression has emerged as the predominant psychiatric affliction affecting individuals. Prior research has substantiated the antidepressant properties exhibited by numerous anesthetics. Sevoflurane, a widely utilized inhalant anesthetic in clinical practice, remains relatively uncharted in terms of its specific antidepressant effects. In this study, we used open field test, forced swimming test and novelty-suppressed feeding test to investigate the anxiety and depression-like behaviors in C57BL/6 mice following the inhalation of sevoflurane. We then used western blotting to scrutinized the expression levels of proteins associated with the brain-derived neurotrophic factor (BDNF)-tryosine receptor kinase B (TrkB) pathway in the hippocampus and prefrontal cortex. To further investigate whether sevoflurane exerts antidepressant-like effects via the BDNF-TrkB pathway, we downregulated TrkB expression by administering siRNA into the lateral ventricle. We found that the inhalation of 2.5 % sevoflurane exerted a significant antidepressant-like effect, accompanied by an elevation in p-TrkB expression levels in the hippocampus and prefrontal cortex. Intriguingly, this antidepressant-like effect was abrogated following the downregulation of TrkB expression through the microinjection of siRNA into the lateral ventricle. In conclusion, this study provides evidence supporting the notion that sevoflurane exerts its antidepressant-like effect via the BDNF-TrkB signaling pathway.

Ag3PO4 enables the generation of long-lived radical cations for visible light-driven [2 + 2] and [4 + 2] pericyclic reactions.

Photocatalytic redox reactions are important for synthesizing fine chemicals from olefins, but the limited lifetime of radical cation intermediates severely restricts semiconductor photocatalysis efficiency. Here, we report that Ag3PO4 can efficiently catalyze intramolecular and intermolecular [2 + 2] and Diels-Alder cycloadditions under visible-light irradiation. The approach is additive-free, catalyst-recyclable. Mechanistic studies indicate that visible-light irradiation on Ag3PO4 generates holes with high oxidation power, which oxidize aromatic alkene adsorbates into radical cations. In photoreduced Ag3PO4, the conduction band electron (eCB-) has low reduction power due to the delocalization among the Ag+-lattices, while the particle surfaces have a strong electrostatic interaction with the radical cations, which considerably stabilize the radical cations against recombination with eCB-. The radical cation on the particle's surfaces has a lifetime of more than 2 ms, 75 times longer than homogeneous systems. Our findings highlight the effectiveness of inorganic semiconductors for challenging radical cation-mediated synthesis driven by sunlight.