Modification of Polymeric Carbon Nitride with Au–CeO2 Hybrids to Improve Photocatalytic Activity for Hydrogen Evolution

The construction of a multi-component heterostructure for promoting the exciton splitting and charge separation of conjugated polymer semiconductors has attracted increasing attention in view of improving their photocatalytic activity. Here, we integrated Au nanoparticles (NPs) decorated CeO₂ (Au–CeO₂) with polymeric carbon nitride (PCN) via a modified thermal polymerization method. The combination of the interfacial interaction between PCN and CeO₂ via N-O or C-O bonds, with the interior electronic transmission channel built by the decoration of Au NPs at the interface between CeO₂ and PCN, endows CeAu–CN with excellent efficiency in the transfer and separation of photo-induced carriers, leading to the enhancement of photochemical activity. The amount-optimized CeAu–CN nanocomposites are capable of producing ca. 80 μmol· H₂ per hour under visible light irradiation, which is higher than that of pristine CN, Ce–CN and physical mixed CeAu and PCN systems. In addition, the photocatalytic activity of CeAu–CN remains unchanged for four runs in 4 h. The present work not only provides a sample and feasible strategy to synthesize highly efficient organic polymer composites containing metal-assisted heterojunction photocatalysts, but also opens up a new avenue for the rational design and synthesis of potentially efficient PCN-based materials for efficient hydrogen evolution.     

Recent Progress in Biosensors for Detection of Tumor Biomarkers

Cancer is a leading cause of death worldwide, with an increasing mortality rate over the past years. The early detection of cancer contributes to early diagnosis and subsequent treatment. How to detect early cancer has become one of the hot research directions of cancer. Tumor biomarkers, biochemical parameters for reflecting cancer occurrence and progression have caused much attention in cancer early detection. Due to high sensitivity, convenience and low cost, biosensors have been largely developed to detect tumor biomarkers. This review describes the application of various biosensors in detecting tumor markers. Firstly, several typical tumor makers, such as neuron-specific enolase (NSE), carcinoembryonic antigen (CEA), prostate-specific antigen (PSA), squamous cell carcinoma antigen (SCCA), carbohydrate, antigen19-9 (CA19-9) and tumor suppressor p53 (TP53), which may be helpful for early cancer detection in the clinic, are briefly described. Then, various biosensors, mainly focusing on electrochemical biosensors, optical biosensors, photoelectrochemical biosensors, piezoelectric biosensors and aptamer sensors, are discussed. Specifically, the operation principles of biosensors, nanomaterials used in biosensors and the application of biosensors in tumor marker detection have been comprehensively reviewed and provided. Lastly, the challenges and prospects for developing effective biosensors for early cancer diagnosis are discussed.     

One-Step Calcination to Gain Exfoliated g-C3N4/MoO2 Composites for High-Performance Photocatalytic Hydrogen Evolution

The difficulty of exposing active sites and easy recombination of photogenerated carriers have always been two critical problems restricting the photocatalytic activity of g-C₃N₄. Herein, a simple (NH₄)₂MoO₄-induced one-step calcination method was successfully introduced to transform bulk g-C₃N₄ into g-C₃N₄/MoO₂ composites with a large specific surface area. During the calcination, with the assistance of NH₃ and water vapor produced by ammonium molybdate, the pyrolytical oxidation and depolymerization of a g-C₃N₄ interlayer were accelerated, finally realizing the exfoliation of the g-C₃N₄. Furthermore, another pyrolytical product of ammonium molybdate was transformed into MoO₂ under an NH₃ atmosphere, which was in situ loaded on the surface of a g-C₃N₄ nanosheet. Additionally, the results of photocatalytic hydrogen evolution under visible light show that the optimal g-C₃N₄/MoO₂ composite has a high specific surface area and much improved performance, which is 4.1 times that of pure bulk g-C₃N₄. Such performance improvement can be attributed to the full exposure of active sites and the formation of abundant heterojunctions. However, with an increasing feed amount of ammonium molybdate, the oxidation degree of g-C₃N₄ was enhanced, which would widen the band gap of g-C₃N₄, leading to a weaker response ability to visible light. The present strategy will provide a new idea for the simple realization of exfoliation and constructing a heterojunction for g-C₃N₄ simultaneously.     

Protective Effect of Flavonoids against Methylglyoxal-Induced Oxidative Stress in PC-12 Neuroblastoma Cells and Its Structure–Activity Relationships

Methylglyoxal-induced oxidative stress and cytotoxicity are the main factors causing neuronal death-related, diabetically induced memory impairment. Antioxidant and anti-apoptotic therapy are potential intervention strategies. In this study, 25 flavonoids with different substructures were assayed for protecting PC-12 cells from methylglyoxal-induced damage. A structure–activity relationship (SAR) analysis indicated that the absence of the double bond at C-2 and C-3, substitutions of the gallate group at the 3 position, the pyrogallol group at the B-ring, and the R configuration of the 3 position enhanced the protection of flavan-3-ols, and a hydroxyl substitution at the 4′ and meta-positions were important for the protection of flavonol. These SARs were further confirmed by molecular docking using the active site of the Keap1–Nrf2 complex as the receptor. The mechanistic study demonstrated that EGCG with the lowest EC₅₀ protected the PC-12 cells from methylglyoxal-induced damage by reducing oxidative stress via the Nrf2/Keap1/HO-1 and Bcl-2/Bax signaling pathways. These results suggested that flavan-3-ols might be a potential dietary supplement for protection against diabetic encephalopathy.     

Antitumor Activity and Mechanism of Action of the Antimicrobial Peptide AMP-17 on Human Leukemia K562 Cells

Cancer is one of the most common malignant diseases in the world. Hence, there is an urgent need to search for novel drugs with antitumor activity against cancer cells. AMP-17, a natural antimicrobial peptide derived from Musca domestica, has antimicrobial activity against Gram-positive bacteria, Gram-negative bacteria, and fungi. However, its antitumor activity and potential mechanism of action in cancer cells remain unclear. In this study, we focused on evaluating the in vitro antitumor activity and mechanism of AMP-17 on leukemic K562 cells. The results showed that AMP-17 exhibited anti-proliferative activity on K562 cells with an IC₅₀ value of 58.91 ± 3.57 μg/mL. The membrane integrity of K562 was disrupted and membrane permeability was increased after AMP-17 action. Further observation using SEM and TEM images showed that the cell structure of AMP-17-treated cells was disrupted, with depressions and pore-like breaks on the cell surface, and vacuolated vesicles in the cytoplasm. Furthermore, further mechanistic studies indicated that AMP-17 induced excessive production of reactive oxygen species and calcium ions release in K562 cells, which led to disturbance of mitochondrial membrane potential and blocked ATP synthesis, followed by activation of Caspase-3 to induce apoptosis. In conclusion, these results suggest that the antitumor activity of AMP-17 may be achieved by disrupting cell structure and inducing apoptosis. Therefore, AMP-17 is expected to be a novel potential agent candidate for leukemia treatment.     

Preparation of Nitrogen and Sulfur Co-Doped Fluorescent Carbon Dots from Cellulose Nanocrystals as a Sensor for the Detection of Rutin

The poor water solubility, large particle size, and low accessibility of cellulose, the most abundant bioresource, have restricted its generalization to carbon dots (CDs). Herein, nitrogen and sulfur co-doped fluorescent carbon dots (N, S-CDs) were hydrothermally synthesized using cellulose nanocrystals (CNC) as a carbon precursor, exhibiting a small particle size and excellent aqueous dispersion. Thiourea was selected as a nitrogen and sulfur dopant to introduce abundant fluorescent functional groups into N, S-CDs. The resulting N, S-CDs exhibited nanoscale size (6.2 nm), abundant functional groups, bright blue fluorescence, high quantum yield (QY = 27.4%), and high overall yield (16.2%). The excellent optical properties of N, S-CDs endowed it to potentially display a highly sensitive fluorescence “turn off” response to rutin. The fluorescence response for rutin allowed a wide linear range of 0–40 mg·L⁻¹, with a limit of detection (LOD) of 0.02 μM, which revealed the potential of N, S-CDs as a rapid and simple sensing platform for rutin detection. In addition, the sustainable and large-scale production of the N, S-CDs in this study paves the way for the successful high-value utilization of cellulose.     

Syringaresinol Alleviates Oxaliplatin-Induced Neuropathic Pain Symptoms by Inhibiting the Inflammatory Responses of Spinal Microglia

Oxaliplatin-induced peripheral neuropathy (OIPN) is a serious side effect that impairs the quality of life of patients treated with the chemotherapeutic agent, oxaliplatin. The underlying pathophysiology of OIPN remains unclear, and there are no effective therapeutics. This study aimed to investigate the causal relationship between spinal microglial activation and OIPN and explore the analgesic effects of syringaresinol, a phytochemical from the bark of Cinnamomum cassia, on OIPN symptoms. The causality between microglial activation and OIPN was investigated by assessing cold and mechanical allodynia in mice after intrathecal injection of the serum supernatant from a BV-2 microglial cell line treated with oxaliplatin. The microglial inflammatory response was measured based on inducible nitric oxide synthase (iNOS), phosphorylated extracellular signal-regulated kinase (p-ERK), and phosphorylated nuclear factor-kappa B (p-NF-κB) expression in the spinal dorsal horn. The effects of syringaresinol were tested using behavioral and immunohistochemical assays. We found that oxaliplatin treatment activated the microglia to increase inflammatory responses, leading to the induction of pain. Syringaresinol treatment significantly ameliorated oxaliplatin-induced pain and suppressed microglial expression of inflammatory signaling molecules. Thus, we concluded that the analgesic effects of syringaresinol on OIPN were achieved via the modulation of spinal microglial inflammatory responses.     

Metabolites Identification and Mechanism Prediction of Neobavaisoflavone In Vitro and In Vivo of Rats through UHPLC-Q-Exactive Plus Orbitrap MS Integrated Network Pharmacology

Neobavaisoflavone is an important isoflavone component isolated from Psoraleae Fructus. It is used extensively worldwide because of its antibacterial, antioxidant, anti-inflammatory, anticancer, and anti-osteoporotic activities. However, there is no systematic and comprehensive research on the metabolism of neobavaisoflavone in vivo and in vitro. The study aimed to analyze the metabolic characteristics and mechanism of neobavaisoflavone for the first time. Firstly, biological samples were pretreated by the solid-phase extraction (SPE) method, methanol precipitation, and acetonitrile precipitation. Secondly, the samples were analyzed on UHPLC-Q-Exactive Plus Orbitrap MS. Thirdly, metabolites were tentatively identified based on retention time, parallel reaction monitoring strategy, diagnostic product ions, and neutral loss fragments. A total of 72 metabolites of neobavaisoflavone were tentatively identified, including 28 in plasma, 43 in urine, 18 in feces, six in the liver, and four in the liver microsome. The results suggested that neobavaisoflavone mainly underwent glucuronidation, sulfation, hydroxylation, methylation, cyclization, hydration, and their composite reactions in vivo and in vitro. In addition, nine active components with high bioavailability and 191 corresponding targets were predicted by the Swiss Drug Design database. The 1806 items of GO and 183 KEGG signaling pathways were enriched. These results showed that metabolites expanded the potential effects of neobavaisoflavone. The present study would provide the scientific basis for the further exploitation and application of neobavaisoflavone.     

Snapshots of key intermediates unveiling the growth from silver ions to Ag70 nanoclusters

Nanoclusters (NCs) are considered as initial states of condensed matter, and unveiling their formation mechanism is of great importance for directional synthesis of nanomaterials. Here, we initiate the reaction of Ag(i) ions under weak reducing conditions. The prolonged reaction period provides a unique opportunity for revealing the five stages of the growth mechanism of 20-electron superatomic Ag₇₀ NCs by a time-dependent mass technique, that is, aggregate (I) → reduction (II) → decomposition and recombination (III) → fusion (IV) → surface recombination and motif enrichment (V), which is different from the formation process applicable to the gold clusters. More importantly, the key intermediates, Ag₁₄ without free electrons (0e) in the first (stage I) and Ag₂₄ (4e) in the second (stage II), were crystallized and structurally resolved, and the later transformation rate towards Ag₇₀ was further controlled by modulating solvents for easy identification of more intermediates. In a word, we establish a reasonable path of gradual expansion in size and electrons from Ag(i) ions to medium-sized 20e Ag₇₀. This work provides new insights into the formation and evolution of silver NCs, and unveils the corresponding optical properties along with the process.

The bottom-up synthesis of “medium-sized” Ag₇₀ (20e) was controlled and tracked, and then revealed. The crystallized key intermediates of Ag₁₄ (0e) and Ag₂₄ (4e) present the growth snapshots of silver nanoclusters.