Photocatalytic Upgrading of Polylactic Acid Waste into Alanine under Mild Conditions.

Polylactic acid (PLA) has attracted increasing interest as a sustainable plastic because it can be degraded into CO2 and H2O in nature. However, this process is sluggish, and even worse, it is a CO2-emitting and carbon resource waste process. Therefore, it is highly urgent to develop a novel strategy for recycling post-consumer PLA to achieve a circular plastic economy. Herein, we report a one-pot photoreforming route for the efficient and selective amination of PLA waste into value-added alanine using CoP/CdS catalysts under mild conditions. Results show the alanine production rate can reach up to 2.4 mmol gcat -1 h-1, with a high selectivity (>75 %) and excellent stability. Time-resolved transient absorption spectra (TAS) reveal that CoP can rapidly extract photogenerated electrons from CdS to accelerate proton reduction, favoring hole-dominated PLA oxidation to coproduce alanine. This study offers an appealing way for upcycling PLA waste and creates new opportunities for green synthesis of amino acids.

Bile acids inhibit ferroptosis sensitivity through activating farnesoid X receptor in gastric cancer cells.

BACKGROUND: Gastric cancer (GC) is associated with high mortality rates. Bile acids (BAs) reflux is a well-known risk factor for GC, but the specific mechanism remains unclear. During GC development in both humans and animals, BAs serve as signaling molecules that induce metabolic reprogramming. This confers additional cancer phenotypes, including ferroptosis sensitivity. Ferroptosis is a novel mode of cell death characterized by lipid peroxidation that contributes universally to malignant progression. However, it is not fully defined if BAs can influence GC progression by modulating ferroptosis. AIM: To reveal the mechanism of BAs regulation in ferroptosis of GC cells. METHODS: In this study, we treated GC cells with various stimuli and evaluated the effect of BAs on the sensitivity to ferroptosis. We used gain and loss of function assays to examine the impacts of farnesoid X receptor (FXR) and BTB and CNC homology 1 (BACH1) overexpression and knockdown to obtain further insights into the molecular mechanism involved. RESULTS: Our data suggested that BAs could reverse erastin-induced ferroptosis in GC cells. This effect correlated with increased glutathione (GSH) concentrations, a reduced GSH to oxidized GSH ratio, and higher GSH peroxidase 4 (GPX4) expression levels. Subsequently, we confirmed that BAs exerted these effects by activating FXR, which markedly increased the expression of GSH synthetase and GPX4. Notably, BACH1 was detected as an essential intermediate molecule in the promotion of GSH synthesis by BAs and FXR. Finally, our results suggested that FXR could significantly promote GC cell proliferation, which may be closely related to its anti-ferroptosis effect. CONCLUSION: This study revealed for the first time that BAs could inhibit ferroptosis sensitivity through the FXR-BACH1-GSH-GPX4 axis in GC cells. This work provided new insights into the mechanism associated with BA-mediated promotion of GC and may help identify potential therapeutic targets for GC patients with BAs reflux.

Highly Efficient Thermally Activated Delayed Fluorescence from Pyrazine-Fused Carbene Au(I) Emitters.

Metal-based thermally activated delayed fluorescence (TADF) is conceived to inherit the advantages of both phosphorescent metal complexes and purely organic TADF compounds for high-performance electroluminescence. Herein a panel of new TADF Au(I) emitters has been designed and synthesized by using carbazole and pyrazine-fused nitrogen-heterocyclic carbene (NHC) as the donor and acceptor ligands, respectively. Single-crystal X-ray structures show linear molecular shape and coplanar arrangement of the donor and acceptor with small dihedral angles of <6.5°. The coplanar orientation and appropriate separation of the HOMO and LUMO in this type of molecules favour the formation of charge-transfer excited state with appreciable oscillator strength. Together with a minor but essential heavy atom effect of Au ion, the complexes in doped films exhibit highly efficient (Φ∼0.9) and short-lived (<1 µs) green emissions via TADF. Computational studies on this class of emitters have been performed to decipher the key reverse intersystem crossing (RISC) pathway. In addition to a small energy splitting between the lowest singlet and triplet excited states (ΔEST ), the spin-orbit coupling (SOC) effect is found to be larger at a specific torsion angle between the donor and acceptor planes which favours the RISC process the most. This work provides an alternative molecular design to TADF Au(I) carbene emitters for OLED application.

Black Phosphorus-Based Semiconductor Heterojunctions for Photocatalytic Water Splitting.

Solar-to-hydrogen (H2 ) conversion has been regarded as a sustainable and renewable technique to address aggravated environmental pollution and global energy crisis. The most critical aspect in this technology is to develop highly efficient and stable photocatalysts, especially metal-free photocatalysts. Recently, black phosphorus (BP), as a rising star 2D nanomaterial, has captured enormous attention in photocatalytic water splitting owing to its widespread optical absorption, adjustable direct band gap, and superior carrier migration characteristics. However, the rapid charge recombination of pristine BP has seriously limited its practical application as photocatalyst. The construction of BP-based semiconductor heterojunctions has been proven to be an effective strategy for enhancing the separation of photogenerated carriers. This Minireview attempts to summarize the recent progress in BP-based semiconductor heterojunctions for photocatalytic water splitting, including type-I and type-II heterojunctions, Z-Scheme systems, and multicomponent heterojunctions. Finally, a brief summary and perspective on the challenges and future directions in this field are also provided.