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Organic p‐type cathodes have captured increasing attention for lithium‐organic batteries due to their high voltage output. However, because of the low electronic and ionic conductivity, the p‐type organic electrode materials often show sluggish reaction kinetics and hence low capacities and poor cyclability. In this work, three conjugated polymers (Pz‐TPPO, Pz‐TPPS, and Pz‐TPP) based on p‐type phenazine linked with triphenyl phosphine are reported with different chemical modifications of phosphorus atom. Through oxidation and sulfuration of phosphorus atoms, the electron‐accepting property strength is increased, resulting in higher electronic conductivity of Pz‐TPPO and Pz‐TPPS. It is also found that the P═O unit in Pz‐TPPO exhibits stronger Li+ coordination, which can bring anions into close proximity to the redox centers, further improving the anion shuttling during charge and discharge. All these lead to the best lithium‐organic battery performance of Pz‐TPPO, such as high voltage output (3.1–3.9 V), high reversible specific capacity (149 mAh g−1 at 0.2 A g−1) and excellent cycle stability. The potential application has also been demonstrated in Pz‐TPPO//graphite full battery. This work provides a novel strategy for designing donor–acceptor (D–A) conjugated polymer by simple phosphorus modification toward high‐performance organic batteries. [ABSTRACT FROM AUTHOR]

While organophosphorus chemistry is gaining attention in a variety of fields, the synthesis of the phosphorus derivatives of amino acids remains a challenging task. Previously reported methods require the deprotonation of the nucleophile, complex reagents or hydrolysis of the phosphonate ester. In this paper, we demonstrate how to avoid these issues by employing phosphonylaminium salts for the synthesis of novel mixed n-alkylphosphonate diesters or amino acid-derived n-alkylphosphonamidates. We successfully applied this methodology for the synthesis of novel N-acyl homoserine lactone analogues with varying alkyl chains and ester groups in the phosphorus moiety. Finally, we developed a rapid, quantitative and high-throughput bioassay to screen a selection of these compounds for their herbicidal activity. Together, these results will aid future research in phosphorus chemistry, agrochemistry and the synthesis of bioactive targets. [ABSTRACT FROM AUTHOR]

Phosphorus‐centered disbiradicals, in which the radical sites exist as individual spin doublets with weak spin‐spin interaction have not been known so far. Starting from monoradicals of the type [⋅P(μ‐NTer)2P−R], we have now succeeded in linking two such monoradical phosphorus centers by appropriate choice of a linker. To this end, biradical [⋅P(μ‐NTer)2P⋅] (1) was treated with 1,6‐dibromohexane, affording the brominated species {Br[P(μ‐NTer)]2}2C6H12 (3). Subsequent reduction with KC8 led to the formation of the disbiradical {⋅[P(μ‐NTer)]2}2C6H12 (4) featuring a large distance between the radical phosphorus sites in the solid state and formally the highest biradical character observed in a P‐centered biradical so far, approaching 100 %. EPR spectroscopy revealed a three‐line signal in solution with a considerably larger exchange interaction than would be expected from the molecular structure of the single crystal. Quantum chemical calculations revealed a highly dynamic conformational space; thus, the two radical sites can approach each other with a much smaller distance in solution. Further reduction of 4 resulted in the formation of a potassium salt featuring the first structurally characterized P‐centered distonic radical anion (5−). Moreover, 4 could be used in small molecule activation. [ABSTRACT FROM AUTHOR]

The synthesis of P‐stereogenic phosphorus compounds has gained considerable attention due to their wide applications across many research fields. Among the available strategies, transition metal‐catalyzed asymmetric transformation of pentavalent phosphoryl (H−P(O)) precursors is particularly appealing. This approach involves a direct C−P bond‐forming process, rendering it straightforward, and it employs readily available, bench‐stable H−P(O) reagents that are compatible with various metal catalysts. Recent years have witnessed significant progress in this field, with a primary focus on asymmetric C−P cross‐couplings and hydrophosphorylations. This Concept article provides a brief summary of recent progress, highlights existing challenges, and discusses future directions in this exciting area. [ABSTRACT FROM AUTHOR]

This review describes the synthesis of polyphosphorhydrazone (PPH) dendrimers,which are highly branched macromolecules, having a phosphorus atom at each branching point. The properties of these PPH dendrimers in the field of catalysis are then described. The review is organized to illustrate in the first part how the specificities of dendrimers could contribute to green chemistry. This concerns in particular the dendritic effect that is an increased efficiency (yield, enantioselectivity, etc.) when the size of the dendrimer increases, the recovery and reuse of the dendritic catalyst, the decreased leaching, and the entrapping of nanoparticles. In a second part, some even greener approaches of catalysis with dendrimers will be displayed, such as catalysis in water, switchable catalysis, and organocatalysis (nometal used). Different types of catalytic reactions have been studied, such as Stille, Suzuki and Sonogashira couplings, Knoevenagel condensations, Michael additions, asymmetric allylic alkylations, O- and N-arylation and vinylation reactions, [2+2+2]-cycloaddition reactions, isomerization of 1-octan-3-ol, Friedel--Crafts acylations, Heck reactions, hydrogenations, hydrations, transfer hydrogenations, amination of β-dicarbonyl compounds, etc. [ABSTRACT FROM AUTHOR]

While organophosphorus chemistry is gaining attention in a variety of fields, the synthesis of the phosphorus derivatives of amino acids remains a challenging task. Previously reported methods require the deprotonation of the nucleophile, complex reagents or hydrolysis of the phosphonate ester. In this paper, we demonstrate how to avoid these issues by employing phosphonylaminium salts for the synthesis of novel mixed n-alkylphosphonate diesters or amino acid-derived n-alkylphosphonamidates. We successfully applied this methodology for the synthesis of novel N-acyl homoserine lactone analogues with varying alkyl chains and ester groups in the phosphorus moiety. Finally, we developed a rapid, quantitative and high-throughput bioassay to screen a selection of these compounds for their herbicidal activity. Together, these results will aid future research in phosphorus chemistry, agrochemistry and the synthesis of bioactive targets.

The supramolecular recognition of anions is increasingly harnessed to achieve the self‐assembly of supramolecular architectures, ranging from cages and polymers to (pseudo)rotaxanes. The cyanostar (CS) macrocycle has previously been shown to form 2 : 1 complexes with organophosphate anions that can be turned into [3]rotaxanes by stoppering. Here we achieved steric control over the assembly of pseudorotaxanes comprising the cyanostar macrocycle and a thread that is based, for the first time, on organo‐pyrophosphonates. Subtle differences in steric bulk on the threads allowed formation of either [3]pseudorotaxanes or [2]pseudorotaxanes. We demonstrate that the threading kinetics are governed by the steric demand of the organo‐pyrophosphonates and in one case, slows down to the timescale of minutes. Calculations show that the dianions are sterically offset inside the macrocycles. Our findings broaden the scope of cyanostar‐anion assemblies and may have relevance for the design of molecular machines whose directionality is a result of relatively slow slipping. [ABSTRACT FROM AUTHOR]

Dendrimers, being highly branched monodispersed macromolecules, predominantly exhibit identical terminal functionalities within their structural framework. Nonetheless, there are instances where the presence of two distinct surface functionalities becomes advantageous for the fulfilment of specific properties. To achieve this objective, one approach involves implementing Janus dendrimers, consisting of two dendrimeric wedges terminated by dissimilar functionalities. The prevalent method for creating these structures involves the synthesis of dendrons that possess a core functionality that complements that of a second dendron, facilitating their coupling to generate the desired dendrimers. In this comprehensive review, various techniques employed in the fabrication of phosphorus-based Janus dendrimers are elucidated, displaying the different coupling methodologies employed between the two units. The advantages of phosphorus dendrimers over classic dendrimers will be shown, as the presence of at least one phosphorus atom in each generation allows for the easy monitoring of reactions and the confirmation of purity through a simple technique such as 31P NMR, as these structures typically exhibit easily interpretable patterns. [ABSTRACT FROM AUTHOR]

Cardiovascular diseases are the primary and fundamental reasons of people death around the world. Precise, fast responding, compact and integrable biosensors are considered as the most important prevention or treatment devices. In this work, remarkable absorbers based on graphene-plasmonic-black phosphorous hybrid structures are proposed. These devices are utilized for bio-sensing applications. The presented device is consisted of different quarter-cylindrical and plate shaped layers of graphene, black phosphorous, Ag, Au and Al 2 O 3 . In order to improve functionality of the presented absorber (improving the absorption's peak value), effects of structural parameters and chemical potential (E f ) on the absorption spectrum are being considered. The proposed structure will be considered as a biosensor for detection of cholesterol concentrations in blood samples (this would help physicians in diagnosis of hypercholesterolemia and prevention of cardiovascular diseases), after improving its characteristics. Finally, it is expected for this biosensor the following remarkable sensitivity, figure of merit, quality factor and detection limit of 6045.6 nm/RIU, 237.61 RIU - 1 , (80.3-90.1) and (2.1e-4-2.26e-5) RIU, respectively. Therefore, the proposed device can be an appropriate candidate for bio-sensing applications in optical integrated circuits., (© 2024. The Author(s).)

The sustainable development strategy shifts water treatment from pollution removal to resource recovery. Here, an electrochemical resource-recovery anaerobic membrane bioreactor (eRAnMBR) that employed a magnesium plate and conductive membrane as dual anodes is presented and shows excellent performance in carbon, nitrogen, and phosphorus recovery, as well as 95% membrane anti-fouling. The Mg 2+ released alters the physicochemical properties of sludge, unblocking the cake layer, and recovers ammonium and phosphate, yielding 60.64% purity and 0.08 g d -1 struvite deposited onto cathode to be separated from sludge. The enhanced direct interspecies electron transfer, along with hydrogen evolution and alkalinity increase due to the electrochemical reactions, significantly increase methane yield and purity (93.97%) of the eRAnMBR. This increased internal energy can cover the additional electricity and electrode consumption. This integrated eRAnMBR reactor boasts the benefits of short process, low maintenance, and low carbon footprint, introducing a concept for the next generation of wastewater treatment., (© 2024. The Author(s).)

Goethite often harbors impurities, such as phosphorus (P) and aluminum (Al), which are incorporated into its structure through direct substitution or coprecipitation with nanocrystalline phases. Understanding the processes that drive the release of P and Al from goethite is of paramount importance for the iron ore industry and for managing nutrient and pollutant behavior in the environment. This study investigates the impact of Fe(II)-catalyzed recrystallization on the release of P and Al from goethite. We evaluated the solubility and extractability of P and Al in suspensions of Al- and P-coprecipitated goethite, treated with 57 Fe-enriched Fe(II) aq under oxygen-free conditions for 30 days at neutral pH and room temperatures. The addition of Fe(II) aq induced the recrystallization of goethite dominant initial synthetic phases (i.e., low P- and Al-containing phases) and the transformation of higher P- and/or Al-bearing starting material that was actually a mixture of goethite and minor amounts of lepidocrocite and feroxyhyte. Our results reveal that Fe(II)-catalyzed mineral and structural evolution led to the repartitioning of P and, to a lesser extent, Al throughout the crystal structure, mineral surface, and aqueous solution. Following a 30 day reaction with Fe(II) aq , we extracted approximately 80, 68.8, 73.9, and 83.2% of P from P-only, low, medium, and high P + Al goethite, respectively. Additionally, we observed total Al removals of approximately 17, 27, and 25% from low, medium, and high P + Al goethite, respectively. The results demonstrate that treating both P-only and P + Al goethite with Fe(II) at room temperature, followed by a 24 h extraction using 1 M NaOH, significantly enhances the overall extractability of P and Al, including both aqueous and surface-adsorbed fractions, compared to Fe(II)-free controls. These findings advance our understanding of the recrystallization process and impurity substitution in goethite, offering promising avenues for developing new environmentally friendly methods to extract P and other impurities from goethitic iron ores at lower temperatures.

Immunotherapy stands as a groundbreaking strategy for cancer treatment, due to its ability to precisely and safely detect and eradicate tumors. However, the efficacy of immunotherapy is often limited by tumor autophagy, a natural defense mechanism that tumors exploit to resist immune attacks. Herein, we introduce a spatiotemporally controlled method to modulate tumor autophagy via sonocatalysis, aiming to improve immunotherapeutic outcomes. Specifically, we synthesized a tumor-targeting nanocatalyst based on a semiconductor heterojunction composed of Barium Titanate (BTO), Black Phosphorus (BP) integrated with Hyaluronic Acid (HA), referred to as BTO/BP-HA. Compared to traditional catalysts, the heterojunction structure enhances energy band bending and rapid electron-hole separation under ultrasonic stimulation, splitting water to generate H 2 . This promotes tumor cell apoptosis by inhibiting mitochondrial respiration and induces immunogenic cell death, triggering immune responses to eliminate tumor cells. However, the concurrent activation of autophagy mitigates the cytotoxic effectiveness of nanocatalysts. Within the nanocatalyst, BP undergoes lysosomal degradation to generate PO 4 3- , which subsequently interacts with H + to generate a conjugated acidic anion, increasing the lysosomal pH. This research ingeniously combines sonocatalysis with tumor autophagy, disrupting the activity of acidic hydrolases to inhibit autophagy, thereby enhancing the immune response and improving the effectiveness of immunotherapy.

Infections associated with medical implants due to bacterial adhesion and biofilm formation are a serious problem, leading to acute health risks to patients by compromising their immune system. Therefore, suppressing biofilm formation on biomedical implants is a challenging task, especially for overcoming the drug resistance of bacterial biofilms. Herein, a synergistic efficient surface coating method was developed to inhibit biofilm formation on a model medical implant by combining the antimicrobial property of trimethyl chitosan (TMC) with either 2D material graphene oxide (GO) or black phosphorus (BP) sheets using layer-by-layer (LbL) self-assembly. The multilayer coatings of TMC/GO and TMC/BP were optimized on the glass surface (a model implant) and characterized by using spectroscopic and microscopy techniques. Next, we investigated the antibiofilm formation properties of the TMC/GO and TMC/BP coatings on glass surfaces against both Gram-negative, Escherichia coli ( E. coli ), and Gram-positive, Bacillus subtilis ( B. subtilis ), bacteria. The antibiofilm formation was studied using crystal violet (CV) and live/dead assays. Both the live/dead and the CV assays confirmed that the TMC/2D material (2DM)-coated surfaces prevented biofilm formation much more effectively compared to the uncoated surfaces. Scanning electron microscopy analyses revealed that the bacteria were affected physically by incubating with TMC/2DM-coated surfaces due to membrane perturbation, thereby preventing cell attachment and biofilm formation. Further, BP composite coatings (TMC/BP) showed a much better ability to thwart biofilm formation than GO composite coatings (TMC/GO). Also, multilayer coatings showed superior cytocompatibility with human foreskin fibroblast (HFF). Our results demonstrate that the developed coatings TMC/2DMs could be potential candidates for thwarting biofilm formation on medical implants.

The management of cadmium (Cd) contamination in soils poses a significant environmental challenge. This study investigates the effectiveness of phosphorus (P)-loaded coconut biochar, synthesized at various pyrolysis temperatures (450°C, 500°C, 550°C, and 600°C), in immobilizing Cd and enhancing P availability in soil environments. The biochar underwent a series of treatments including activation and P enrichment, followed by incubation trials to evaluate its performance in Cd immobilization and P bioavailability enhancement across varying soil concentrations (0.5 %, 1.0 %, and 2.0 %) over time periods of 15, 30, and 45 days. Remediation progress was monitored using phytotoxicity assessments with radish (Raphanus sativus) root length as a bioindicator, supplemented by urease activity analyses. Notably, the activation process increased the P loading capacity of biochar produced at 450°C, 500°C, and 550°C by 54.6 %, 72.4 %, and 51.8 %, respectively, while reducing the P retention capacity of biochar prepared at 600°C by 31.0 %. The biochar activated at 550°C presented the highest efficiency in remediating Cd-contaminated soils. Key findings indicate that the enhanced specific surface area and oxygenated functional group content of the activated biochar facilitated Cd adsorption and P uptake. The P-loaded biochar exhibited a substantial adsorption capacity for Cd, particularly effective at lower concentrations, rendering it highly suitable for soil remediation purposes. Additionally, the study revealed that the application of biochar led to an increase in soil pH, resulting in precipitation of Cd as hydroxide species and formation of insoluble complexes with phosphate ions, thereby reducing its bioavailability. In summary, incorporating P-loaded biochar into soil significantly improved soil quality and enhanced Cd passivation in contaminated soils. The utilization of biochar produced at 550°C, which exhibited optimal performance, suggests a practical and sustainable approach for soil remediation. Future research endeavors should prioritize the refinement of the biochar production process to enhance cost-effectiveness while maintaining high P loading efficiency., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Inc.)

Herein, we developed a rapid, one-step, and cost-effective methodology based on the fabrication of water-soluble self-nitrogen, sulfur, and phosphorus co-doped black seed carbon quantum dots (BSQDs) via microwaveirradiation in six minutes. Our synthesis approach is superior to those in the literature as they involved long-time heating (12 h) with sulfuric acid and sodium hydroxide and/or high temperatures (200 °C). A full factorial design was applied to obtain the most efficient synthesis conditions.BSQDs displayed excitation-independent emissions, demonstrating the purity of the synthesized BSQDs, with a maximum fluorescence at 425 nm after excitation at 310 nm. Eltrombopag olamine is an anti-thrombocytopenia drug that is also reported to cause toxicity in river water based on its Persistence, Bioaccumulation, and Toxicity (PBT). The synthesized BSQDs were employed as the first fluorometric sensor for environmental and bioanalysis of eltrombopag. The fluorescence of BSQDs decreased with increasing concentrations of eltrombopag, with excellent selectivity and sensitivity down to 30 ppb. BSQDs were successfully applied as sensing probes for the detection of eltrombopag in medical tablets, spiked and real human plasma samples, and river water samples, with an overall recovery of at least 97 %. The good tolerance to high levels of foreign components and co-administered drugs indicates good selectivity and versatility of the proposed methodology. Plasma pharmacokinetic parameters such as t 1/2 , C max , and t max of eltrombopag were evaluated to be 9.91 h, 16.0 μg mL -1 , and 5 h, respectively. Moreover, the green character of the BSQDs as a sensor was proved by various analytical greenness scales., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Wastewater containing phosphorus is often added by industrial activities, which is bad for the environment. In this study, composite biochar (PG-RS700) was prepared from phosphogypsum (PG) and rape straw (RS) for the treatment of phosphate in wastewater. SEM, FTIR, XRD and XPS characterization results showed that PG and RS were successfully combined. When PG-RS700 was dosed at 1.5 g/L and the phosphate solution concentration was 50 mg/L and pH = 8, the phosphate removal rate was 100% and the adsorption capacity was three times higher than the corresponding pure PG and RS. The quasi-secondary kinetic model indicated that the adsorption mechanism was chemisorption, and the maximum adsorption capacity for phosphate in the Langmuir isotherm model was 102.25 mg/g. Through pot experiment, the phosphorus adsorbed material obviously promoted the growth of plants. PG-RS700 can be used as a powerful adsorbent to treat phosphate in water and return it to soil as phosphate fertilizer., (© 2024. The Author(s), under exclusive licence to Springer Nature B.V.)

Photothermal therapy (PTT) encounters challenges of rapid thermal loss and potential tissue damage. In response, we propose a Heat-Boost and Lock implant coating strategy inspired by the thermal adaptation of biological membranes, enabling precise local photothermal utilization. This coating incorporates a poly(tannic acid) (pTA) bridging layer on implants, facilitating stable layer-by-layer integration of a black phosphorus (BP) photothermal layer and a top cell membrane Heat-Boost and Lock layer. The cell membrane layer significantly curtails photothermal loss (extending the heat retention by 17.62%) and stores energy within its phospholipid bilayer, boosting photothermal effects near implants (achieving a temperature increasement of 275%). Theoretical analysis indicates that these local heat preservation properties of the cell membrane arise from its low thermal conductivity and phase-change properties. In a Staphylococcus aureus -infected bone implant model, our coating demonstrates precise antibacterial action around implants (reach an antibacterial ratio of 99.52%). The synergetic locking function of cell membrane and pTA delays BP biodegradation, ensuring favorable photothermal stability and long-term osteo-inductive performance (increasing the bone volume fraction by 53.45%). Beyond providing an endogenic biointerface, this strategy extends the application of cell membrane in local thermal management, offering possibilities for effective and safe PTT modalities.

Hydrogen peroxide-based Fenton reaction can effectively degrade many small-molecule fluorescent dyes, leading to notable alterations in fluorescence signals. Additionally, the two-dimensional black phosphorus/platinum nanocomposite (BP/Pt) demonstrates exceptional catalase (CAT) characteristics. Based on these, a colorimetric-fluorescence dual-mode signal output pattern based on BP/Pt-Fenton reaction-rhodamine B tandem reaction system is reported. The physical adsorption property of the BP/Pt nanozymes was utilized to couple with antibodies, thus constructing a novel dual-mode nanozyme-based immuno-sensing assay (NISA). By using the migratory antibiotic enrofloxacin (ENR) as the target, the NISA provided highly sensitive detection with the detection limits of 0.058 ng/mL for colorimetric-mode and 0.025 ng/mL for fluorescence-mode and achieved accurate quantitative detection in environmental water and crucian carp samples. This work provides an innovative design for monitoring antibiotics in the environment and broadens the idea for the application of nanozymes and Fenton systems in immunosensing assays., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Austria, part of Springer Nature.)

Struvite recovery shows significant potential for simultaneously recovering nitrogen (N) and phosphorus (P) from swine wastewater but is challenged by the occurrence and transformation of antibiotic residuals. Electrochemically mediated struvite precipitation with sacrificial magnesium anode (EMSP-Mg) is promising due to its automation and chemical-free merits. However, the fate of antibiotics remains underexplored. We investigated the behavior of sulfadiazine (SD), an antibiotic frequently detected but less studied than others within the EMSP-Mg system. Significantly less SD (≤ 5%) was co-precipitated with recovered struvite in EMSP-Mg than conventional chemical struvite precipitation (CSP) processes (15.0 to 50.0%). The reduced SD accumulation in struvite recovered via EMSP was associated with increased pH and electric potential differences, which likely enhanced the electrostatic repulsion between SD and struvite. In contrast, the typical strategies used in enhancing P removal in the EMSP-Mg system, including increasing the Mg/P ratio or the Mg-release rates, have shown negligible effects on SD adsorption. Furthermore, typical coexisting ions (Ca 2+ , Cl - , and HCO 3 - ) inhibited SD adsorption onto recovered products. These results provide new insights into the interactions between antibiotics and struvite within the EMSP-Mg system, enhancing our understanding of antibiotic migration pathways and aiding the development of novel EMSP processes for cleaner struvite recovery., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

The effect of humic acid extracted from peat (AHt) on improving the struvite (STR) fertilizing efficiency is explored. To this end, a soil incubation study is correlated to plant assays comparing STR, STR-AHt, and superphosphate (SSP). Characterization techniques confirm the incorporation of the AHt into the STR. The P-pool distribution of STR and SSP is similar in the soil incubation, with STR-AHt presenting a higher labile P at 90 days passing from 10 to 15% P from SSP and STR to 25% P with STR-AHt. However, when applied to barley and tomato, STR yields more shoot P content, aboveground biomass, and residual P in soil than SSP. STR-AHt does not improve the STR results. The poor correlation observed between soil incubation and plant trials highlights the role of the rhizosphere in testing the fertilizer efficiency of STR. Mechanistic assays indicate the key role of rhizosphere pH. Finally, molecular modeling reveals a higher stabilization of STR with AHt, which could reduce P release decreasing the fertilizing potential of STR-AHt, as observed in the pot trials.

The spatiotemporal regulation of ion transport in living cell membrane channels has immense potential for providing novel therapeutic approaches for the treatment of currently intractable diseases. So far, most strategies suffer from uncontrolled ion transport and limited tumor therapy effects. On the premise of low toxicity to healthy tissues, enhancing the degree of ion overloading and the effect of tumor treatment still remains a challenging concern. Herein, an innovative strategy for synergistic ion channel therapy and hypoxic microenvironment activated chemotherapy is proposed. Biocompatible AQ4N/black phosphorus quantum dot clusters@liposomes (AQ4N/BPCs@Lip) nanocomplexes are site-specifically immobilized on the living cell membrane by a metabolic labeling strategy, eliminating the need for modifying or genetically encoding channel structures. Ascribing to the localized temperature increase of BPCs under NIR light irradiation, Ca 2+ overinflux can be remotely controlled and the overloading degree was increased; moreover, the local released AQ4N can only be activated in the tumor cell, while it has no toxicity to normal cells. Compared with single intracellular Ca 2+ overloading, the tumor cell viabilities decrease 2-fold with synergetic Ca 2+ overloading-induced ion channel therapy and hypoxic microenvironment activated chemotherapeutics. Our study demonstrates the example of a remote-controlled ion influx and drug delivery system for tumor therapy.

This study evaluated the influence of organic matter (OM) constituents on the potential for recovery of P from wastewaters when FeCl 3 treatment is employed for P removal. The presence of OM constituents did not influence P release from Fe-P sludges when alkaline and ascorbic acid treatments were employed. However, the overall recovery of P from wastewater was impacted by the presence of selected OM constituents through the reduction of P uptake during coagulation. The presence of protein and humic matter showed remarkably low P removal values (3.0 ± 0.4% and 23 ± 1% respectively) when compared to an inorganic control recipe (62 ± 2%). Elevated soluble Fe (SFe) residuals in the presence of proteins (87 ± 5%) and humics (51 ± 1%) indicated interactions between Fe(III) cations and negatively charged functional groups like hydroxyl, carboxyl, and phenolic groups available in these organics. Significant negative correlations between P removal and residual SFe were observed suggesting Fe solubilization by OM constituents was the mechanism responsible for reduced P removal. The findings of this study identify, for the first time, the impact of OM constituents on overall P recovery when Fe(III) salts are employed and provide insights into recoveries that can be expected when Fe is added to primary, secondary treated, and industrial wastewaters. PRACTITIONER POINTS: Low P removal values were observed for protein and humic dominated wastewater recipes. Iron(III) solubilization counted for P removal reduction by proteins and humic acids. There is no effect of OM on P release from Fe-P sludge at pH 10 and ascorbic acid treatments. OM and agent employed to release P from sludges affected overall recovery of P., (© 2024 The Author(s). Water Environment Research published by Wiley Periodicals LLC on behalf of Water Environment Federation.)

Phosphorus (P) overloading in aquatic environments has long-been recognized as the leading cause of water quality deterioration, harmful algal bloom, and eutrophication. This study investigated P removal performance by five cost-effective carbonaceous materials (CMs) in flow-through packed column systems. These CMs include biochars pyrolyzed from feedstocks of Eucalyptus (E-biochar) and Douglas fir (D-biochar), commercial biochar (C-biochar), iron oxide-coated biochar (Fe-biochar), and commercial activated carbon (AC). The physicochemical properties of CMs, such as specific surface area (SSA), pore volume, pore diameter, elemental composition, and surface charge, were characterized. The packed column experimental results showed that P removal performance followed the order: E-biochar < D-biochar < C-biochar < Fe-biochar < AC. Specifically, the sorption capacity of 1 mg/L of P in packed columns was 0.0036 mg P/g E-biochar, 0.0111 mg P/g D-biochar, 0.0369 mg P/g D-biochar, 0.077 mg P/g Fe-biochar, and 0.088 mg P/g AC, respectively. The largest SSA (1012 m 2 /g) and pore volume (0.57 cm 3 /g) of AC accounted for the most outstanding P removal efficiency mainly by physical sorption, while electrostatic interaction explained the high P removal by Fe-biochar (SSA as low as 32.4 m 2 /g). Our findings provide direct practical implications for effectively removing P in water by cost-effective CMs., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

In this study, we fabricated phosphorus-modified carbon felt electrode anodes for chloride oxidation in saline solutions to produce HClO via electrocatalysis, forming a compound fungicide saline applicable for debridement and disinfection. A low-cost phosphorus-modified carbon felt electrode (P@CF) with high chlorine evolution reaction activity was synthesized to address the reduced efficiency of CER and the solution's pH increase. Heteroatoms P and O were introduced into the carbon felt by phosphoric acid activation followed by heat treatment. The maximum active chlorine concentration on the P@CF electrode could reach 616.8 mg/L in 60 min under the optimal synthesis conditions of a phosphoric acid mass fraction of 30%, a phosphoric acid impregnation time of 3 h, and a heat treatment temperature of 300 °C. The active chlorine concentration was 1.8 times higher on the P@CF electrode compared to the original carbon felt electrode. The optimal reaction conditions for the generation of active chlorine were as follows: salt concentration of 9 g/L, voltage of 7 V, and electrode spacing of 2 cm as verified by response surfaces. This electrolysis reaction follows one-stage reaction kinetics. Subsequently, the disinfection efficacy of the produced disinfectants was examined. The prepared disinfectant was also compared to a commercially available hypochlorite disinfectant, showing similar disinfection effects on E. coli for both., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Phosphorus (P) pollution in aquatic environments poses significant environmental challenges, necessitating the development of effective remediation strategies, and biochar has emerged as a promising adsorbent for P removal at the cost of extensive research resources worldwide. In this study, a machine learning approach was proposed to simulate and predict the performance of biochar in removing P from water. A dataset consisting of 190 types of biochar was compiled from literature, encompassing various variables including biochar characteristics, water quality parameters, and operating conditions. Subsequently, the random forest and CatBoost algorithms were fine-tuned to establish a predictive model for P adsorption capacity. The results demonstrated that the optimized CatBoost model exhibited high prediction accuracy with an R 2 value of 0.9573, and biochar dosage, initial P concentration in water, and C content in biochar were identified as the predominant factors. Furthermore, partial dependence analysis was employed to examine the impact of individual variables and interactions between two features, providing valuable insights for adsorbent design and operating condition optimization. This work presented a comprehensive framework for applying a machine learning approach to address environmental issues and provided a valuable tool for advancing the design and implementation of biochar-based water treatment systems., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Nitrogen (N) addition can greatly influence soil inorganic phosphorus (Pi) and organic phosphorus (Po) transformations. However, whether and how the N compound forms may differentially affect the soil P fractions remain unclear. Here, we investigated the responses of soil Pi (labile Pi, moderately-occluded Pi, and recalcitrant Pi) and Po fractions (labile Po and stable Po) to varying addition rates of three N compounds ((NH 4 ) 2 SO 4 , NH 4 NO 3 , and urea) in a meadow steppe in northern China. Our studies revealed that with increasing N addition rate, soil labile and moderately-occluded Pi increased, accompanied by decreases in soil recalcitrant Pi. This shift was attributed to N-induced soil acidification, which accelerated the conversion of recalcitrant Pi into labile and moderately-occluded Pi. Soil labile Po decreased with increasing rate of N addition, whilst soil stable Po was not affected. Regardless of the compound forms, N addition increased soil Olsen-P, suggesting a potential alleviation of P limitation in this grassland ecosystem. The effect of N addition on soil labile Pi was significantly greater with addition of urea than with addition of either (NH 4 ) 2 SO 4 or NH 4 NO 3 , indicating that urea was more efficient in enhancing soil P availability. Addition of (NH 4 ) 2 SO 4 imposed a more pronounced positive effect on soil moderately-occluded Pi than the addition of either NH 4 NO 3 or urea, mainly due to the greater mobilization of recalcitrant Pi as a result of higher soil acidification strength of (NH 4 ) 2 SO 4 . These findings underscore the importance of considering the distinct effects of different N compounds when studying grassland soil P dynamics and availability in response to N addition., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

Dissolved organic matter (DOM) is a heterogeneous pool of compounds and exhibits diverse adsorption characteristics with or without phosphorous (P) competition. The impacts of these factors on the burial and mobilization of organic carbon and P in aquatic ecosystems remain uncertain. In this study, an algae-derived DOM (ADOM) and a commercially available humic acid (HA) with distinct compositions were assessed for their adsorption behaviors onto iron (oxy)hydroxides (FeOx), both in the absence and presence of phosphate. ADOM contained less aromatics but more protein-like and highly unsaturated structures with oxygen compounds (HUSO) than HA. The adsorption capacity of FeOx was significantly greater for ADOM than for HA. Protein-like and HUSO compounds in ADOM and humic-like compounds and macromolecular aromatics in HA were preferentially adsorbed by FeOx. Moreover, ADOM demonstrated a stronger inhibitory effect on phosphate adsorption than HA. This observation suggests that the substantial release of autochthonous ADOM by algae could elevate internal P loading and pose challenges for the restoration of restore eutrophic lakes. The presence of phosphate suppressed the adsorption of protein-like compounds in ADOM onto FeOx, resulting in an increase in the relative abundance of protein-like compounds and a decrease in the relative abundance of humic-like compounds in post-adsorption ADOM. In contrast, phosphate exhibited no discernible impact on the compositional fractionation of HA. Collectively, our results show the source-composition characters of DOM influence the immobilization of both DOM and P in aquatic ecosystems through adsorption processes. The preferential adsorption of proteinaceous compounds within ADOM and aromatics within HA highlights the potential for the attachment with FeOx to diminish the original source-specific signatures of DOM, thereby contributing to the shared DOM characteristics observed across diverse aquatic environments., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier B.V.)

Inspired by the synthesis of polyurethane, a multifunctional fabric with hydrophobic and long-lasting flame retardancy was prepared through the phase separation and interfacial reaction process between PEI (polyethyleneimine)/BX (borax) aqueous solution and isocyanate terminated polydimethylsiloxane (PDMS-NCO) in tetrahydrofuran solution. The limit oxygen index of the treated fabric increased from 18.0 % to 33.7 %, and the total heat release decreased by 34.2 %. The enhancement of flame retardant performance and thermal stability is attributed to the enhanced char-forming capacity. After 50 cycles of water washing, the cotton fabric can still pass the vertical flammability test because of the curing effect of PDMS-NCO on functional additives. Furthermore, SEM analysis revealed that the formation of nano-rough structures on the fibers was promoted by phase separation, thus leading an increased water contact angle of sample to 139°. The materials utilized in this modified process do not contain elements such as F, Cl, Br, and P, indicating its potential as an environmentally friendly methodology for fabric functionalization., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. All the authors listed have approved the manuscript enclosed., (Copyright © 2024. Published by Elsevier B.V.)

Near-infrared (NIR)-responsive metal-free carbon co-catalysts that convert glucose into H 2 O 2 to generate reactive oxygen species (ROS) are developed from phosphorus-doped carbon nitride (P-C 3 N 4 ) and graphene quantum dots (GQD) composites, for enhanced photocatalytic cancer therapy by light exposure in the targeted tumor microenvironment. Upon irradiation, the NIR light is converted by GQD with up-conversion function into visible light to excite P-C 3 N 4 for photocatalytic conversion of glucose into H 2 O 2 , which subsequently decomposes into ROS. ROS thus generated exhibits an excellent anticancer efficacy for efficient cancer therapy with minimal side effects, as evidenced by both in vitro and in vivo studies. This study demonstrates, for the first time, a cancer therapeutic of GQD/P-C 3 N 4 composite that utilizes a two-step cascade effect using initially NIR-triggered GQD nanoparticles to activate P-C 3 N 4 to photocatalytically generate ROS for effective and targeted cancer therapy., (© 2024 The Author(s). Advanced Materials published by Wiley‐VCH GmbH.)

Recycling phosphorus from waste activated sludge (WAS) is an effective method to address the nonrenewable nature of phosphorus and mitigate environmental pollution. To overcome the challenge of low phosphorus recovery from WAS due to insufficient disintegration, a method using a citric acid-based natural deep eutectic solvent (CA-NADES) assisted with low-temperature pretreatment was proposed to efficiently release and recover phosphorus. The results of 31 P nuclear magnetic resonance (NMR) confirmed that low-temperature pretreatment promoted the conversion of organic phosphorus (OP) to inorganic phosphorus (IP) and enhanced the effect of CA-NADES. Changes in the three-dimensional excitation-emission matrix (3D-EEM) and flow cytometry (FCM) indicated that the method of CA-NADES with low-temperature thermal simultaneously release IP and OP by disintegrating sludge flocs, dissolving extracellular polymeric substances (EPS) structure, and cracking cells. When 5 % (v/v) of CA-NADES was added and thermally treated at 60 °C for 30 min, 43 % of total phosphorus (TP) was released from the sludge. The concentrations of proteins and polysaccharides reached 826 and 331 mg/L, respectively, which were 6.30 and 14.43 times higher than those of raw sludge. The dewatering and settling of the sludge were also improved. Metals were either enriched in the solid phase or released into the liquid phase in small quantities (most efficiencies of less than 10 %) for subsequent clean recovery. The released phosphorus was successfully recovered as vivianite with a rate of 90 %. This study develops an efficient, green, and sustainable method for phosphorus recovery from sludge using NADES and provides new insights into the high-value conversion of sludge., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

In this study, a 4-(hydroxymethyl)-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane 1-oxide (PEPA)-functionalized acrylate monomer, PEPAA, is designed and utilized for the synthesis of macromolecular flame retardants poly(PEPAA-co-AM) with varying PEPAA/AM ratio through copolymerization with acrylamide (AM). The poly(PEPAA-co-AM) is then incorporated into polypropylene (PP) to prepare PP/poly(PEPAA-co-AM) composites. The flame retardant effect of poly(PEPAA-co-AM) on PP is investigated using cone calorimetric test (CCT), and compared with that of PEPAA homopolymer (P-PEPAA), AM homopolymer (PAM), and blends of P-PEPAA/PAM. The results demonstrate that, in comparison with P-PEPAA, PAM, and blends of P-PEPAA/PAM, the incorporation of poly(PEPAA-co-AM) significantly enhances the flame retardancy of PP. Notably, the best flame retardancy is achieved when the ratio of PEPAA/AM copolymerization in poly(PEPAA-co-AM) is 2/8. The morphology and composition of residual chars from combustion are analyzed using SEM-EDS while the residual graphitization degree is examined through Raman spectroscopy. Additionally, TG-FTIR-MS is utilized to investigate the pyrolysis products in gas phase during thermal decomposition of poly(PEPAA-co-AM). Based on these experimental results, a flame retardant mechanism for poly(PEPAA-co-AM) is proposed. The PP/poly(PEPAA-co-AM) composites not only retain the excellent processing properties of pure PP but also exhibit enhanced mechanical properties., (© 2024 Wiley‐VCH GmbH.)

The durable flame-retardant functional coating of polyester/cotton (T/C) blend fabrics is both interesting and challenging. In this study, a novel in-situ polymerization strategy for phosphorus/nitrogen-based flame-retardant on T/C blend samples was developed through the polycondensation of tetramethylolphosphonium sulfate, dicyandiamide, and anionic cyclic phosphate ester. The chemical structure of the polycondensation compounds, as well as the surface morphology, combustion behavior, flame-retardant capacity, washing durability and flame-retardant mechanism of the coated T/C blend fabrics, were investigated. The coated T/C blend fabrics demonstrated excellent self-extinguishing performance, with the damaged length decreasing to as low as 8.0 cm and the LOI reaching 28 %. Moreover, the peak heat release rate of the coated T/C blend fabrics decreased by 39.7 %. The superior flame retardancy can be attributed to the enhanced dehydration and carbonization by phosphate groups in the condensed phase, as well as the quenching effect and diluting effect in the gas phase. Additionally, the coated T/C blend fabrics exhibited remarkable washing durability and still achieved self-extinguishing after 65 washing cycles, and the in-situ deposition of insoluble three-dimensional polycondensation compounds onto the T/C blend fabrics was beneficial. The flame-retardant coating had a minor impact on the whiteness, tensile strength and breathability of the T/C blend fabrics., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

To solve the problems of flammability and smoldering of cotton fabric, its flame-retardant finishing was executed with biomass wool keratin (WK) and cyclic phosphate ester (CPE) through the soaking and baking process. The synergistic mechanism of WK low-temperature melting and CPE catalytic dehydration prompted the formation of protective carbonization layer on cotton fabric surface, and this protective layer reduced its pyrolysis rate, inhibited the production of combustible materials and improved its flame retardancy. The results of synchronous thermal analysis indicate that the initial decomposition temperature of WK and CPE is lower than that of cotton fabric, and they precede the endothermic degradation before fabric main body. This effectively promotes the low-temperature carbonization of cotton fabric and inhibits its pyrolysis. The initial decomposition temperature of WK/CPE treated fabrics advances by 47.9 °C-97.8 °C, presenting significant low-temperature carbonization trend. Moreover, they form 3.0 %-20.0 % aromatic structural char before the pyrolysis of cotton cellulose due to the low-temperature dehydration and carbonization reactions. The damage length after vertical burning is only 4.0 cm for treated fabric with five layers, its after-flame and smoldering disappear, and its limiting oxygen index value increases to 28.7 %. This research provides an effective idea for the flammability and smoldering problems of cotton fabric., Competing Interests: Declaration of competing interest We declare that we have no financial and personal relationships with other people or organization that can inappropriately influence our work, there is no professional or other personal interest of any nature or kind in any product, service and/or company that could be construed as influencing the position presented in, or the review of, the manuscript entitled., (Copyright © 2024 Elsevier B.V. All rights reserved.)

The interaction between organic phosphorus (OP) and iron oxide significantly influences the phosphorus cycle in the natural environment. In shallow lakes, intense oxidation-reduction fluctuations constantly alter the existing form of iron oxides, but little is known about their impact on the adsorption and fractionation of OP molecules. In this study, electrospray ionization coupled with Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR MS) was used to investigate the fractionation of OP from alkali-extracted sediment induced by crystalline goethite and amorphous ferrihydrite adsorption at a molecular scale. The results showed that ferrihydrite and goethite both exhibited high OP adsorption, and the adsorption amount decreased as the pH increased. The adsorption kinetics matched the pseudo-second-order equation. The ESI-FT-ICR MS analysis showed that 91 P-containing formulas were detected in the alkaline-extracted sediment solution. Ferrihydrite and goethite adsorbed 51 and 24 P-containing formulas, respectively, with adsorption rates of 56.0 % and 26.4 %. Ferrihydrite could adsorb more OP compounds than goethite, but no obvious molecular species selectivity was observed during the adsorption. The P-containing compounds, including unsaturated hydrocarbons-, lignin/carboxyl-rich alicyclic molecule (CRAM)-, tannin-, and carbohydrate-like molecular compounds, were more suitable for iron oxide adsorption. The double bond equivalence (DBE) is a valuable parameter that indicates OP fractionation during adsorption, and P-containing compounds with lower DBE values such as lipid- and protein-like molecular were prone to remain in the solution after adsorption. These research results provide insights into the biogeochemical cycling process of P in the natural environment., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Inc. All rights reserved.)

Infectious bone defects resulting from surgery, infection, or trauma are a prevalent clinical issue. Current treatments commonly used include systemic antibiotics and autografts or allografts. Nevertheless, therapies come with various disadvantages, including multidrug-resistant bacteria, complications arising from the donor site, and immune rejection, which makes artificial implants desirable. However, artificial implants can fail due to bacterial infections and inadequate bone fusion after implantation. Thus, the development of multifunctional bone substitutes that are biocompatible, antibacterial, osteoconductive, and osteoinductive would be of great clinical importance. This study designs and prepares 2D graphene oxide (GO) and black phosphorus (BP) reinforced porous collagen (Col) scaffolds as a viable strategy for treating infectious bone defects. The fabricated Col-GO@BP scaffold exhibited an efficient photothermal antibacterial effect under near-infrared (NIR) irradiation. A further benefit of the NIR-controlled degradation of BP was to promote biomineralization by phosphorus-driven and calcium-extracted phosphorus in situ. The abundant functional groups in GO could synergistically capture the ions and enhance the in situ biomineralization. The Col-GO@BP scaffold facilitated osteogenic differentiation of bone marrow-derived mesenchymal stem cells (BMSC) by leveraging its mild photothermal effect and biomineralization process, which upregulated heat shock proteins (HSPs) and activated PI3K/Akt pathways. Additionally, systematic in vivo experiments demonstrated that the Col-GO@BP scaffold obviously promotes infectious bone repair through admirable photothermal antibacterial performance and enhanced vascularization. As a result of this study, we provide new insights into the photothermal activity of GO@BP nanosheets, their degradation, and a new biological application for them.

Understanding the variations in soil aggregate composition, as well as the contents and stoichiometry of organic carbon (C), total nitrogen (N) and total phosphorus (P), in the surface layer of Cryptomeria japonica plantations with different stand ages can provide a theoretical basis for the optimized management of plantations and the improvement of soil fertility in the Rainy Area of West China. With the dry-sieving method, we measured the contents of soil aggregates with different sizes in the 0-15 and 15-30 cm soil layers across C. japonica plantations with five distinct developmental stages at Hongya Forestry Farm, Sichuan Province, including young stands (7 years old), middle-aged stands (13 years old), nearly mature stands (24 years old), mature stands (33 years old), and over-mature stands (53 years old). We further analyzed the C, N and P contents and ecological stoichiometric characteristics of soil aggregates. The results showed that the particle size composition of soil aggregates in C. japonica plantations varied among stand ages. The nearly mature and mature stands had higher proportion of large aggregates (0.5-1 and 1-2 mm), whereas the nearly mature stand had a lower proportion of micro-aggregates (0.053-0.25 mm) and the silt-plus-clay fraction (<0.053 mm). Moreover, the C, N and P contents and stoichiometric ratios in soil aggregate showed a unimodal pattern, which increased initially and then decreased with stand age, with peak values in the nearly mature and mature plantations. Furthermore, the C, N and P contents in aggregates in 0-15 cm soil layer were higher than that in the 15-30 cm soil layer. The highest C and N contents were found in the aggregates with particle sizes of 0.5-1 and 0.25-0.5 mm. In conclusion, the near-mature and mature stands of C. japonica plantations have higher nutrient content in soil aggregate, underscoring these stages was critical for maintaining soil fertility and advancing sustainable management practices.

The impact of water on catalyst activity remains inconclusive due to its dependence on the specific reaction environment. To maximize the exploitation of water's promoting effect, we employed ammonia selective catalytic reduction (NH 3 -SCR) as a probe reaction and proposed a phosphorus modification strategy for Cu-ZSM-5 catalysts. The objective of this approach was to construct water-adaptive microstructures through directional arrangement. To investigate the effect of phosphorus on the transformation of framework copper sites in humid environments, we conducted comprehensive characterizations and density functional theory calculation. Results reveal that water molecules cleave the oxygen bridges between phosphorus oxide and copper, leading to the formation of active isolated [Cu(OH)] + groups and phosphate. The phosphate species weaken the interaction between exchanged Cu 2+ groups and the zeolite framework, leading to the generation of highly migratory hydrated Cu 2+ species. This work will potentially guide the rational design of water-adaptive catalysts for gas pollution abatement in a humid environment.

Struvite recovery from wastewater offers a sustainable phosphorus and nitrogen source, yet it harbors the challenge of variable antibiotic residues, notably oxytetracycline (OTC), increasing the ecological risk during subsequent use. Despite the need, mechanisms behind these residues and regulatory solutions remain obscure. We characterized OTC in recovered struvite and showed that increased dissolved organic matter (DOM) enhanced OTC accumulation, while PO 4 3- suppressed it. NH 4 + modulated OTC levels through the saturation index (SI), with a rise in SI significantly reducing OTC content. Additionally, excess Mg 2+ formed complexes with OTC and DOM (humic acid, HA), leading to increased residue levels. Complexation was stronger at higher pH, whereas electrostatic interactions dominated at lower pH. The primary binding sites for antibiotics and DOM were Mg-OH and P-OH groups in struvite. OTC's dimethylamino, amide, and phenolic diketone groups primarily bound to struvite and DOM, with the carboxyl group of DOM serving as the main binding site. Mg 2+ complexation was the primary pathway for OTC transportation, whereas electrostatic attraction of PO 4 3- dominated during growth. Controlling magnesium (Mg) dosage and adjusting pH were effective for reducing OTC in recovered products. Our findings provided insights into the intricate interactions between struvite and antibiotics, laying the groundwork for further minimizing antibiotic residues in recovered phosphorus products., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Phosphonates are widely used scale inhibitors, but the residual phosphonates in drainage are challenging to remove because of their chelating capacity and resistance to biodegradation. Here, we reported a highly efficient and robust Fe-electrocoagulation (Fe-EC) system for phosphonate removal. Surprisingly, we found for the first time that phosphonates like NTMP were more efficiently removed under anoxic conditions (80% of total soluble phosphorus (TSP) in 4 min) than oxic conditions (0% of TSP within 6 min) in NaCl solution. A similar phenomenon was observed when other phosphonates, such as EDTMP and DTPMP, were removed, highlighting the importance of iron complexation and floc formation toward phosphonate removal with Fe-EC. We also showed that the removal efficiency of NTMP by electrochemically in-situ formed flocs (97%) was much higher than post-adsorption systems (ex-situ, 40%), revealing that the growth of flocs consumed the active site for NTMP adsorption. Beyond the removal of TSP, 10 % of NTMP-P was also degraded after the electrolysis phase, evidenced by the evolution of phosphate-P. However, this did not happen in anoxic or chemical coagulation processes, which confirms the formation of reactive oxygen species via Fe(II) oxidation in the oxic Fe-EC system. The primary removal mechanism of phosphonates is due to their complexation with iron (hydr)oxide generated in the Fe-EC system by forming a Fe-O-P bond. Encouragingly, the Fe-EC system exhibits comparable or even better performance in treating phosphonate-laden wastewater (i.e., cooling water). Our preliminary cost calculation suggests the proposed system (€ 0.009/m 3 ) has a much lower OPEX under oxic conditions than existing approaches. This study sheds light on the removal mechanism of phosphonate and the treatment of phosphonate-laden wastewater by playing with the iron complexion and flocs formation in classical Fe-EC systems., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

This study investigated the influence of plant-derived biochar (PB) and animal-derived biochar (AB) on behavior of heavy metals and phosphorus fractions during sewage sludge composting. PB was highly effective in reducing the bioavailability of Zn and Cu by 39% and 50%, respectively, while AB decreased the bioavailability of Pb (30%) and Cd (12%). Both biochar increased available phosphorus by over 38%. Acid extractable and bioavailable Pb in AB, and water-soluble, oxidizable and total Zn, acid extractable and oxidizable Cu in PB were positively correlated with moderately resistant organic phosphorus (MROP). Besides, in AB, Cd had strong and positive correlation with highly resistant organic phosphorus (HROP). This suggested biochar facilitated the formation of stable organometallic complexes through binding metal ions to phosphorus fractions, with notable differences based on biochar source. FT-IR showed biochar promoted humification, with PB enhancing carboxyl and polysaccharide formation, while AB encouraged quinone and aryl ether structures. These surface functional groups on the biochar likely contributed to heavy metals and phosphorus binding through chelation, adsorption, and electron shuttling., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Pyrolysis of animal manure at high temperature is necessary to effectively immobilize heavy metals, while the available phosphorus (P) level in biochar is relatively low, rendering it unsuitable for use as fertilizer. In this study, the pretreatment of swine manure with different potassium (K) sources (KOH, K 2 CO 3 , CH 3 COOK and C 6 H 5 K 3 O 7 ) was conducted to produce a biochar with enhanced P availability and heavy metals immobility. The addition of all K compounds lowered the peak temperature of decomposition of cellulose in swine manure. The percentage of ammonium citrate and formic acid extractable P in biochar increased with K addition compared to undoped biochar, with CH 3 COOK and C 6 H 5 K 3 O 7 showing greater effectiveness than KOH and K 2 CO 3 , however, water- extractable P did not exhibit significant changes. Additionally, the available and dissolved Si increased due to the doping of K, with KOH and K 2 CO 3 having a stronger effect than CH 3 COOK and C 6 H 5 K 3 O 7 . X-Ray Diffraction (XRD) and Fourier Transform Infrared Spectroscopy (FTIR) analysis revealed that K addition led to the formation of soluble CaKPO 4 and silicate. In addition, the incorporation of K promoted the transformation of labile copper (Cu) and znic (Zn) into the stable fraction while simultaneously reducing their environmental risk. Our study suggest that the co-pyrolysis of swine manure and organic K represents an effective and valuable method for producing biochar with optimized P availability and heavy metals immobility., (© 2024. The Author(s).)

In vivo phosphorus-31 ( 31 P) magnetic resonance spectroscopy (MRS) imaging (MRSI) is an important non-invasive imaging tool for studying cerebral energy metabolism, intracellular nicotinamide adenine dinucleotide (NAD) and redox ratio, and mitochondrial function. However, it is challenging to achieve high signal-to-noise ratio (SNR) 31 P MRS/MRSI results owing to low phosphorus metabolites concentration and low phosphorous gyromagnetic ratio (γ). Many works have demonstrated that ultrahigh field (UHF) could significantly improve the 31 P-MRS SNR. However, there is a lack of studies of the 31 P MRSI SNR in the 10.5 Tesla (T) human scanner. In this study, we designed and constructed a novel 31 P- 1 H dual-frequency loop-dipole probe that can operate at both 7T and 10.5T for a quantitative comparison of 31 P MRSI SNR between the two magnetic fields, taking into account the RF coil B 1 fields (RF coil receive and transmit fields) and relaxation times. We found that the SNR of the 31 P MRS signal is 1.5 times higher at 10.5T as compared to 7T, and the power dependence of SNR on magnetic field strength (B 0 ) is 1.9.

Background: Sequestering carbon dioxide (CO 2 ) in agricultural soils promises climate change mitigation as well as sustainable ecosystem services. In order to stabilize crop residues as soil carbon (C), addition of mineral nutrients in excess to crop needs is suggested as an inevitable practice. However, the effect of two macronutrients i.e ., nitrogen (N) & phosphorus (P), on C cycling has been found contradictory. Mineral N usually decreases whereas mineral P increases the soil organic C (SOC) mineralization and microbial biomass. How the addition of these macronutrients in inorganic form to an organic-matter poor soil affect C cycling remains to be investigated., Methods: To reconcile this contradiction, we tested the effect of mineral N (120 kg N ha -1 ) and/or P (60 kg N ha -1 ) in presence or absence of maize litter (1 g C kg -1 soil) on C cycling in an organic-matter poor soil (0.87% SOC) in a laboratory incubation. Soil respiration was measured periodically during the incubation whereas various soil variables were measured at the end of the incubation., Results: Contrary to literature, P addition stimulated soil C mineralization very briefly at start of incubation period and released similar total cumulative CO 2 -C as in control soil. We attributed this to low organic C content of the soil as P addition could desorb very low amounts of labile C for microbial use. Adding N with litter built up the largest microbial biomass (144% higher) without inducing any further increase in CO 2 -C release compared to litter only addition. However, adding P with litter did not induce any increase in microbial biomass. Co-application of inorganic N and P significantly increased C mineralization in presence (19% with respect to only litter amended) as well as absence (41% with respect to control soil) of litter. Overall, our study indicates that the combined application of inorganic N and P stabilizes added organic matter while depletes the already unamended soil., Competing Interests: Tanvir Shahzad and Sabir Hussain are Academic Editors for PeerJ., (© 2024 Anwar et al.)

Basalt fiber (BF) with modification of iron (Fe-MBF) and calcium (Ca-MBF) were filled into constructed wetland-microbial fuel cell (CW-MFC) for innovative comparison of improved performance under perfluorooctanoic acid (PFOA) exposure. More enhancement on nitrogen and phosphorus removal was observed by Fe-MBF than Ca-MBF, with significant increase of ammonium (NH 4 + -N) removal by 3.36-5.66 % (p < 0.05) compared to control, even under PFOA stress. Markedly higher removal efficiency of PFOA by 4.76-8.75 % (p < 0.05) resulted from Fe-MBF, compared to Ca-MBF and control BF groups. Besides, superior electrochemical performance was found in Fe-MBF group, with maximum power density 28.65 % higher than control. Fe-MBF caused higher abundance of dominant microbes on electrodes ranged from phylum to family. Meanwhile, ammonia oxidizing bacteria like Nitrosomonas was more abundant in Fe-MBF group, which was positively correlated to NH 4 + -N and total nitrogen removal. Some other functional genera involved in denitrification and phosphorus-accumulation were enriched by Fe-MBF on electrodes and MBF carrier, including Dechloromonas, Candidatus&#95;Competibacter, and Pseudomonas. Additionally, there were more biomarkers in Fe-MBF group, like Pseudarcobacter and Acidovorax, conducive to nitrogen and iron cycling. Most functional genes of nitrogen, carbon, and sulfur metabolisms were up-regulated with Fe-MBF filling, causing improvement on nitrogen removal., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

To address the problem of the weak natural restoration ability of oligotrophic groundwater environments, a novel N/P controlled-release material (CRM) for biostimulation, prepared by an improved method, was developed. CRMs can encapsulate N and P (N/P) salts for sustained release in aquifers. Paraffin-based CRMs can be used to control N/P release rates by adjusting the particle size of CRMs and the mass ratio of the paraffin. The developed CRMs had a more remarkable adaptability to groundwater than other materials. Specifically, 0.4-cm CRMs released N/P stably and efficiently over a wide temperature range (7-25 ℃), and the release properties of various CRMs were not affected by pH. The release of N/P followed Fickian diffusion, and a dissolution-diffusion model was established to elucidate the mechanism of the controlled release. In contrast to bare N/P, CRMs obviously enhanced the biodegradation rate of phenol and prolonged the effectiveness of supplying N/P. The degradation rate of phenol in the CRM system increased by 20.8 %. The different supply modes of N/P, CRMs and bare N/P, resulted in differences in salinity. Metagenomic analysis showed that this difference changed the proportion of various phenol-degrading genera and thus changed the abundance of genes associated with the phenol degradation pathway., Competing Interests: Declaration of Competing Interest We declare that the authors declare no competing financial interest., (Copyright © 2024 Elsevier B.V. All rights reserved.)

This study investigated the relationship between microplastic (MP) presence and pollutant removal in granular sludge sequencing batch reactors (GSBRs). Two types of MPs, polyethylene (PE) and polyethylene terephthalate (PET), were introduced in varying concentrations to assess their effects on microbial community dynamics and rates of nitrogen, phosphorus, and organic compound removal. The study revealed type-dependent variations in the deposition of MPs within the biomass, with PET-MPs exhibiting a stronger affinity for accumulation in biomass. A 50 mg/L dose of PET-MP decreased COD removal efficiency by approximately 4 % while increasing P-PO 4 removal efficiency by around 7 % compared to the control reactor. The rate of nitrogen compounds removal decreased with higher PET-MP dosages but increased with higher PE-MP dosages. An analysis of microbial activity and gene abundance highlighted the influence of MPs on the expression of the nosZ and ppk1 genes, which code enzymes responsible for nitrogen and phosphorus transformations. The study also explored shifts in microbial community structure, revealing alterations with changes in MP dose and type. This research contributes valuable insights into the complex interactions between MP, microbial communities, and pollutant removal processes in GSBR systems, with implications for the sustainable management of wastewater treatment in the presence of MP., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Neonicotinoids pose significant environmental risks due to their widespread use, persistence, and challenges in elimination. This study explores the effectiveness of Fe/Mn biochar in enhancing the removal efficiency of neonicotinoids in recirculating constructed wetlands (RCWs). Results demonstrated that incorporating Fe/Mn biochar into RCWs significantly improved the removal of COD, NH 4 + -N, TN, TP, imidacloprid (IMI), and acetamiprid (ACE). However, the simultaneous presence of IMI and ACE in the RCWs hindered the elimination of NH 4 + -N, TN, and TP from wastewater. The enhanced removal of nutrients and pollutants by Fe/Mn biochar was attributed to its promotion of carbon, nitrogen, and phosphorus cycling in RCWs, along with its facilitation of the adsorption and biodegradation of IMI and ACE. Metagenomics analysis demonstrated that Fe/Mn biochar altered the structure and diversity of microbial communities in RCWs. A total of 17 biodegradation genes (BDGs) and two pesticide degradation genes (PDGs) were identified within RCWs, with Fe/Mn biochar significantly increasing the abundance of BDGs such as cytochrome P450. The potential host genera for these BDGs/PDGs were identified as Betaproteobacteria, Acidobacteria, Nitrospiraceae, Gemmatimonadetes, and Bacillus. This study offers valuable insights into how Fe/Mn biochar enhances pesticide removal and its potential application in constructed wetland systems for treating pesticide-contaminated wastewater., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. No interests to declare., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Phosphate-solubilizing bacteria (PSB) are important but often overlooked regulators of uranium (U) cycling in soil. However, the impact of PSB on uranate fixation coupled with the decomposition of recalcitrant phosphorus (P) in mining land remains poorly understood. Here, we combined gene amplicon sequencing, metagenome and metatranscriptome sequencing analysis and strain isolation to explore the effects of PSB on the stabilization of uranate and P availability in U mining areas. We found that the content of available phosphorus (AP), carbonate-U and Fe-Mn-U oxides in tailings was significantly (P < 0.05) higher than their adjacent soils. Also, organic phosphate mineralizing (PhoD) bacteria (e.g., Streptomyces) and inorganic phosphate solubilizing (gcd) bacteria (e.g., Rhodococcus) were enriched in tailings and soils, but only organic phosphate mineralizing-bacteria substantially contributed to the AP. Notably, most genes involved in organophosphorus mineralization and uranate resistance were widely present in tailings rather than soil. Comparative genomics analyses supported that organophosphorus mineralizing-Streptomyces species could increase soil AP content and immobilize U(VI) through organophosphorus mineralization (e.g., PhoD, ugpBAEC) and U resistance related genes (e.g., petA). We further demonstrated that the isolated Streptomyces sp. PSBY1 could enhance the U(VI) immobilization mediated by the NADH-dependent ubiquinol-cytochrome c reductase (petA) through decomposing organophosphorous compounds. This study advances our understanding of the roles of PSB in regulating the fixation of uranate and P availability in U tailings., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)