Lactylation: The emerging frontier in post-translational modification.

Lactate, a metabolic byproduct, has gained recognition as a highly influential signaling molecule. Lactylation, an emerging form of post-translational modification derived from lactate, plays a crucial role in numerous cellular processes such as inflammation, embryonic development, tumor proliferation, and metabolism. However, the precise molecular mechanisms through which lactylation governs these biological functions in both physiological and pathological contexts remain elusive. Hence, it is imperative to provide a comprehensive overview of lactylation in order to elucidate its significance in biological processes and establish a foundation for forthcoming investigations. This review aims to succinctly outline the process of lactylation modification and the characterization of protein lactylation across diverse organisms. Additionally, A summary of the regulatory mechanisms of lactylation in cellular processes and specific diseases is presented. Finally, this review concludes by delineating existing research gaps in lactylation and proposing primary directions for future investigations.

Construction of Frustrated Lewis Pairs in Poly(heptazine imide) Nanosheets via Hydrogen Bonds for Boosting CO2 Photoreduction.

The creation of frustrated Lewis pairs on catalyst surface is an effective strategy for tuning CO2 activation. The critical step in the formation of frustrated Lewis pairs is the spatial effect of proximal Lewis acid-Lewis base pairs. Here, we demonstrate a facile surface functionalization methodology that enables hydrogen bonding between N and H atoms to mediate the construction of frustrated Lewis pairs in poly(heptazine imide), thereby increasing the propensity to activate CO2 molecules. Experimental and theoretical results show that the construction of active hydrogen bonding regions can facilitate the bending of CO2 molecules. Furthermore, the delocalization of electron clouds induced by the hydrogen bonding-mediated frustrated Lewis pairs can promote the heterolytic cleavage and photocatalytic conversion of CO2. This work highlights the potential of utilizing hydrogen bonding-mediated strategy in heterogeneously photocatalytic activation of CO2 over polymer materials.

Inhalation of ferrate-disinfected Escherichia coli caused lung injury via endotoxin-induced oxidative stress and inflammation response.

Ferrate (Fe(VI)) is an environmentally friendly disinfectant that is widely used to eradicate microbes in reclaimed water. However, the potential health risks associated with inhalation of Fe(VI)-treated bacteria-laden reclaimed water remains uncertain. We aimed to explore the inhalation hazards and potential mechanisms of K2FeO4-treated Escherichia coli (E. coli, ATCC 25922). Our findings indicated that Fe(VI) disinfection induced a dose- and time-dependent E. coli inactivation, accompanied by a rapid release of the bacterial endotoxin, lipopolysaccharide (LPS). Scanning electron microscopy (SEM) observations indicate that Fe(VI)-induced endotoxin production consists of at least two stages: initial binding of endotoxin to bacteria and subsequent dissociation to release free endotoxin. Furthermore, Fe(VI) disinfection was not able to effectively eliminate pure or E. coli-derived endotoxins. The E. coli strain used in this study lacks lung infection capability, thus the inhalation of bacteria alone failed to induce severe lung injury. However, mice inhaled exposure to Fe(VI)-treated E. coli showed severe impairment of lung structure and function. Moreover, we observed an accumulation of neutrophil/macrophage recruitment, cell apoptosis, and ROS generation in the lung tissue of mice subjected to Fe(VI)-treated E. coli. RNA sequencing (RNA-seq) and PCR results revealed that genes involved with endotoxin stimuli, cell apoptosis, antioxidant defence, inflammation response, chemokines and their receptors were upregulated in response to Fe(VI)-treated E. coli. In conclusion, Fe(VI) is ineffective in eliminating endotoxins and can trigger secondary hazards owing to endotoxin release from inactivated bacteria. Aerosol exposure to Fe(VI)-treated E. coli causes considerable damage to lung tissue by inducing oxidative stress and inflammatory responses.

Aqueous degradation of tioxazafen: Kinetics, products, pathways, and toxicity.

Tioxazafen (TXF) is the first 1,2,4-oxadiazole nematicide. In the present study, the aqueous degradation of TXF was investigated in terms of hydrolysis and photolysis. Under the irradiation of simulated sunlight, TXF degraded very fast in ultrapure water and buffers with half-lives (t1/2s) <8.3 min. A sole photoproduct (PP) PP228a was isolated, and identified by spectroscopic means (UV, IR, HRMS, and 1H NMR) to be the thiophen-3-yl isomer converted from its thiophen-2-yl parent. Comparing with TXF, PP228a had quite extended t1/2s ranging from 6.9 to 7.9 d. The photolysis kinetics of TXF and PP228a showed no pH-dependence, and varied for each individual compound as affected by nitrate, fulvic acid, and humic acid. Besides, both compounds were hydrolytically stable. 6 PPs of PP228a were identified, with two of them being its isomers. The mechanisms involved in the process included the biradical photosensitization, photoinduced electron transfer, and ring contraction-ring expansion reactions. The 48 h-EC50 to Daphnia magna was 0.808 mg/L for PP228a comparing to >1.12 mg/L for TXF, while the results of Vibrio fischeri assays indicated that one or more PPs of PP228a might have higher toxicity.

Evaluating the added value of synthetic magnetic resonance imaging in predicting sentinel lymph node status in breast cancer.

Background: The noninvasive prediction of sentinel lymph node (SLN) metastasis using quantitative magnetic resonance imaging (MRI), particularly with synthetic MRI (syMRI), is an emerging field. This study aimed to explore the potential added benefits of syMRI over conventional MRI and diffusion-weighted imaging (DWI) in predicting metastases in SLNs. Methods: This retrospective study consecutively enrolled 101 patients who were diagnosed with breast cancer (BC) and underwent SLN biopsy from December 2022 to October 2023 at the Affiliated Hospital of Jiangnan University. These patients underwent preoperative MRI including conventional MRI, DWI, and syMRI and were categorized into two groups according to the postoperative pathological results: those with and without metastatic SLNs. MRI morphological features, DWI, and syMRI-derived quantitative parameters of breast tumors were statistically compared between these two groups. Binary logistic regression was used to separately develop predictive models for determining the presence of SLN involvement, with variables that exhibited significant differences being incorporated. The performance of each model was evaluated through receiver operating characteristic (ROC) curve analysis, including the area under the curve (AUC), sensitivity, and specificity. Results: Compared to the group of 54 patients with BC but no metastatic SLNs, the group of 47 patients with BC and metastatic SLNs had a significantly larger maximum axis diameter [metastatic SLNs: median 2.40 cm, interquartile range (IQR) 1.50-3.00 cm; no metastatic SLNs: median 1.80 cm, IQR 1.37-2.50 cm; P=0.03], a higher proton density (PD) (78.44±11.92 vs. 69.20±10.63 pu; P<0.001), and a lower apparent diffusion coefficient (ADC) (metastatic SLNs: median 0.91×10-3 mm2/s, IQR 0.79-1.01 mm2/s; no metastatic SLNs: median 1.02×10-3 mm2/s, IQR 0.92-1.12 mm2/s; P=0.001). Moreover, the prediction model with maximum axis diameter and ADC yielded an AUC of 0.71 [95% confidence interval (CI): 0.618-0.802], with a sensitivity of 78.72% and a specificity of 51.85%; After addition of syMRI-derived PD to the prediction model, the AUC increased significantly to 0.86 (AUC: 0.86 vs. 0.71; 95% CI: 0.778-0.922; P=0.002), with a sensitivity of 80.85% and a specificity of 81.50%. Conclusions: Combined with conventional MRI and DWI, syMRI can offer additional value in enhancing the predictive performance of determining SLN status before surgery in patients with BC.

Novel Coumarins Derivatives for A. baumannii Lung Infection Developed by High-Throughput Screening and Reinforcement Learning.

With the increasing resistance of Acinetobacter baumannii (A. baumannii) to antibiotics, researchers have turned their attention to the development of new antimicrobial agents. Among them, coumarin-based heterocycles have attracted much attention due to their unique biological activities, especially in the field of antibacterial infection. In this study, a series of coumarin derivatives were synthesized and screened for their bactericidal activities (Ren et al. 2018; Salehian et al. 2021). The inhibitory activities of these compounds on bacterial strains were evaluated, and the related mechanism of the new compounds was explored. Firstly, the MIC values and bacterial growth curves were measured after compound treatment to evaluate the antibacterial activity in vitro. Then, the in vivo antibacterial activities of the new compounds were assessed on A. baumannii-infected mice by determining the mice survival rates, counting bacterial CFU numbers, measuring inflammatory cytokine levels, and histopathology analysis. In addition, the ROS levels in the bacterial cells were measured with DCFH-DA detection kit. Furthermore, the potential target and detailed mechanism of the new compounds during infection disease therapy were predicted and evidenced with molecular docking. After that, ADMET characteristic prediction was completed, and novel, synthesizable, drug-effective molecules were optimized with reinforcement learning study based on the probed compound as a training template. The interaction between the selected structures and target proteins was further evidenced with molecular docking. This series of innovative studies provides important theoretical and experimental data for the development of new anti-A. baumannii infection drugs.

Granzyme B Promotes Proliferation, Migration and EMT Process in Gastric Cancer.

Granzyme B (GZMB), a critical member of the Gr gene family, is known to play an essential role in diverse physiological and pathological processes such as inflammation, acute and chronic inflammatory diseases, and cancer progression. In this study, we delve deeper into the role of GZMB within the context of gastric cancer (GC) to examine its expression patterns and functional implications. To accomplish this, we applied a combination of quantitative real-time polymerase chain reaction, western blotting, and immunohistochemistry techniques. These methodologies allowed us to accurately gauge GZMB expression levels in GC tissues and investigate their correlation with various clinical-pathological variables. Our secondary focus was to discern the regulatory influence of GZMB on GC cell biology. We used an array of assays including cell counting kit-8 (CCK-8), colony formation, 5-ethynyl-2'-deoxyuridine, and migration assays. The effect of GZMB on gastric cancer progression was further validated through a subcutaneous xenograft mouse model. Our findings underscored that GZMB mRNA and protein levels were upregulated in GC tissues, a feature that showed a significant correlation with GC staging. We also discovered that a decrease in GZMB expression via knockdown experiments suppressed the proliferation and migration capabilities of GC cells. This effect was manifested through diminished expression levels of epithelial-mesenchymal transition (EMT) markers. In stark contrast, the overexpression of GZMB through plasmid transfection appeared to enhance the proliferation and migration abilities of GC cells. This was coupled with an upregulation in EMT expression. Our study concludes by emphasizing that GZMB promotes the growth, migration, and EMT processes in gastric cancer. In vitro, cell-based experiments and in vivo xenograft mouse models confirm this. Our findings provide a more comprehensive understanding of GZMB's role in gastric cancer pathogenesis, potentially opening doors for novel therapeutic strategies targeting this molecular pathway.

B/P/N flame retardant based on diboraspiro rings groups for improving the flame retardancy, char formation properties and thermal stability of cotton fabrics.

Developing flame retardant cotton fabrics (CF) is crucial for minimizing the harm caused by fires to people. To improve the flame retardancy of CF, this paper has synthesized a novel flame retardant called diboraspiro tetra phosphonate ammonium salt (N-PDBDN). The structure of N-PDBDN has been analyzed using FT-IR and NMR. Treating CF with N-PDBDN can increase the limiting oxygen index (LOI) to 36.2 % with a weight gain of 10.1 %. Moreover, even after undergoing 50 laundering cycles (LCs), the LOI remains at 27.1 %, indicating good flame retardancy and durability. Scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) show the presence of P and N elements on N-PDBDN treated CF, suggesting successful bonding between N-PDBDN and cellulose. Thermogravimetric analysis (TGA) results demonstrate that the addition of N-PDBDN significantly enhances the thermal stability and carbon formation ability of CF. Furthermore, cone calorimetry tests reveal reduced heat release rates (HRR), prolonged time to ignition (TTI), and 38 % lower total heat release (THR) in CF treated with N-PDBDN compared with pure cotton. Finally, a potential flame retardant mechanism involving N-PDBDN is proposed. These findings indicate that incorporating an ammonium phosphate group into CF can effectively improve the flame retardancy and durability.

A Broadened Class of Donor-Acceptor Stacked Macrometallacyclic Adducts of Different Coinage Metals.

A yet-outstanding supramolecular chemistry challenge is isolation of novel varieties of stacked complexes with finely-tuned donor-acceptor bonding and optoelectronic properties, as herein reported for binary adducts comprising two different cyclic trinuclear complexes (CTC@CTC'). Most previous attempts focused only on 1-2 factors among metal/ligand/substituent combinations, resulting in heterobimetallic complexes. Instead, here we show that, when all 3 factors are carefully considered, a broadened variety of CTC@CTC' stacked pairs with intuitively-enhanced intertrimer coordinate-covalent bonding strength and ligand-ligand/metal-ligand dispersion are attained (dM-M' 2.868(2) Å; ΔE>50 kcal/mol, an order of magnitude higher than aurophilic/metallophilic interactions). Significantly, CTC@CTC' pairs remain intact/strongly-bound even in solution (Keq 4.67×105 L/mol via NMR/UV-vis titrations), and the gas phase (mass spectrometry revealing molecular peaks for the entire CTC@CTC' units in sublimed samples), rather than simple co-crystal formation. Photo-/electro-luminescence studies unravel metal-centered phosphorescence useful for novel all metal-organic light-emitting diodes (MOLEDs) optoelectronic device concepts. This work manifests systematic design of supramolecular bonding and multi-faceted spectral properties of pure metal-organic macrometallacyclic donor/acceptor (inorganic/inorganic) stacks with remarkably-rich optoelectronic properties akin to well-established organic/organic and organic/inorganic analogues.

Linkage-Mediated Electronic Structure Modulation in Multicomponent Covalent Organic Frameworks for Dramatically Promoted Photocatalytic Hydrogen Evolution.

Linkage chemistry is an essential aspect to covalent organic framework (COF) applications; it is highly desirable to precisely modulate electronic structure mediated directly by linkage for efficient COF-based photocatalytic hydrogen evolution, which however, remains substantially challenging. Herein, as a proof of concept, a collection of robust multicomponent pyrene-based COFs with abundant donor-acceptor (D-A) interactions has been judiciously designed and synthesized through molecularly engineering linkage for photogeneration of hydrogen. Controlled locking and conversion of linkage critically contribute to continuously regulating COFs' electronic structures further to optimize photocatalytic activities. Remarkably, the well-modulated optoelectronic properties turn on the average hydrogen evolution rate from zero to 15.67 mmol g-1 h-1 by the protonated quinoline-linked COF decorated with the trifluoromethyl group (TT-PQCOF-CF3). Using diversified spectroscopy and theoretical calculations, we show that multiple modifications toward linkage synergistically lead to the redistribution of charge on COFs with extended π-conjugation and reinforced D-A effect, making TT-PQCOF-CF3 a promising material with significantly boosted carrier separation and migration. This study provides important guidance for the design of high-performance COF photocatalysts based on the strategy of linkage-mediated electronic structure modulation in COFs.

Preparation and application of halogen-free and efficient Si/P/N-containing flame retardants on cotton fabrics.

Cotton fabric is extensively utilized due to its numerous applications, but the flammability associated with cotton fabric poses potential security risks to individuals. A halogen-free efficient flame retardant named poly [(tetramethylcyclosiloxyl spirocyclic pentaerythritol)-piperazin phosphate] (PCPNTSi) was developed to consolidate the fire retardance of cotton fabrics. After PCPNTSi treatment, the limiting oxygen index (LOI) of cotton fabric with 30 % weight gain (CP3) was raised to 32.8 %. In the vertical flammability test (VFT), CP3 has self-extinguished performance with a char length of 8.7 cm. The heat release rate (HRR) of cotton fabric with 20 % weight gain (CP2) is 78.8 % lower than that of pure cotton fabric (CP0). In addition, the total smoke release (TSP) of CP2 is 41.7 % lower than that of CP0, indicating PCPNTSi gives cotton fabric a good capability to inhibit smoke release. Finally, the possible flame retardant mechanism was discussed by the data of scanning electron microscope (SEM), energy dispersive spectrometer (EDS), X-ray photoelectron spectroscopy (XPS), Fourier Transform infrared spectroscopy (FT-IR) and thermogravimetric infrared spectroscopy (TG-IR). The results show that PCPNTSi is an intumescent flame retardant acting in both gas phase and solid phase.

Selective Hydrogenation of Azobenzene to Hydrazobenzene via Proton-Coupled Electron Transfer from a Polyoxotungstate Cluster.

In this report, we describe proton-coupled electron transfer (PCET) reactivity at the surface of the Keggin-type polyoxotungstate cluster [nBu4N]3[PWVI12O40] (PW12) in acetonitrile. Bond dissociation free energies (BDFEs) of the O-H groups generated upon reduction of PW12 in the presence of acid are determined through the construction of a potential-pKa diagram. The surface O-H bonds are found to be weak (BDFE(O-H)avg < 48 kcal mol-1), comparable to the BDFE of H2. This is consistent with the observed formation of H2 upon addition of a suitably strong organic acid, H2NPh2+ (pKa MeCN = 5.98), to the reduced form of the cluster. The one-electron reduced form of PW12 is isolated and used in conjunction with acid to realize the stoichiometric semihydrogenation of azobenzene via PCET from the surface of the reduced cluster.

Nanostructured SnO2 Thin Films Based on a Convenient Chemical Deposition for Sensitive Detection of Ethanol.

A specific matrix sensor that can operate at low temperatures and has a high sensing response is crucial for monitoring flammable VOC gases. In this study, a nanostructured SnO2 thin film was successfully produced using a suitable chemical deposition method, and its sensing properties were comprehensively analyzed. The SEM images revealed that the thin film of the nanostructured SnO2 is made up of two different sizes of broccoli-like structure nanoparticles. The sensor, which is based on this unique micronano structure, demonstrated a high sensing response (44), low operating temperature (200 °C), and fast response time (6s). Additionally, the nanostructured sensor exhibited excellent resistance to humidity interference and long-term stability. Moreover, DFT is employed to evaluate the electronic properties and to systematically explain the gas sensing mechanism of the nanostructured sensor based on the SnO2 thin film.

Impact of Surface Ligand Identity and Density on the Thermodynamics of H Atom Uptake at Polyoxovanadate-Alkoxide Surfaces.

An understanding of how molecular structure influences the thermodynamics of H atom transfer is critical to designing efficient catalysts for reductive chemistries. Herein, we report experimental and theoretical investigations summarizing structure-function relationships of polyoxovanadate-alkoxides that influence bond dissociation free energies of hydroxide ligands located at the surface of the cluster. We evaluate the thermochemical descriptors of O-H bond strength for a series of clusters, namely [V6O13-x(OH)x(TRIOLR)2]-2 (x = 2, 4, 6; R = NO2, Me) and [V6O11-x(OMe)2(OH)x(TRIOLNO2)2]-2, via computational analysis and open circuit potential measurements. Our findings reveal that modifications to the TRIOL ligand (e.g., changing from the previously reported electron withdrawing nitro-backed ligand to the electron-donating methyl variant) have limited influence on the strength of surface O-H bonds as a result of near complete thermodynamic compensation in these systems (i.e., correlated changes in redox potential and cluster basicity). In contrast, changes in surface density of alkoxide ligands via direct alkoxylation of the polyoxovanadate-alkoxide surface result in measurable increases in bond dissociation free energies of surface O-H bonds for the mixed-valent derivatives. Our findings indicate that the extent of (de)localization of electron density across the cluster core has an impact on the bond dissociation free energies of surface O-H bonds across all oxidation states of the assembly.

Ultimately Adaptive Fluid Interfacial Phospholipid Membranes Unveiled Unanticipated High Cellular Mechanical Work.

Living cells actively interact biochemically and mechanically with the surrounding extracellular matrices (ECMs) and undergo dramatic morphological and dimensional transitions, concomitantly remodeling ECMs. However, there is no suitable method to quantitatively discuss the contribution of mechanical interactions in such mutually adaptive processes. Herein, a highly deformable "living" cellular scaffold is developed to evaluate overall mechanical energy transfer between cell and ECMs. It is based on the water-perfluorocarbon interface decorated with phospholipids bearing a cell-adhesive ligand and fluorescent tag. The bioinert nature of the phospholipid membranes prevents the formation of solid-like protein nanofilms at the fluid interface, enabling to visualize and quantify cellular mechanical work against the ultimately adaptive model ECM. A new cellular wetting regime is identified, wherein interface deformation proceeds to cell flattening, followed by its eventual restoration. The cellular mechanical work during this adaptive wetting process is one order of magnitude higher than those reported with conventional elastic platforms. The behavior of viscous liquid drops at the air-water interface can simulate cellular adaptive wetting, suggesting that overall viscoelasticity of the cell body predominates the emergent wetting regime and regulates mechanical output. Cellular-force-driven high-energy states on the adaptive platform can be useful for cell fate manipulation.

Kj-mhpC Enzyme in Klebsiella jilinsis 2N3 Is Involved in the Degradation of Chlorimuron-Ethyl via De-Esterification.

Microbial degradation is a highly efficient and reliable approach for mitigating the contamination of sulfonylurea herbicides, such as chlorimuron-ethyl, in soil and water. In this study, we aimed to assess whether Kj-mhpC plays a pivotal role in the degradation of chlorimuron-ethyl. Kj-mhpC enzyme purified via prokaryotic expression exhibited the highest catalytic activity for chlorimuron-ethyl at 35 °C and pH 7. Bioinformatic analysis and three-dimensional homologous modeling of Kj-mhpC were conducted. Additionally, the presence of Mg+ and Cu2+ ions partially inhibited but Pb2+ ions completely inhibited the enzymatic activity of Kj-mhpC. LC/MS revealed that Kj-mhpC hydrolyzes the ester bond of chlorimuron-ethyl, resulting in the formation of 2-(4-chloro-6-methoxypyrimidine-2-amidoformamidesulfonyl) benzoic acid. Furthermore, the point mutation of serine at position 67 (Ser67) confirmed that it is the key amino acid at the active site for degrading chlorimuron-ethyl. This study enhanced the understanding of how chlorimuron-ethyl is degraded by microorganisms and provided a reference for bioremediation of the environment polluted with chlorimuron-ethyl.

Preparation and thermostability of a Si/P/N synergistic flame retardant containing triazine ring structure for cotton fabrics.

A new synergistic flame retardant named Bisiminopropyl trimethoxysilane-1,3,5-triazine-O-bicyclic pentaerythritol phosphate (BTPODE) was synthesized, which is a type of Si/P/N flame retardant. This was accomplished by grafting aminopropyl trimethoxysilane and bicyclic pentaerythritol phosphate onto a triazine ring structure, serving as an intermediate. The structure of BTPODE was determined using nuclear magnetic resonance (1H NMR, 13C NMR, and 31P NMR) and Fourier transform infrared spectroscopy (FT-IR). SEM was used to detect the surface morphology of cotton fabrics, which suggested that BTPODE had been resoundingly stick to cotton fabrics. The flame retardant properties of cotton fabrics were evaluated by measuring the limiting oxygen index (LOI) and conducting vertical flammability experiments. Cotton fabrics with a weight gain of 20.73 % achieved an LOI value of 32.5 %. Thermogravimetric (TG) experiments demonstrated the samples' good thermostability. Furthermore, under nitrogen conditions, the char residue of cotton fabric with a weight gain of 20.73 % was 36.85 %. The cone calorimetry test (CONE) showed a significant reduction in the TSP value, indicating a certain level of smoke suppression performance. Finally, based on the obtained experimental results, the fire-retardant mechanism principle of the flame retardant was deduced.

Fluctuation of lysosomal protein degradation in neural stem cells of the postnatal mouse brain.

Lysosomes are intracellular organelles responsible for degrading diverse macromolecules delivered from several pathways, including the endo-lysosomal and autophagic pathways. Recent reports have suggested that lysosomes are essential for regulating neural stem cells in developing, adult and aged brains. However, the activity of these lysosomes has yet to be monitored in these brain tissues. Here, we report the development of a new probe to measure lysosomal protein degradation in brain tissue by immunostaining. Our results indicate that lysosomal protein degradation fluctuates in neural stem cells of the hippocampal dentate gyrus, depending on age and brain disorders. Neural stem cells increase their lysosomal activity during hippocampal development in the dentate gyrus, but aging and aging-related disease reduce lysosomal activity. In addition, physical exercise increases lysosomal activity in neural stem cells and astrocytes in the dentate gyrus. We therefore propose that three different stages of lysosomal activity exist: the state of increase during development, the stable state during adulthood and the state of reduction due to damage caused by either age or disease.

Exploration of the biodegradation pathway and enhanced removal of imazethapyr from soil by immobilized Bacillus marcorestinctum YN1.

Excessive or inappropriate applications of imazethapyr cause severe ecological deteriorations and health risks in human. A novel bacterial strain, i.e., Bacillus marcorestinctum YN1, was isolated to efficiently degrade imazethapyr, with the degradation pathways and intermediates predicted. Protein mass spectrometry analysis identified enzymes in strain YN1 potentially involved in imazethapyr biodegradation, including methylenetetrahydrofolate dehydrogenase, carbon-nitrogen family hydrolase, heme degrading monooxygenase, and cytochrome P450. The strain YN1 was further immobilized with biochar (BC600) prepared from mushroom waste (i.e., spent mushroom substrate) by pyrolysis at 600 °C to evaluate its degrading characteristics of imazethapyr. Scanning electron microscope observation showed that strain YN1 was adsorbed in the rich pore structure of BC600 and the adsorption efficiency reached the maximum level of 88.02% in 6 h. Both energy dispersive X-ray and Fourier transform infrared spectroscopy analyses showed that BC600 contained many elements and functional groups. The results of liquid chromatography showed that biochar-immobilized strain YN1 (IBC-YN1) improved the degradation rate of imazethapyr from 79.2% to 87.4%. The degradation rate of imazethapyr by IBC-YN1 could still reach 81.0% in the third recycle, while the bacterial survival rate was 67.73% after 180 d storage at 4 °C. The treatment of IBC-YN1 significantly shortened the half-life of imazethapyr in non-sterilized soil from 35.51 to 11.36 d, and the vegetative growth of imazethapyr sensitive crop plant (i.e., Cucumis sativus L.) was significantly increased in soil remediated, showing that the inhibition rate of root length and fresh weight were decreased by 12.45% and 38.49% respectively. This study exhanced our understanding of microbial catabolism of imazethapyr, and provided a potential in situ remediation strategy for improving the soil environment polluted by imazethapyr.

Achieving Long-Lived Charge Separated State through Ultrafast Interfacial Hole Transfer in Redox Sites-Isolated CdS Nanorods for Enhanced Photocatalysis.

As opposed to natural photosynthesis, a significant challenge in a semiconductor-based photocatalyst is the limited hole extraction efficiency, which adversely affects solar-to-fuel efficiency. Recent studies have demonstrated that photocatalysts featuring spatially isolated dual catalytic oxidation/reduction sites can yield enhanced hole extraction efficiencies. However, the decay dynamics of excited states in such photocatalysts have not been explored. Here a ternary barbell-shaped CdS/MoS2/Cu2S heterostructure is prepared, comprising CdS nanorods (NRs) interfaced with MoS2 nanosheets at both ends and Cu2S nanoparticles on the sidewall. By using transient absorption (TA) spectra, highly efficient charge separation within the CdS/MoS2/Cu2S heterostructure are identified. This is achieved through directed electron transfer to the MoS2 tips at a rate constant of >8.3 × 109 s-1 and rapid hole transfer to the Cu2S nanoparticles on the sidewall at a rate of >6.1 × 1010 s-1, leading to an exceptional overall charge transfer constant of 2.3 × 1011 s-1 in CdS/MoS2/Cu2S. The enhanced hole transfer efficiency results in a remarkably prolonged charge-separated state, facilitating efficient electron accumulation within the MoS2 tips. Consequently, the ternary CdS/MoS2/Cu2S heterostructure demonstrates a 22-fold enhancement in visible-light-driven H2 generation compare to pure CdS nanorods. This work highlights the significance of efficient hole extraction in enhancing the solar-to-H2 performance of semiconductor-based heterostructure.