Unlocking the Potential of Oxidative Asymmetric Catalysis with Continuous Flow Electrochemistry.

In the field of catalytic asymmetric synthesis, the less-treated path lies in oxidative catalytic asymmetric transformations. The hurdles of pinpointing the appropriate chemical oxidants and addressing their compatibility issues with catalysts and functionalities present significant challenges. Organic electrochemistry, employing traceless electrons for redox reactions, is underscored as a promising solution. However, the commonly used electrolysis in batch cells introduces its own set of challenges, hindering the advancement of electrochemical asymmetric catalysis. Here we introduce a microfluidic electrochemistry platform with single-pass continuous flow reactors that exhibits a wide-ranging applicability to various oxidative asymmetric catalytic transformations. This is exemplified through the sulfenylation of 1,3-dicarbonyls, dehydrogenative C-C coupling, and dehydrogenative alkene annulation processes. The unique properties of microfluidic electrochemical reactors not only eliminate the need for chemical oxidants but also enhance reaction efficiency and reduce the use of additives and electrolytes. These salient features of microfluidic electrochemistry expedite the discovery and development of oxidative asymmetric transformations. In addition, the continuous production facilitated by parallel single-pass reactors ensures straightforward reaction upscaling, removing the necessity for reoptimization across various scales, as evidenced by direct translation from milligram screening to hectogram asymmetric synthesis.

Effectiveness of Electroencephalography Neurofeedback for Improving Working Memory and Episodic Memory in the Elderly: A Meta-Analysis.

Background and Objective: Existing evidence indicates the potential benefits of electroencephalography neurofeedback (NFB) training for cognitive function. This study aims to comprehensively review all available evidence investigating the effectiveness of NFB on working memory (WM) and episodic memory (EM) in the elderly population. Material and Methods: A systematic search was conducted across five databases to identify clinical trials examining the impact of NFB on memory function in healthy elderly individuals or those with mild cognitive impairment (MCI). The co-primary outcomes focused on changes in WM and EM. Data synthesis was performed using a random-effects meta-analysis. Results: Fourteen clinical trials (n = 284) were included in the analysis. The findings revealed that NFB was associated with improved WM (k = 11, reported as Hedges' g = 0.665, 95% confidence [CI] = 0.473 to 0.858, p < 0.001) and EM (k = 12, 0.595, 0.333 to 0.856, p < 0.001) in the elderly, with moderate effect sizes. Subgroup analyses demonstrated that NFB had a positive impact on both WM and EM, not only in the healthy population (WM: k = 7, 0.495, 0.213 to 0.778, p = 0.001; EM: k = 6, 0.729, 0.483 to 0.976, p < 0.001) but also in those with MCI (WM: k = 6, 0.812, 0.549 to 1.074, p < 0.001; EM: k = 6, 0.503, 0.088 to 0.919, p = 0.018). Additionally, sufficient training time (totaling more than 300 min) was associated with a significant improvement in WM (k = 6, 0.743, 0.510 to 0.976, p < 0.001) and EM (k = 7, 0.516, 0.156 to 0.876, p = 0.005); however, such benefits were not observed in groups with inadequate training time. Conclusions: The results suggest that NFB is associated with enhancement of both WM and EM in both healthy and MCI elderly individuals, particularly when adequate training time (exceeding 300 min) is provided. These findings underscore the potential of NFB in dementia prevention or rehabilitation.

Animal DNA Typing and Its Research Progress in Forensic Medicine.

With the advance of molecular biology, DNA analysis technology has been widely applied in forensic science. Non-human DNA analysis can be used in some special cases and has unique forensic value to provide investigation clues and trial basis. Animal DNA typing plays a more prominent role in the detection of all kinds of non-human DNA related cases and is the main content of forensic non-human DNA analysis. This paper reviews the development history, present situation, advantages and disadvantages of animal DNA typing according to its technology, characteristic, challenges facing forensic science application scenarios, and also its future development.

Zwitterionic Polymer Gradient Interphases for Reversible Zinc Electrochemistry in Aqueous Alkaline Electrolytes.

Aqueous alkaline zinc batteries are of scientific and technological interest because of the potential they offer for cost-effective and safe storage of electrical energy. Poor electrochemical reversibility and shape change of the Zn anode, propensity of Zn to become passivated by surface oxides and hydroxide films upon prolonged exposure to the electrolyte, and electroreduction of water are well-studied but remain unsolved challenges. Here, we create and study electrochemical and transport properties of precise, spatially tunable zwitterionic polymer interphases grown directly on Zn using an initiated-chemical vapor deposition polymerization methodology. In aqueous alkaline media, spatial gradients in composition─from the polymer-electrolyte interface to the solid-polymer interface─promote highly reversible redox reactions at high current density (20 mA cm-2) and high areal capacity (10 mAh cm-2). Via molecular dynamics and experimental analyses, we conclude that the interphases function by regulating the distribution and activity of interfacial water molecules, which simultaneously enables fast ion transport and suppression of surface passivation and the hydrogen evolution reaction. To illustrate the practical relevance of our findings, we study aqueous Zn||NiOOH and Zn||air batteries and observe that zwitterionic polymer interphases produce extended life at high currents and high areal capacity.

Particulate matter 2.5 exposure induces epithelial-mesenchymal transition via PI3K/AKT/mTOR pathway in human retinal pigment epithelial ARPE-19 cells.

Exposure to particulate matter 2.5 (PM2.5) has been linked to ocular surface diseases, yet knowledge of the molecular mechanism impacted on retina pathogenesis is limited. Therefore, the purpose of this study was to explore the effects and involved factors of PM2.5 exposure in human retinal pigment epithelial APRE-19 cells. Our data revealed a decreased cell viability and an increased migratory ability in APRE-19 cells after PM2.5 stimulation. The MMP-2 and MMP-9 protein levels were markedly increased while the MMPs regulators TIMP-1 and TIMP-2 were significantly reduced in PM2.5-exposed APRE-19 cells. PM2.5 also increased pro-MMP-2 expression in the cell culture supernatants. Additionally, PM2.5 promoted the EMT markers through the activation of PI3K/AKT/mTOR pathway. Moreover, the ICAM-1 production was also remarkably increased by PM2.5 but reduced by PI3K/AKT inhibitor LY294002 in APRE-19 cells. Taken together, these results suggest that PM2.5 promotes EMT in a PI3K/AKT/mTOR-dependent manner in the retinal pigment epithelium.

Validation of the short falls efficacy scale-international for Taiwanese community-dwelling older adults: Associations with fall history, physical frailty, and quality of life.

The FES-I is widely used to measure the fear of falling. However, studies linking the Chinese version of the FES-I to frailty and quality of life among older adults are still limited. Thus, this study examined the association of the full 16-item FES-I and the 7-item short FES-I with fall history, physical frailty, and quality of life among older Taiwanese adults. A total of 751 community-dwelling older adults in Taipei City participated in this study. Data analyses included logistic and linear regression models. The 16-item and the short FES-I were strongly correlated (Spearman rho = 0.963), and both scales are reliable. The 7-item FES-I was positively associated with fall history and physical frailty and negatively associated with the physical (b = -0.65, p < 0.001) and mental (b = -0.59, p < 0.001) components of health-related quality of life, independent of physical frailty. Thus, the short FES-I can be used to increase the feasibility of health screenings of older adults in Chinese-speaking contexts.

Selective Permeable Lithium-Ion Channels on Lithium Metal for Practical Lithium-Sulfur Pouch Cells.

Lithium metal batteries are considered a promising candidate for high-energy-density energy storage. However, the strong reducibility and high reactivity of lithium lead to low Coulombic efficiency when contacting oxidants, such as lithium polysulfide caused by the serious "shuttle effect" in lithium-sulfur batteries. Herein we design selectively permeable lithium-ion channels on lithium metal surface, which allow lithium ions to pass through by electrochemical overpotential, while the polysulfides are effectively blocked due to the much larger steric hindrance than lithium ions. The selective permeation of lithium ions through the channels is further elucidated by the molecular simulation and visualization experiment. Consequently, a prolonged cycle life of 75 cycles and high Coulombic efficiency of 99 % are achieved in a practical Li-S pouch cell with limited amounts of lithium and electrolyte, confirming the unique role the selective ion permeation plays in protecting highly reactive alkali metal anodes in working batteries.

An anion-immobilized composite electrolyte for dendrite-free lithium metal anodes.

Lithium metal is strongly regarded as a promising electrode material in next-generation rechargeable batteries due to its extremely high theoretical specific capacity and lowest reduction potential. However, the safety issue and short lifespan induced by uncontrolled dendrite growth have hindered the practical applications of lithium metal anodes. Hence, we propose a flexible anion-immobilized ceramic-polymer composite electrolyte to inhibit lithium dendrites and construct safe batteries. Anions in the composite electrolyte are tethered by a polymer matrix and ceramic fillers, inducing a uniform distribution of space charges and lithium ions that contributes to a dendrite-free lithium deposition. The dissociation of anions and lithium ions also helps to reduce the polymer crystallinity, rendering stable and fast transportation of lithium ions. Ceramic fillers in the electrolyte extend the electrochemically stable window to as wide as 5.5 V and provide a barrier to short circuiting for realizing safe batteries at elevated temperature. The anion-immobilized electrolyte can be applied in all-solid-state batteries and exhibits a small polarization of 15 mV. Cooperated with LiFePO4 and LiNi0.5Co0.2Mn0.3O2 cathodes, the all-solid-state lithium metal batteries render excellent specific capacities of above 150 mAh⋅g-1 and well withstand mechanical bending. These results reveal a promising opportunity for safe and flexible next-generation lithium metal batteries.

Scalable Photoelectrochemical Dehydrogenative Cross-Coupling of Heteroarenes with Aliphatic C-H Bonds.

Heteroarenes are structural motifs found in many bioactive compounds and functional materials. Dehydrogenative cross-coupling of heteroarenes with aliphatic C-H bonds provides straightforward access to functionalized heteroarenes from readily available materials. Established methods employ stoichiometric chemical oxidants under conditions of heating or light irradiation. By merging electrochemistry and photochemistry, we have achieved efficient photoelectrochemical dehydrogenative cross-coupling of heteroarenes and C(sp3 )-H donors through H2 evolution, without the addition of metal catalysts or chemical oxidants. Mechanistically, the C(sp3 )-H donor is converted to a nucleophilic carbon radical through H-atom transfer with chlorine atom, which is produced by light irradiation of anodically generated Cl2 from Cl- . The carbon radical then undergoes radical substitution to the heteroarene to afford alkylated heteroarene products.

ROSA: Resource-Oriented Service Management Schemes for Web of Things in a Smart Home.

A Pervasive-computing-enriched smart home environment, which contains many embedded and tiny intelligent devices and sensors coordinated by service management mechanisms, is capable of anticipating intentions of occupants and providing appropriate services accordingly. Although there are a wealth of research achievements in recent years, the degree of market acceptance is still low. The main reason is that most of the devices and services in such environments depend on particular platform or technology, making it hard to develop an application by composing the devices or services. Meanwhile, the concept of Web of Things (WoT) is becoming popular recently. Based on WoT, the developers can build applications based on popular web tools or technologies. Consequently, the objective of this paper is to propose a set of novel WoT-driven plug-and-play service management schemes for a smart home called Resource-Oriented Service Administration (ROSA). We have implemented an application prototype, and experiments are performed to show the effectiveness of the proposed approach. The results of this research can be a foundation for realizing the vision of "end user programmable smart environments".

High-Operation-Temperature Plasmonic Nanolasers on Single-Crystalline Aluminum.

The recent development of plasmonics has overcome the optical diffraction limit and fostered the development of several important components including nanolasers, low-operation-power modulators, and high-speed detectors. In particular, the advent of surface-plasmon-polariton (SPP) nanolasers has enabled the development of coherent emitters approaching the nanoscale. SPP nanolasers widely adopted metal-insulator-semiconductor structures because the presence of an insulator can prevent large metal loss. However, the insulator is not necessary if permittivity combination of laser structures is properly designed. Here, we experimentally demonstrate a SPP nanolaser with a ZnO nanowire on the as-grown single-crystalline aluminum. The average lasing threshold of this simple structure is 20 MW/cm(2), which is four-times lower than that of structures with additional insulator layers. Furthermore, single-mode laser operation can be sustained at temperatures up to 353 K. Our study represents a major step toward the practical realization of SPP nanolasers.

Rapid screening of residual pesticides on fruits and vegetables using thermal desorption electrospray ionization mass spectrometry.

RATIONALE: Conventional mass spectrometry is encumbered by laborious and inconvenient sample pretreatment. Ambient thermal desorption electrospray ionization mass spectrometry (TD-ESI-MS) is most noted for its rapid, simple, and sensitive detection capabilities. In this study, TD-ESI-MS was used to rapidly characterize residual pesticides on the surfaces of fruits and vegetables. METHODS: A direct sampling probe was used to obtain analytes from sample surfaces. MS and MS/MS analyses were performed on fruits and vegetables via TD-ESI-MS. External calibration curves and reproducibility tests were performed using liquid pesticide standards. Pesticide decay and distribution on samples was studied, as well as the removal of residual pesticides via soaking in water or detergent baths. RESULTS: Since sample pretreatment was unnecessary, an analysis was completed in approximately 15 s or less, with no visible sample damage. Mass spectra were obtained for 22 pesticides. Linear calibrations (R(2) from 0.9414-0.999) had limits of detection as low as 0.5 µg·L(-1), with satisfactory reproducibilities for liquids and solids. Pesticides on sample surfaces decayed over 2 weeks under ambient conditions. Residual pesticides localized at the fruit peel. Detergent baths removed more pesticide than water baths. CONCLUSIONS: TD-ESI-MS was used to rapidly screen residual pesticides in liquids and solids. Pesticides were found on fruits and vegetables, where the decay, distribution, and removal of pesticides on samples were also explored. Due to short analysis times, the technique allows for high-throughput analyses for applications in food and environmental safety.

Association Between Atopic Dermatitis and Aging: Clinical Observations and Underlying Mechanisms.

As one of the most prevalent chronic inflammatory skin diseases, atopic dermatitis (AD) increasingly affects the aging population. Amid the ongoing global aging trend, it's essential to recognize the intricate relationship between AD and aging. This paper reviews existing knowledge, summarizing clinical observations of associations between AD and aging-related diseases in various systems, including endocrine, cardiovascular, and neurological. Additionally, it discusses major theories explaining the correlation, encompassing skin-mucosal barriers, systemic inflammation and stress, genes, signal transduction, and environmental and behavioral factors. The association between AD and aging holds significant importance, both in population and basic perspectives. While further research is warranted, this paper aims to inspire deeper exploration of inflammation/allergy-aging dynamics and the timely management of elderly patients with AD.

Substitution mutation induced migration anomaly of a D10S2325 allele on capillary electrophoresis.

Microvariants of short tandem repeat (STR) have been reported for different commercially available multiplex STR systems. Sequence length variations caused by variant mechanisms were the central cause of these abnormal phenomena. Here, we reported a novel electrophoretic mobility of the variant allele 13 of D10S2325 in the Investigator HDplex(TM) Kit, which was induced by a special sequence structure containing a poly-G tract (ttg ggg ggg) as a result of only one single base substitution in the flanking regions of the core repeat structure. This migration anomaly can pose a potential risk of wrong designation of some off-ladder alleles in STR loci. Furthermore, population genetic data of the Investigator HDplex(TM) Kit in the Chinese Han population are also reported.

Case Report: Cadonilimab-related toxic epidermal necrolysis-like reactions successfully treated with supplemental Adalimumab.

Cadonilimab is the first bi-specific antibody approved for certain malignancies in June 2022, which has a modified Fc structure to reduce immune-related adverse events. To date, no reports have described Cadonilimab-related toxic epidermal necrolysis (TEN). Here, we report the first case of TEN-like reactions occurring during the treatment of hepatocellular carcinoma with Cadonilimab in combination with Lenvatinib and transarterial chemoembolization, successfully treated with supplemental Adalimumab. We confirmed Cadonilimab as the culprit and observed significant improvement in the patient's condition following Adalimumab treatment. The case emphasizes the potential risk of Cadonilimab inducing TEN, and suggests that supplemental Adalimumab could be a favorable option for treating refractory Cadonilimab-related TEN.

Study on the molecular mechanism of anti-liver cancer effect of Evodiae fructus by network pharmacology and QSAR model.

Introduction: Evodiae Fructus (EF) is the dried, near ripe fruit of Euodia rutaecarpa (Juss.) Benth in Rutaceae. Numerous studies have demonstrated its anti-liver cancer properties. However, the molecular mechanism of Evodiae fructus against liver cancer and its structure-activity connection still require clarification. Methods: We utilized network pharmacology and a QSAR (2- and 3-dimensional) model to study the anti-liver cancer effect of Evodiae fructus. First, by using network pharmacology to screen the active substances and targets of Evodiae fructus, we investigated the signaling pathways involved in the anti-liver cancer actions of Evodiae fructus. The 2D-QSAR pharmacophore model was then used to predict the pIC50 values of compounds. The hiphop method was used to create an ideal 3D-QSAR pharmacophore model for the prediction of Evodiae fructus compounds. Finally, molecular docking was used to validate the rationality of the pharmacophore, and molecular dynamics was used to disclose the stability of the compounds by assessing the trajectories in 10 ns using RMSD, RMSF, Rg, and hydrogen bonding metrics. Results: In total, 27 compounds were acquired from the TCMSP and TCM-ID databases, and 45 intersection targets were compiled using Venn diagrams. Network integration analysis was used in this study to identify SRC as a primary target. Key pathways were discovered by KEGG pathway analysis, including PD-L1 expression and PD-1 checkpoint pathway, EGFR tyrosine kinase inhibitor resistance, and ErbB signaling pathway. Using a 2D-QSAR pharmacophore model and the MLR approach to predict chemical activity, ten highly active compounds were found. Two hydrophobic features and one hydrogen bond acceptor feature in the 3D-QSAR pharmacophore model were validated by training set chemicals. The results of molecular docking revealed that 10 active compounds had better docking scores with SRC and were linked to residues via hydrogen and hydrophobic bonds. Molecular dynamics was used to show the structural stability of obacunone, beta-sitosterol, and sitosterol. Conclusion:Pharmacophore 01 has high selectivity and the ability to distinguish active and inactive compounds, which is the optimal model for this study. Obacunone has the optimal binding ability with SRC. The pharmacophore model proposed in this study provides theoretical support for further screening effective anti-cancer Chinese herbal compounds and optimizing the compound structure.

Mollugin induced oxidative DNA damage via up-regulating ROS that caused cell cycle arrest in hepatoma cells.

Mollugin has been proven to have anti-tumor activity. However, its potential anti-tumor mechanism remains to be fully elaborated. Herein, we investigated the growth inhibition of HepG2 cells, as well as the anti-tumor effect of mollugin and its molecular mechanism on H22-tumor bearing mice. In vitro, mollugin was shown to have a strong inhibitory effect on HepG2 cells in a concentration-dependent manner. Mollugin induced S-phase arrest of HepG2 cells, and increased intracellular reactive oxygen species (ROS) levels. Comet assay demonstrated that mollugin induced DNA damage in HepG2 cells, as well as an increase in the expression of p-H2AX. In addition, mollugin induced changes in cyclin A2 and CDK2. However, the addition of antioxidant glutathione (GSH) was able to reverse the effect of mollugin. In vivo, mollugin significantly inhibited tumor growth and reduced the tendency of tumor volume growth in mice. The tumor cell density was found to be decreased in the administration group, and the content of ROS in the tumor tissue significantly increased. The expression of p-H2AX, cyclin A2 and CDK2 were consistent with in vitro results. Mollugin demonstrated anti-hepatocellular carcinoma activity in vitro and in vivo, and its anti-hepatocellular carcinoma activity was found to be related to DNA damage and cell cycle arrest induced by excessive ROS production in cells.

Spallation Characteristics of Single Crystal Aluminum with Copper Nanoparticles Based on Atomistic Simulations.

In this study, the effects of Cu nanoparticle inclusion on the dynamic responses of single crystal Al during shockwave loading and subsequent spallation processes have been explored by molecular dynamics simulations. At specific impact velocities, the ideal single crystal Al will not produce dislocation and stacking fault structure during shock compression, while Cu inclusion in an Al-Cu nanocomposite will lead to the formation of a regular stacking fault structure. The significant difference of a shock-induced microstructure makes the spall strength of the Al-Cu nanocomposite lower than that of ideal single crystal Al at these specific impact velocities. The analysis of the damage evolution process shows that when piston velocity up ≤ 2.0 km/s, due to the dense defects and high potential energy at the interface between inclusions and matrix, voids will nucleate preferentially at the inclusion interface, and then grow along the interface at a rate of five times faster than other voids in the Al matrix. When up ≥ 2.5 km/s, the Al matrix will shock melt or unloading melt, and micro-spallation occurs; Cu inclusions have no effect on spallation strength, but when Cu inclusions and the Al matrix are not fully diffused, the voids tend to grow and coalescence along the inclusion interface to form a large void.

Association Between Dietary Inflammatory Index and Mental Health: A Systematic Review and Dose-Response Meta-Analysis.

Objective: We aimed to systematically evaluate the association between Dietary Inflammatory Index (DII) and mental health. Methods: We searched PubMed, Embase, and Web of Science from their inception to December 31, 2020. Categorical meta-analysis and dose-response meta-analysis were performed to evaluate the association between DII and mental health. Results: A total of 16 studies were included in this meta-analysis. Compared with the lowest DII category, the highest category was significantly associated with a variety of mental health outcomes, with the following pooled odds ratios (ORs) and 95% confidence intervals (95% CIs): 1.28 (1.17-1.39) for symptoms of depression, 1.27 (1.08-1.49) for symptoms of anxiety, 1.85 (1.43-2.40) for distress, and 4.27 (1.27-14.35) for schizophrenia. Furthermore, there was a linear dose-response relationship between DII and symptoms of depression in that a 1-unit increment in DII was associated with an increased risk of 6% for symptoms of depression (OR: 1.06, 95% CI: 1.03-1.19). Conclusion: The present study indicates that more pro-inflammatory diet, as estimated by the higher DII score, is associated with symptoms of mental disorder. It may be of clinical and public health significance regarding the development of novel nutritional psychiatry approaches to promote good mental health.

Network pharmacology and molecular docking reveal the mechanism of Scopoletin against non-small cell lung cancer.

AIMS: Scopoletin is a natural anticarcinogenic and antiviral coumarin component. Many studies have proved its anti-cancer effect, and after the preliminary screening of this study, Scopoletin had the best inhibitory effect on Non-small cell lung cancer (NSCLC). But its mechanism for treating NSCLC is still unclear. Therefore, network pharmacology and molecular docking technology were used to explore the potential anti-NSCLC targets and pathways of Scopoletin. The results were verified in vitro. MAIN METHODS: First, Scopoletin was isolated from Fennel and screened to conduct cell proliferation assay on Human lung cancer cell line A549, Human colon cancer cell line HCT-116 and Human hepatoma cell line HepG2 respectively, through the MTT test. Then, the key targets and related pathways were screened through Protein-protein Interaction (PPI) network and "component-target-pathway" (C-TP) network constructed by network pharmacology. And the key targets were selected to dock with Scopoletin via molecular docking. A549 and Human normal lung epithelial cell BEAS-2B were used to verify the results, finally. KEY FINDINGS: Through MTT, A549 was chosen as the test cancer cell. From network pharmacology, 16 targets, 27 signaling pathways and 16 GO items were obtained (P < 0.05). The results of PPI network and molecular docking showed that EGFR, BRAF and AKT1 were the key targets of Scopoletin against NSCLC, which were consistent with the western-blot results. SIGNIFICANCE: Through network pharmacology, molecular docking and experiments in vitro, Scopoletin was verified to against NSCLC through RAS-RAF-MEK-ERK pathway and PI3K/AKT pathway.