Circumventing bottlenecks in H2O2 photosynthesis over carbon nitride with iodine redox chemistry and electric field effects.

Artificial photosynthesis using carbon nitride (g-C3N4) holds a great promise for sustainable and cost-effective H2O2 production, but the high carrier recombination rate impedes its efficiency. To tackle this challenge, we propose an innovative method involving multispecies iodine mediators (I-/I3-) intercalation through a pre-photo-oxidation process using potassium iodide (suspected deteriorated "KI") within the g-C3N4 framework. Moreover, we introduce an external electric field by incorporating cationic methyl viologen ions to establish an auxiliary electron transfer channel. Such a unique design drastically improves the separation of photo-generated carriers, achieving an impressive H2O2 production rate of 46.40 mmol g-1 h-1 under visible light irradiation, surpassing the most visible-light H2O2-producing systems. Combining various advanced characterization techniques elucidates the inner photocatalytic mechanism, and the application potential of this photocatalytic system is validated with various simulation scenarios. This work presents a significative strategy for preparing and applying highly efficient g-C3N4-based catalysts in photochemical H2O2 production.

Buffer-free ozone-ferrate(VI) systems for enhanced oxidation of electron-deficient contaminants: Synergistic enhancement effects, systematic toxicity assessment, and practical applications.

The combination of ozone (O3) and ferrate (Fe(VI)) oxidation technology demonstrates substantial potential for practical applications, though it has been underreported, resulting in gaps in comprehensive activity assessments and thorough exploration of its mechanisms. This study reveals that the previous use of a borate buffer solution obscured certain synergistic reactions between O3 and Fe(VI), causing a reduction of activity by ∼40 % when oxidizing the electron-deficient pollutant atrazine. Consequently, we reassessed the activity and mechanisms using a buffer-salt-free O3/Fe(VI) system. Our findings showed that the hydroxyl radical (·OH) served as the predominant active species, responsible for an impressive 95.9 % of the oxidation activity against electron-deficient pollutants. Additional experiments demonstrated that the rapid production of neglected and really important superoxide radicals (·O2-) could facilitate the decomposition of O3 to generate ·OH and accelerate the reduction of Fe(VI) to Fe(V), reactivating O3 to produce ·OH anew. Intriguingly, as the reaction progressed, the initially depleted Fe(VI) was partially regenerated, stabilizing at over 50 %, highlighting the significant potential of this combined system. Moreover, this combined system could achieve a high mineralization efficiency of 80.4 % in treating actual coking wastewater, complemented by extensive toxicity assessments using Escherichia coli, wheat seeds, and zebrafish embryos, showcasing its robust application potential. This study revisits and amends previous research on the O3/Fe(VI) system, providing new insights into its activity and synergistic mechanisms. Such a combined technology has potential for the treatment of difficult-to-degrade industrial wastewater.

Direct Electron Transfer-Driven Nontoxic Oligomeric Deposition of Sulfonamide Antibiotics onto Carbon Materials for In Situ Water Remediation.

The rising in situ chemical oxidation (ISCO) technologies based on polymerization reactions have advanced the removal of emerging contaminants in the aquatic environment. However, despite their promise, uncertainties persist regarding their effectiveness in eliminating structurally complex contaminants, such as sulfonamide antibiotics (SAs). This study elucidated that oligomerization, rather than mineralization, predominantly governs the removal of SAs in the carbon materials/periodate system. The amine groups in SAs played a crucial role in forming organic radicals and subsequent coupling reactions due to their high f- index and low bond orders. Moreover, the study highlighted the robust adhesion of oligomers to the catalyst surface, facilitated by enhanced van der Waals forces and hydrophobic interactions. Importantly, plant and animal toxicity assessments confirmed the nontoxic nature of oligomers deposited on the carbon material surface, affirming the efficacy of carbon material-based ISCO in treating contaminated surface water and groundwater. Additionally, a novel classification approach, Δlog k, was proposed to differentiate SAs based on their kinetic control steps, providing deeper insights into the quantitative structure-activity relationship (QSAR) and facilitating the selection of optimal descriptors during the oligomerization processes. Overall, these insights significantly enhance our understanding of SAs removal via oligomerization and demonstrate the superiority of C-ISCO based on polymerization in water decontamination.

Rejuvenation of peripheral immune cells attenuates Alzheimer's disease-like pathologies and behavioral deficits in a mouse model.

Immunosenescence contributes to systematic aging and plays a role in the pathogenesis of Alzheimer's disease (AD). Therefore, the objective of this study was to investigate the potential of immune rejuvenation as a therapeutic strategy for AD. To achieve this, the immune systems of aged APP/PS1 mice were rejuvenated through young bone marrow transplantation (BMT). Single-cell RNA sequencing revealed that young BMT restored the expression of aging- and AD-related genes in multiple cell types within blood immune cells. The level of circulating senescence-associated secretory phenotype proteins was decreased following young BMT. Notably, young BMT resulted in a significant reduction in cerebral Aß plaque burden, neuronal degeneration, neuroinflammation, and improvement of behavioral deficits in aged APP/PS1 mice. The ameliorated cerebral amyloidosis was associated with an enhanced Aß clearance of peripheral monocytes. In conclusion, our study provides evidence that immune system rejuvenation represents a promising therapeutic approach for AD.

NnSUS1 encodes a sucrose synthase involved in sugar accumulation in lotus seed cotyledons.

Fresh lotus seeds are gaining favor with consumers for their crunchy texture and natural sweetness. However, the intricacies of sugar accumulation in lotus seeds remain elusive, which greatly hinders the quality improvement of fresh lotus seeds. This study endeavors to elucidate this mechanism by identifying and characterizing the sucrose synthase (SUS) gene family in lotus. Comprising five distinct members, namely NnSUS1 to NnSUS5, each gene within this family features a C-terminal glycosyl transferase1 (GT1) domain. Among them, NnSUS1 is the predominately expressed gene, showing high transcript abundance in the floral organs and cotyledons. NnSUS1 was continuously up-regulated from 6 to 18 days after pollination (DAP) in lotus cotyledons. Furthermore, NnSUS1 demonstrates co-expression relationships with numerous genes involved in starch and sucrose metabolism. To investigate the function of NnSUS1, a transient overexpression system was established in lotus cotyledons, which confirmed the gene's contribution to sugar accumulation. Specifically, transient overexpression of NnSUS1 in seed cotyledons leads to a significant increase in the levels of total soluble sugar, including sucrose and fructose. These findings provide valuable theoretical insights for improving sugar content in lotus seeds through molecular breeding methods.

Double charge flips of polyamide membrane by ionic liquid-decoupled bulk and interfacial diffusion for on-demand nanofiltration.

Fine design of surface charge properties of polyamide membranes is crucial for selective ionic and molecular sieving. Traditional membranes face limitations due to their inherent negative charge and limited charge modification range. Herein, we report a facile ionic liquid-decoupled bulk/interfacial diffusion strategy to elaborate the double charge flips of polyamide membranes, enabling on-demand transformation from inherently negative to highly positive and near-neutral charges. The key to these flips lies in the meticulous utilization of ionic liquid that decouples intertwined bulk/interfacial diffusion, enhancing interfacial while inhibiting bulk diffusion. These charge-tunable polyamide membranes can be customized for impressive separation performance, for example, profound Cl-/SO42- selectivity above 470 in sulfate recovery, ultrahigh Li+/Mg2+ selectivity up to 68 in lithium extraction, and effective divalent ion removal in pharmaceutical purification, surpassing many reported polyamide nanofiltration membranes. This advancement adds a new dimension to in the design of advanced polymer membranes via interfacial polymerization.

DNA Nanospheres Assisted Spatial Confinement Signal Amplification for MicroRNA Imaging in Live Cancer Cells.

DNA assemblies are commonly used in biosensing, particularly for the detection and imaging of microRNAs (miRNAs), which are biomarkers associated with tumor progression. However, the difficulty lies in the exploration of high-sensitivity analytical techniques for miRNA due to its limited presence in living cells. In this study, we introduced a DNA nanosphere (DS) enhanced catalytic hairpin assembly (CHA) system for the detection and imaging of intracellular miR-21. The single-stranded DNA with four palindromic portions and extending sequences at the terminal was annealed for assembling DS, which avoided the complex sequence design and high cost of long DNA strands. Benefiting from the multiple modification sites of DS, functional hairpins H1 (modified with Cy3 and BHQ2) and H2 were grafted onto the surface of DS for assembling DS-H1-H2 using a hybridization reaction. The DS-H1-H2 system utilized spatial confinement and the CHA reaction to amplify fluorescence signals of Cy3. This enabled highly sensitive and rapid detection of miR-21 in the range from 0.05 to 3.5 nM. The system achieved a limit of determination (LOD) of 2.0 pM, which was 56 times lower than that of the control CHA circuit with freedom hairpins. Additionally, the sensitivity was improved by 8 times. Moreover, DS-H1-H2 also showed an excellent imaging capability for endogenous miR-21 in tumor cells. This was due to enhanced cell internalization efficiency, accelerated reaction kinetics, and improved biostability. The imaging strategy was shown to effectively monitor the dynamic content of miR-21 in live cancer cells and differentiate various cells. In general, the simple nanostructure DS not only enhanced the detection and imaging capability of the conventional probe but also could be easily integrated with the reported DNA-free probe, indicating a wide range of potential applications.

2D/2D heterojunctions for rapid and self-cleaning removal of antibiotics via visible light-assisted peroxymonosulfate activation: Efficiency, synergistic effects, and applications.

Developing eco-friendly and efficient technologies for treating antibiotic wastewater is crucial. Traditional methods face challenges in incomplete removal, high costs, and secondary pollution. Heterogeneous peroxymonosulfate (PMS) activation assisted by visible light shows promise, but suitable activators remain a huge challenge. Here, we synthesized cost-effective carbon nitride/bismuth bromide oxide (CN/BiOBr) heterojunctions. Such a heterojunction achieved rapid PMS activation, achieving over 90.00% tetracycline (TC) removal only within 1 min (kobs of 2.23 min-1), surpassing previous systems by nearly 1-2 orders of magnitude and even remarkably superior to the popular single-atom catalysts. The system exhibited self-cleaning properties, maintaining activity after 8 cycles and stability across a wide pH range (3.01 to 9.03). Quenching experiments and theoretical calculations elucidated the exclusive •O2- species involvement and removal pathways. Eco-toxicity assessment and total organic carbon results confirmed simultaneous degradation, detoxification, and mineralization. This system also showed excellent resistance to environmental factors, e.g., coexisting anions, varying pH, and water sources, and demonstrated potential in coking and medical wastewater purification. This study presents a novel technique for rapidly decontaminating antibiotic wastewater through visible light-assisted PMS activation and introduces innovative bionic catalytic oxidation combining light and darkness for practical applications.

Iodine-catalyzed regioselective direct sulfenylation of uracil with sulfonyl hydrazide as sulfur source under solvent free conditions.

A facile method was developed for the selective thioetherification of uracils using sulfonyl hydrazide as the thioetherification reagent. This method offers advantages such as avoiding the use of additives and expensive metal catalysts, and providing good to excellent yields of various uracil thioethers. Experimental studies have demonstrated that the reaction follows a free radical pathway. Notably, the reaction can be carried out without solvent.

Self-Flipping Solar Seesaw Evaporators Leverage Scaling to De-Scale.

Salt scaling poses a significant obstacle to the practical implementation of solar-driven evaporation for desalination. Attempts to mitigate scaling by enhancing mass transfer often lead to a compromise in evaporation efficiency due to associated heat loss. In the present work, a novel seesaw evaporator with a Janus structure to harness scaling for periodic self-descaling is reported. The seesaw evaporators are facilely fabricated by delignifying balsa wood and subsequently single-sided spray-coating it with soot and polydimethylsiloxane (PDMS). This unique Janus structure enables the evaporator to float on the brine while ensuring an ample supply of solution for evaporation. During evaporation, salt ions are transported directionally toward the cocked end of the evaporator to form scaling, triggering the seesaw evaporator to flip once a threshold is reached. The accumulated salts re-dissolve back into the solution. By adjusting the tilt angle, the evaporator can achieve an impressive evaporation rate of up to 2.65 kg m-2  h-1 when evaporating an 8 wt.% NaCl solution. Remarkably, these evaporators maintain a stable evaporation rate during prolonged 120 h operation and produce ≈3.93-6.35 L m⁻2 ·day⁻¹ of freshwater from simulated brines when assembled into an evaporation device.

Prognostic value of red blood cell distribution width combined with chloride in predicting short- and long-term mortality in critically ill patients with congestive heart failure: Findings from the MIMIC-IV database.

Background: Hypochloremia and red blood cell distribution width (RDW) play important roles in congestive heart failure (CHF) pathophysiology, and they were associated with the prognosis of CHF. However, the prognostic value of chloride combined with RDW in patients with CHF remains unknown. Methods: We retrospectively analyzed critically ill patients with CHF. The database was derived from the Medical Information Mart for Intensive Care IV v2.0 (MIMIC-IV-v2.0) database. Results: In the final analysis, 5376 critically ill patients with CHF were included, and 2428 patients (45.2 %) experienced 5-year mortality. The restricted cubic spline model revealed a positive correlation between RDW and 5-year mortality, whereas chloride showed a U-shaped correlation with 5-year mortality. The median values of RDW and chloride were used to classify patients into four groups: high chloride/low RDW, low chloride/low RDW, high chloride/high RDW, and low chloride/high RDW. We observed the prognostic value of RDW combined with chloride in the Cox proportional hazard model, in predicting 5-year mortality, in-hospital mortality and 1-year mortality. Furthermore, we discovered that patients with chronic kidney disease (CKD) had a higher 5-year mortality risk than patients without CKD. Conclusion: We found the translational potential role of chloride combined with RDW in prioritizing patients at high risk for short- and long-term mortality in a cohort of critically ill patients with CHF. Prospective multicenter investigations are warranted to validate our results.

Embedding electronic perpetual motion into single-atom catalysts for persistent Fenton-like reactions.

In our quest to leverage the capabilities of the emerging single-atom catalysts (SACs) for wastewater purification, we confronted fundamental challenges related to electron scarcity and instability. Through meticulous theoretical calculations, we identified optimal placements for nitrogen vacancies (Nv) and iron (Fe) single-atom sites, uncovering a dual-site approach that significantly amplified visible-light absorption and charge transfer dynamics. Informed by these computational insights, we cleverly integrated Nv into the catalyst design to boost electron density around iron atoms, yielding a potent and flexible photoactivator for benign peracetic acid. This exceptional catalyst exhibited remarkable stability and effectively degraded various organic contaminants over 20 cycles with self-cleaning properties. Specifically, the Nv sites captured electrons, enabling their swift transfer to adjacent Fe sites under visible light irradiation. This mechanism accelerated the reduction of the formed "peracetic acid-catalyst" intermediate. Theoretical calculations were used to elucidate the synergistic interplay of dual mechanisms, illuminating increased adsorption and activation of reactive molecules. Furthermore, electron reduction pathways on the conduction band were elaborately explored, unveiling the production of reactive species that enhanced photocatalytic processes. A six-flux model and associated parameters were also applied to precisely optimize the photocatalytic process, providing invaluable insights for future photocatalyst design. Overall, this study offers a molecule-level insight into the rational design of robust SACs in a photo-Fenton-like system, with promising implications for wastewater treatment and other high-value applications.

Design of Photothermal "Ion Pumps" for Achieving Energy-Efficient, Augmented, and Durable Lithium Extraction from Seawater.

Extracting lithium from seawater has emerged as a disruptive platform to resolve the issue of an ever-growing lithium shortage. However, achieving highly efficient and durable lithium extraction from seawater in an energy-efficient manner is challenging, as imposed by the low concentration of lithium ions (Li+) and high concentration of interfering ions in seawater. Here, we report a facile and universal strategy to develop photothermal "ion pumps" (PIPs) that allow achieving energy-efficient, augmented, and durable lithium extraction from seawater under sunlight. The key design of PIPs lies in the function fusion and spatial configuration manipulation of a hydrophilic Li+-trapping nanofibrous core and a hydrophobic photothermal shell for governing gravity-driven water flow and solar-driven water evaporation. Such a synergetic effect allows PIPs to achieve spontaneous, continuous, and augmented Li+ replenishment-diffusion-enrichment, as well as circumvent the impact of concentration polarization and scaling of interfering ions. We demonstrate that our PIPs exhibit dramatic enhancement in Li+ trapping rate and outstanding Li+ separation factor yet have ultralow energy consumption. Moreover, our PIPs deliver ultrastable Li+ trapping performance without scaling even under high-concentration interfering ions for 140 h operation, as opposed to the significant decrease of nearly 55.6% in conventional photothermal configuration. The design concept and material toolkit developed in this work can also find applications in extracting high-value-added resources from seawater and beyond.

Sativene Sesquiterpenoids from the Plant Endophytic Fungus Bipolaris victoriae S27 and Their Potential as Plant-Growth Regulators.

Thirteen new sativene sesquiterpenoids (1 and 3-14), one new natural product (2), and 16 known compounds (15-30) were isolated from the endophytic fungus Bipolaris victoriae S27. Their structures were elucidated by extensive spectroscopic analysis, NMR and ECD calculations, and X-ray crystal diffractions. Compound 1 represented the first example of sativene sesquiterpenoids with a 6/5/3/5-caged tetracyclic ring system. All obtained compounds were evaluated for their plant-growth regulatory activity. The results showed that 1, 3, 4, 6, 8, 11, 12, 17, 19, 26, and 27 could suppress the growth of Arabidopsis thaliana, while 2, 5, 13, 15, 18, and 25 showed promoting effects. Among them, compound 3 showed the most potent plant-growth inhibitory activity, which is obviously superior to that of the marked herbicide glyphosate.

FLOWERING LOCUS T genes control floral induction in lotus.

The transition to flowering is a vital process in the lotus life cycle that significantly impacts its ornamental value and seed production. However, the molecular basis of floral transition in lotus remains largely unknown. Here, eight homologous FLOWERING LOCUS T (FT) genes were initially characterized in lotus, which were designated as NnFT1-NnFT8. All of these genes were found to possess the conserved PEBP domain and exhibited high transcript levels in both lotus leaves and floral organs. The proNnFT:ß-glucuronidase (GUS) assay exhibited GUS staining in the vascular tissues of leaves. Furthermore, subcellular localization revealed that NnFT proteins were present in various cellular organelles, including the nucleus, cytoplasm, and endoplasmic reticulum. Overexpression of two NnFT homologs, NnFT2 and NnFT3, rescued the late flowering phenotype in the Arabidopsis ft-10 mutant, indicating the stimulative roles of NnFTs in floral induction. Moreover, NnFTs demonstrated interactions with a bZIP transcription factor, FLOWERING LOCUS D (NnFD), both in vitro and in vivo. These findings will not only deepen our understanding of the regulatory mechanism underlying lotus floral transition, but also provide valuable genetic resources for creating new lotus varieties with extended blooming periods using molecular strategies in the future.

Selaginellin derivatives from Selaginella tamariscina and evaluation for anti-breast cancer activity.

A phytochemical investigation of Selaginella tamariscina led to the isolation of 17 selaginellin derivatives. Their inhibitory activities against breast cancer cells were screened, and preliminary structure-activity relationships were also established. Among them, dimeric selaginellin 17 showed potential activity against MDA-MB-231 cells with an IC50 value of 3.2 ± 0.1 µM, corresponding to 4-fold higher potency than the reference compound 5-FU (IC50 14.8 ± 0.2 µM). Mechanistic studies indicated that 17 could cause G2/M phase arrest in MDA-MB-231 cells and induce apoptosis accompanied by increased ROS levels.

[Selection and validation of reference genes for quantitative real-time PCR analysis in Paeonia veitchii].

Paeonia veitchii and P. lactiflora are both original plants of the famous Chinese medicinal drug Paeoniae Radix Rubra in the Chinese Pharmacopoeia. They have important medicinal value and great potential in the flower market. The selection of stable and reliable reference genes is a necessary prerequisite for molecular research on P. veitchii. In this study, two reference genes, Actin and GAPDH, were selected as candidate genes from the transcriptome data of P. veitchii. The expression levels of the two candidate genes in different tissues(phloem, xylem, stem, leaf, petiole, and ovary) and different growth stages(bud stage, flowering stage, and dormant stage) of P. veitchii were detected using real-time fluorescence quantitative technology(qRT-PCR). Then, the stability of the expression of the two reference genes was comprehensively analyzed using geNorm, NormFinder, BestKeeper, ΔCT, and RefFinder. The results showed that the expression patterns of Actin and GAPDH were stable in different tissues and growth stages of P. veitchii. Furthermore, the expression levels of eight genes(Pv-TPS01, Pv-TPS02, Pv-CYP01, Pv-CYP02, Pv-CYP03, Pv-BAHD01, Pv-UGT01, and Pv-UGT02) in different tissues were further detected based on the transcriptome data of P. veitchii. The results showed that when Actin and GAPDH were used as reference genes, the expression trends of the eight genes in different tissues of P. veitchii were consistent, validating the reliability of Actin and GAPDH as reference genes for P. veitchii. In conclusion, this study finds that Actin and GAPDH can be used as reference genes for studying gene expression levels in different tissues and growth stages of P. veitchii.

Nomogram based on pretreatment hepatic and renal function indicators for survival prediction of locally advanced esophageal squamous cell carcinoma with treatment of neoadjuvant chemoradiotherapy plus surgery.

The parameters for survival prediction of esophageal squamous cell carcinoma (ESCC) patients treated with neoadjuvant chemoradiotherapy (NCRT) combined with surgery are unclear. Here, we aimed to construct a nomogram for survival prediction of ESCC patients treated with NCRT combined with surgery based on pretreatment serological hepatic and renal function tests. A total of 174 patients diagnosed as ESCC were enrolled as a training cohort from July 2007 to June 2019, and approximately 50% of the cases (n = 88) were randomly selected as an internal validation cohort. Univariate and multivariate Cox survival analyses were performed to identify independent prognostic factors to establish a nomogram. Predictive accuracy of the nomogram was evaluated by Harrell's concordance index (C-index) and calibration curve. ALT, ALP, TBA, TP, AST, TBIL and CREA were identified as independent prognostic factors and incorporated into the construction of the hepatic and renal function test nomogram (HRFTNomogram). The C-index of the HRFTNomogram for overall survival (OS) was 0.764 (95% CI 0.701-0.827) in the training cohort, which was higher than that of the TNM staging system (0.507 (95% CI 0.429-0.585), P < 0.001). The 5-year OS calibration curve of the training cohort demonstrated that the predictive accuracy of the HRFTNomogram was satisfactory. Moreover, patients in the high-risk group stratified by the HRFTNomogram had poorer 5-year OS than those in the low-risk group in the training cohort (27.4% vs. 80.3%, P < 0.001). Similar results were observed in the internal validation cohort. A novel HRFTNomogram might help predict the survival of locally advanced ESCC patients treated with NCRT followed by esophagectomy.

pH-Driven Efficacy of the Ferrate(VI)-Peracetic Acid System in Swift Sulfonamide Antibiotic Degradation: A Deep Dive into Active Species Evolution and Mechanistic Insights.

In the realm of wastewater treatment, the power of ferrate (Fe(VI)) and peracetic acid (PAA) as oxidants stands out. But their combined might is where the enhancement truly lies. Their collaborative effect intensifies, but the underlying mechanics, especially across varying pH levels and pollutant types, still lurks in obscurity. Our study delved into the sophisticated oxidation interplay among Fe(VI)-PAA, Fe(VI)-H2O2, and standalone Fe(VI) systems. Notably, at a pH of 9.0, boasting a kinetic constant of ∼0.127 M-1·s-1, the Fe(VI)-PAA system annihilated the pollutant sulfamethoxazole, outpacing its counterparts by a staggering 48.73-fold when compared to the Fe(VI)-H2O2 system and 105.58-fold when using Fe(VI) individually. The behavior of active species─such as the dynamic •OH radicals and high-valent iron species (Fe(IV)/Fe(V))─shifted with pH variations, leading to distinct degradation pathways. Our detailed exploration pinpoints the behaviors of certain species across pH levels from 3.0 to 9.0. In more acidic environments, the •OH species proved indispensable for the system's reactivity. Conversely, as the pH inclined, degradation was increasingly steered by high-valent iron species. This intensive probe demystifies Fe(VI) interactions, deepening our understanding of the capabilities of the Fe(VI)-centered system and guiding us toward cleaner water solutions. Importantly, pH value, often underappreciated, holds the reins in organic wastewater decontamination. Embracing this key player is vital as we strategize for more expansive systems in upcoming ventures.