Diester Research Articles

Abiotic Acyl Transfer Cascades Driven by Aminoacyl Phosphate Esters and Self-Assembly.

Biochemical acyl transfer cascades, such as those initiated by the adenylation of carboxylic acids, are central to various biological processes, including protein synthesis and fatty acid metabolism. Designing cascade reactions in aqueous media remains challenging due to the need to control multiple, sequential reactions in a single pot and manage the stability of reactive intermediates. Herein, we developed abiotic cascades using aminoacyl phosphate esters, the synthetic counterparts of biological aminoacyl adenylates, to drive sequential chemical reactions and self-assembly in a single pot. We demonstrated that the structural elements of amino acid side chains (aromatic versus aliphatic) significantly influence the reactivity and half-lives of aminoacyl phosphate esters, ranging from hours to days. This behavior, in turn, affects the number of couplings we can achieve in the network and the self-assembly propensity of activated intermediate structures. The cascades are constructed using bifunctional peptide substrates featuring side chain nucleophiles. Specifically, aromatic amino acids facilitate the formation of transient thioesters, which preorganized into spherical aggregates and further couple into chimeric assemblies composed of esters and thioesters. In contrast, aliphatic amino acids, which lack the ability to form such structures, predominantly undergo hydrolysis, bypassing further transformations after thioester formation. Additionally, in mixtures containing multiple aminoacyl phosphate esters and peptide substrates, we achieved selective product formation by following a distinct pathway that favors subsequent reactions through reactivity changes and self-assembly. By coupling chemical reactions with molecules of varying reactivity time scales, we can drive multiple reaction clocks with distinct lifetimes and self-assembly dynamics, facilitating precise temporal and structural regulation.

Introducing Phosphate Ester into DAPhen by Propyl Enhanced the Selectivity for UO22+ over Th4.

A new type of phenanthroline carboxamide(DAPhen)-phosphate ester ligand (L1/L2) was synthesized for the selective separation of U(VI) over Th(IV). Liquid-liquid extraction experiments showed that the introduction of phosphate ester could increase the extraction ability of ligands for U(VI), especially L2, which showed high selectivity for the separation of U(VI) over Th(IV). The slope analysis indicated that L1 could form 1:1 and 1:2 complexes with U(VI) and 1:1 complexes with Th(IV). NMR titration revealed that the DAPhen unit of ligands combined with one U(VI) to form 1:1 complexes, and then the phosphate ester unit of the 1:1 complexes further combined with another U(VI) to form 1:2 complexes. Ligands provide only the DAPhen unit to Th(IV) to form 1:1 complexes. The crystal structures found 1:2 complexes of L1 and U(VI), 1:1 complexes of L2 and U(VI), and 1:1 complexes of L1 and Th(IV). The larger stability constant (log β) of the 1:1 complexes of L2 with U(VI) than that of the 1:1 complexes of L1 with U(VI) showed that the binding ability of U(VI) with the DAPhen unit of L2 is stronger than that of U(VI) with the DAPhen unit of L1. This study provides new ideas for designing extractants with excellent properties.

Catalytic Hydrolysis of Paraoxon by Immobilized Copper(II) Complexes of 1,4,7-Triazacyclononane Derivatives.

Organophosphate neuroactive agents represent severe security threats in various scenarios, including military conflicts, terrorist activities and industrial accidents. Addressing these threats necessitates effective protective measures, with a focus on decontamination strategies. Adsorbents such as bentonite have been explored as a preliminary method for chemical warfare agent immobilization, albeit lacking chemical destruction capabilities. Chemical decontamination, on the other hand, involves converting these agents into non-toxic or less toxic forms. In this study, we investigated the hydrolytic activity of a Cu(II) complex, previously studied for phosphate ester hydrolysis, as a potential agent for chemical warfare decontamination. Specifically, we focused on a ligand featuring a thiophene anchor bound through an aliphatic spacer, which exhibited high hydrolytic activity in its Cu(II) complex form in our previous studies. Paraoxon, an efficient insecticide, was selected as a model substrate for hydrolytic studies due to its structural resemblance to specific chemical warfare agents and due to the presence of a chromogenic 4-nitrophenolate moiety. Our findings clearly show the hydrolytic activity of the studied Cu(II) complexes. Additionally, we demonstrate the immobilization of the studied complex onto a solid substrate of Amberlite XAD4 via copolymerization of its thiophene side group with dithiophene. The hydrolytic activity of the resultant material towards paraoxon was studied, indicating its potential utilization in organophosphate neuroactive agent decontamination under mild conditions and the key importance of surface adsorption of paraoxon on the polymer surface.

A novel, portable, and cost-effective turbidimetric sensor for sensitive alkaline phosphatase activity assay

The development of enzyme activity analysis methods is critical for precise and rapid assessments of enzyme activity levels within biological systems, facilitating a more profound comprehension of physiological functions and disease mechanisms. Alkaline phosphatase (ALP) participates in various physiological processes involving phosphate ester hydrolysis. Altered ALP activity levels are often indicative of different diseases, underscoring the necessity for accurate ALP activity determination in medical diagnostics. This study innovatively applies turbidity as a physical variable, proposing a turbidimetric sensor based on an enhanced ammonium molybdate reagent for phosphate analysis. By integrating this with the ALP substrate p-nitrophenyl phosphate, a turbidimetric sensor was devised and employed for ALP activity analysis. The proposed turbidimetric sensor demonstrated high sensitivity both for phosphate (0.18 μmol/L) and ALP activity (0.03 mU/mL) assay. In practical applications, this turbidimetric sensor has been effectively employed to detect ALP activity in mouse feces, showcasing its potential for auxiliary diagnosis of inflammatory bowel disease. Significantly, this novel turbidity-based approach offers not only swift and straightforward procedures but also remarkable portability and cost-efficiency. Requiring solely a handheld turbidimeter and eliminating the need for bulky instruments, this approach holds significant potential for point-of-care testing applications.

Highly efficient flame retardancy and fire spread behavior of rigid polyurethane foams with extremely low content of flame retardant

In recent years, flame-retardant rigid polyurethane foam (RPUF) has once again captured the scholars’ attention due to the growing the growing demands in the field of building energy efficiency. However, the inherent flammability of RPUF is high and the complexities of its flame-retardant mechanisms remain inadequately understood. In this study, a modified biomass material, amino starch phosphate ester was successfully synthesized which was then combined with expandable graphite (EG) and incorporated into RPUF. The research delved into the optimal ratio and minimal flame-retardant additive required to achieve the stringent UL-94 V-0 rating, while also thoroughly investigating the flame retardancy and thermal properties of the composite system. The findings revealed that with just 6 wt.% of flame retardants, the RPUF achieved the UL-94 V-0 rating, with a 41.1 % reduction in peak heat release rate (pHRR) and a 23.7 % decrease in total heat release (THR). Additionally, it diminishes the flame's size and width, leading to quicker extinction, while also lowering the internal combustion temperature of the polyurethane, thereby delaying both preheating and combustion times. The synergistic interaction between amino starch phosphate ester and EG during combustion results in the formation of a dense, continuous char layer, effectively inhibiting the pyrolysis and combustion of RPUF. This study provides a theoretical foundation for the development of efficient flame-retardant systems for RPUF.

A novel durable and soft cotton flame retardant containing phosphonamide phosphate ester with ammonium phosphonate group

A novel durable and soft cotton flame retardant containing phosphonamide phosphate ester with ammonium phosphonate group

A novel efficient flame-retardant curing agent for epoxy resin based on P-N synergistic effect: Bio-based benzoxazine phosphate ester

Most epoxy resins on the market have low thermal stability and flammable defects. As a potential curing agent for epoxy resin, polybenzoxazine (PBz) can effectively improve the thermal properties of the resin due to its low heat release capacity (HRC) and rigid aromatic ring support, and its raw materials can be derived from renewable resources. Here, we have successfully developed a molecular design strategy to obtain a trifunctional benzoxazine monomer with phosphate ester. Firstly, guaiacol-ethanolamine benzoxazine monomer (GE) was synthesized by Mannich condensation using guaiacol and ethanolamine as raw materials. Then trifunctional benzoxazine phosphate ester (TBP) was synthesized by the nucleophilic reaction of GE with phosphorus oxychloride. Finally, the epoxy resin DGEBA was cured by TBP to obtain a PBz modified epoxy resin (EP-TBP polymer) with Tg of 113.7 °C and char yield of 37.4 %. Due to the introduction of TBP rich in phosphorus and nitrogen, it releases phosphorus radicals and nitrogen-containing inert gases during combustion, which leads to quenching effect and dilution effect. In addition, TBP can also promote the dehydration and dehydrogenation of the polymer and accelerate the formation of the aromatic hybrid char layer. Therefore, the THR of TBP modified epoxy resin is 49.3 % lower than that of epoxy resin without TBP, and the char yield is 47 times higher. And when the phosphorus content is 1.76 %, the flame-retardant grade can reach V-0. In addition, the introduction of TBP also enhanced the mechanical properties, adhesion properties and hydrophobicity properties of the polymer. It is worth mentioning that under alkaline conditions, the phosphate ester in the structure of EP-TBP polymer will undergo ammonolysis reaction with ethanolamine, and the resulting oligomers will be dissolved in it, thereby achieving rapid degradation of EP-TBP polymer. This work is to develop a high-performance multifunctional epoxy resin flame retardant curing agent based on renewable raw materials, and provide important insights for the subsequent development of halogen-free bio-based PBz flame retardant materials.

Improving oral absorption of a rapidly crystallizing parent drug using prodrug strategy: Comparison of phosphate versus glycine based prodrugs

With an increasing number of Biopharmaceutical Classification System (BCS) II/IV pipeline compounds, solubilizing and supersaturating formulation strategies are becoming prevalent. Beyond formulation and solid form strategies, prodrugs are also employed to overcome solubility-limited absorption of poorly water-soluble compounds. Prodrugs can potentially yield supersaturated systems upon conversion to the parent drug intraluminally and thus enhance absorption. However, supersaturation also increases the driving force for crystallization, resulting in low solution concentrations, which can potentially negate the advantage of prodrugs. In this work, two unique solubility-enhancing prodrugs, phosphate and glycine esters, were investigated for a rapidly crystallizing parent drug. Ex vivo absorption studies using rat tissue and in vivo studies in dogs were performed. Conversion rate of the phosphate prodrug to the parent was dependent on the milieu and increased ∼24-fold in the presence of intestinal contents as medium and tissue relative to neat buffer. In contrast, conversion of the glycine prodrug was minimal under any conditions tested, suggesting that the conversion occurs after absorption into the enterocytes. Phosphate prodrug showed a non-linear increase in parent drug absorptive flux across rat intestinal tissue with concentration when intestinal contents were used as donor media. This was attributed to rapid conversion and high supersaturation of the parent drug which subsequently resulted in crystallization at high doses in the donor chamber. Glycine prodrug did not undergo complete conversion at high doses and was absorbed unchanged on the basolateral side, indicating saturation of the converting enzymes in the enterocytes. The combined flux (parent drug and glycine) showed a linear increase with dose and crystallization was not observed. Under physiological conditions, glycine prodrug that is absorbed unchanged from the intestine can potentially undergo complete conversion in hepatocytes after absorption and make the parent drug systemically available. Thus, glycine prodrug provided overall higher absorption compared to phosphate prodrug. The observed flux levels for both the prodrugs were higher compared to the parent drug alone, highlighting an advantage to use of a prodrug strategy to improve absorption of such compounds. Oral dosing in a dog PK study revealed that the bioavailability using the phosphate prodrug was ∼50% whereas, it was ∼100% with glycine prodrug, supporting the in vitro observations.

Rapid hydrolysis rates of thio- and phosphate esters constrain the origin of metabolism to cool, acidic to neutral environments

Rapid hydrolysis rates of thio- and phosphate esters constrain the origin of metabolism to cool, acidic to neutral environments

Intelligent Supramolecular Modification for Implants: Endogenous Regulation of Bone Defect Repair in Osteoporosis.

Addressing osteoporosis-related bone defects, a supramolecular strategy is innovated for modifying carbon fiber reinforced polyether ether ketone (CF/PEEK) composites. By covalently attaching intelligent macromolecules via in situ RAFT polymerization, leveraging the unique pathological microenvironment in patients with iron-overloaded osteoporosis, intelligent supramolecular modified implant surface possesses multiple endogenous modulation capabilities. After implantation, surface brush-like macromolecules initially resist macrophage adhesion, thereby reducing the level of immune inflammation. Over time, the molecular chains undergo conformational changes due to Fe (III) mediated supramolecular self-assembly, transforming into mechanistic signals. These signals are then specifically transmitted to pre-osteoblast cell through the binding capacity of the KRSR short peptide at the molecular terminus, induced their osteogenic differentiation via the YAP/β-catenin signaling axis. Furthermore, osteoblasts secrete alkaline phosphatase (ALP), which significantly hydrolyzes phosphate ester bonds in surface macromolecular side groups, resulting in the release of alendronate (ALN). This process further improves the local osteoporotic microenvironment. This intelligent surface modification tailors bone repair to individual conditions, automatically realize multiple endogenous regulation once implanted, and truly realize spontaneous activation of a series of responses conducive to bone repair in vivo. It is evidenced by improved bone regeneration in iron-overloaded osteoporotic rabbits and supported by in vitro validations.

Aryl phosphate ester-induced pericardial edema in zebrafish embryos is influenced by the ionic composition of exposure media

Pericardial edema – fluid accumulation within the pericardium – is a frequently observed malformation in zebrafish embryo-based chemical toxicity screens. We recently discovered that the severity of triphenyl phosphate (TPHP)-induced pericardial edema was dependent on the ionic strength of exposure media. TPHP is an aryl phosphate ester (APE) widely used as a plasticizer and flame retardant. APEs are characterized by having one or more aryl groups bound to a phosphate center, with TPHP containing only unsubstituted aryl groups. Therefore, the objective of this study was to begin investigating whether, similar to TPHP, pericardial edema induced by other structurally related APEs is dependent on the ionic composition of exposure media. We first mined the peer-reviewed literature to identify other APEs that 1) induced pericardial edema in zebrafish embryos within a minimum of three peer-reviewed publications, and 2) demonstrated a statistically significant induction of pericardial edema in at least 70 % of the studies evaluated. Based on this meta-analysis, we identified four other APEs that caused pericardial edema in zebrafish embryos: isopropylated triphenyl phosphate (IPTPP), cresyl diphenyl phosphate (CDP), tricresyl phosphate (TMPP), and 2-ethylhexyl diphenyl phosphate (EDHPHP). Using TPHP as a positive control and pericardial edema as a readout, we developed concentration-response curves for all four APEs based on static exposure from 24 to 72 h post-fertilization (hpf). We then conducted co-exposures with D-Mannitol (an osmotic diuretic) and exposures within reverse osmosis (RO) water determine whether the ionic composition of exposure media mitigated APE-induced pericardial edema at 72 hpf. Using pericardial edema as an endpoint, the approximate EC50s for TPHP (positive control), IPTPP, CDP, TMPP, and EDHPHP were 6.25, 3.125, 3.125, 25, and 100 µM, respectively, based on exposure from 24 to 72 hpf. Interestingly, similar to our findings with TPHP, co-exposure with D-Mannitol and exposure within ion-deficient water significantly mitigated IPTPP- CDP-, TMPP-, and EDHPHP-induced pericardial edema in zebrafish embryos, suggesting that chemically-induced pericardial edema may be 1) dependent on the ionic composition of exposure media and 2) driven by a disruption in osmoregulation across the embryonic epidermis. Therefore, similar to other assay parameters, our findings underscore the need to standardize the osmolarity of exposure media in order to minimize the potential for false positive/negative hits in zebrafish embryo-based chemical toxicity screens conducted around the world.

Synthesis and characterization of the dental adhesive monomer 10-MDP

Many studies have demonstrated the excellent performance of 10-MDP (10-methacryloyloxydecyl dihydrogen phosphate) as a functional monomer for dental adhesive materials and as a primer for ceramic surfaces. Although adhesive performance is affected by the purity level of 10-MDP, this parameter is rarely described, and possible byproducts have been suggested in the literature, but have not been identified to date. The present study aims to present an accessible 10-MDP synthesis strategy with easily handled reagents and address the characterization challenges, especially in identifying byproducts. 10-MDP was synthesized from 10-hydroxydecyl methacrylate and phosphorus pentoxide in acetone. The final product was characterized by nuclear magnetic resonance (NMR), infrared spectroscopy (FTIR) and mass spectrometry MALDITOF/TOF. The main chemical groups associated with 10-MDP were identified by 1H, 31P, and 13C NMR analyses. Only mass spectrometry analyses (MALDITOF/TOF) could identify the presence of dimers as byproducts. Its proposed chemical structure indicates that the dimers were formed by the reaction between the phosphate ester groups and others formed by the reaction of the methacrylic group of 10-MDP molecules. Careful adjustment of the synthesis conditions to reduce the formation of these byproducts is also described. The results indicate that the characterization of 10-MDP batches as raw materials is an important task because, depending on the byproduct present, its ability to polymerize or acid etching capacity may be compromised.

Effect of Electric Fields on the Decomposition of Phosphate Esters.

Phosphate esters decompose on metal surfaces and form protective polyphosphate films. For many applications, such as in lubricants for electric vehicles and wind turbines, an understanding of the effect of electric fields on molecular decomposition is urgently required. Experimental investigations have yielded contradictory results, with some suggesting that electric fields improve tribological performance, while others have reported the opposite effect. Here, we use nonequilibrium molecular dynamics (NEMD) simulations to study the decomposition of tri-n-butyl phosphate (TNBP) molecules nanoconfined between ferrous surfaces (iron and iron oxide) under electrostatic fields. The reactive force field (ReaxFF) method is used to model the effects of chemical bonding and molecular dissociation. We show that the charge transfer with the polarization current equalization (QTPIE) method gives more realistic behavior compared to the standard charge equilibration (QEq) method under applied electrostatic fields. The rate of TNBP decomposition via carbon-oxygen bond dissociation is faster in the nanoconfined systems than that in the bulk due to the catalytic action of the surfaces. In all cases, the application of an electric field accelerates TNBP decomposition. When electric fields are applied to the confined systems, the phosphate anions are pulled toward the surface with high electric potential, while the alkyl cations are pulled to the surface with lower potential, leading to asymmetric film growth. Analysis of the temperature- and electric field strength-dependent dissociation rate constants using the Arrhenius equation suggests that, on reactive iron surfaces, the increased reactivity under an applied electric field is driven mostly by an increase in the pre-exponential factor, which is linked to the number of molecule-surface collisions. Conversely, the accelerated decomposition of TNBP on iron oxide surfaces can be attributed to a reduction in the activation energy with increasing electric field strength. Single-molecule nudged-elastic band (NEB) calculations also show a linear reduction in the energy barrier for carbon-oxygen bond breaking with electric field strength, due to stabilization of the charged transition state. The simulation results are consistent with experimental observations of enhanced and asymmetric tribofilm growth under electrostatic fields.

Understanding the impact of pre-digestion thermal hydrolysis process on PFAS in anaerobically digested biosolids

Per- and poly-fluoroalkyl substances (PFAS) present in biosolids are influenced by their source, treatment processes, and the dynamics of water resource recovery facilities (WRRF). Understanding these effects is vital for informed decisions in treatment process selection, however, comprehensive studies are sparse. This study examined the impact of anaerobic digestion (AD) and the addition of a thermal hydrolysis process (THP) before AD on PFAS in the solids stream at a WRRF. Targeted analysis of 58 PFAS (linear and branched) and suspect screening of the solid stream before and after AD as well as THP, with the total PFAS (ΣPFAS) concentrations ranging between 244 and 566 μg/kgdw. Precursor and intermediate PFAS, mainly di-substituted polyfluoroalkyl phosphate esters (diPAPs) followed by fluorotelomer carboxylic acids (FTCAs), were the dominant contributors (62–96 mol % ΣPFAS) in all 5 sample types. AD impacts were observed both before and after deploying THP altering the relative contribution of different PFAS classes through biotransformation, with an increase in PFCAs and a decrease in diPAPs. However, we observed that THP reduced the % of precursor conversion as well as conversion of the FTCA intermediates in the AD process as evidenced by a substantial increase in FTCAs post-THP + AD and lower PFCA generation compared to AD only. Total PFAS organofluorine (∑FPFAS) decreased by 28% pre- and post-AD, which on total fluorine (TF) showed a larger reduction to 43%. Fluoride was <3% of the TF in all cases, thus, the greater reduction in TF vs ∑FPFAS could be volatile losses of PFAS and other non-PFAS F-containing molecules. After THP installation, a 32% decrease in (∑FPFAS) was observed in the combined THP-AD system whereas adjusted total organofluorine increased by ∼43%. Overall, achieving higher solids handling capacity and energy neutrality with the THP addition did not lead to a significant difference in quantifiable PFAS concentrations compared to AD-only.

Rate of hydrolysis of the phosphate esters of B vitamins is reduced by zinc deficiency: Invitro and invivo.

Extracellular hydrolysis of the phosphate esters of B vitamins (B1, B2, and B6) is crucial for their cellular uptake and metabolism. Although a few zinc-dependent enzymes have been implicated in these processes, their exact mechanisms of action remain largely unknown. This study investigated the potential involvement of phosphate group hydrolyzing enzymes in the hydrolysis of B vitamin phosphate esters. We evaluated enzyme activity in membrane lysates prepared from cells transiently transfected with these enzymes or those endogenously expressing them. Specifically, we investigated how zinc deficiency affects the rate of hydrolysis of B vitamin phosphate esters in cellular lysates. Assessment of the activities of zinc-dependent ectoenzymes in the lysates prepared from cells cultured in zinc-deficient conditions and in the serum of rats fed zinc-deficient diets revealed that zinc deficiency reduced the extracellular hydrolysis activity of B vitamin phosphate esters. Furthermore, our findings explain the similarities between several symptoms of B vitamin and zinc deficiencies. Collectively, this study provides novel insights into the diverse symptoms of zinc deficiency and could guide the development of appropriate clinical strategies.

Phosphate ester-linked carbonized polymer nanosheets to limit microbiological contamination in aquaculture water

In this study, we developed a simple, low-temperature method to synthesize carbonized polymer nanosheets (CPNSs) using sodium alginate, a biopolymer derived from algae, and diammonium hydrogen phosphate. These nanosheets are produced through a solid-state pyrolysis at 180 °C, involving dehydration, cross-linking through phosphate ester bonds, and subsequent carbonization, forming 2D structured CPNSs. These synthesized CPNSs exhibit excellent bacterial adsorption capabilities, particularly against V. parahaemolyticus and S. aureus. When applied to ordinary filter paper, the CPNS-modified paper efficiently filters bacteria from aquaculture water, removing over 98% of V. parahaemolyticus within two hours and maintaining effectiveness after 24 h. In contrast, control filter paper showed significantly reduced efficiency over the same period. Our filtration tests demonstrated enhanced survival rates for shrimp in aquaculture systems, highlighting the potential of CPNSs-modified filter paper as a suitable treatment to reduce the microbiological contamination levels in recirculating aquaculture systems in the event of a disease outbreak.

Per- and polyfluoroalkyl substances behavior: Insights from autothermal thermophilic aerobic digestion - Storage nitrification-denitrification reactors

Per- and polyfluoroalkyl substances (PFAS) have emerged as significant environmental contaminants due to their persistence, bioaccumulative properties, and potential adverse impacts on health and ecosystems. Water Resource Recovery Facilities (WRRFs) play a crucial role in the management of PFAS, given their widespread presence in consumer products and subsequent reintroduction into the environment. This study investigated the dynamics of PFAS within the solids stream treatment processing that utilized autothermal thermophilic aerobic digestion (ATAD) followed by a storage nitrification-denitrification reactor (SNDR). PFAS analysis included 60 PFAS analyzed via liquid chromatography-triple quadrupole time-of-flight mass spectrometry of pre-ATAD, post-ATAD, and post-SNDR samples. Complexities such as volatile solids loss during the treatment processes were considered in assessing the effect of ATAD and SNDR on PFAS concentrations. Significant changes were observed in the relative contributions of various PFAS classes throughout the treatment processes due to biotransformation; similar changes were reflected in both 2019 and 2021. The relative contribution of perfluoroalkyl alkyl acids (PFAAs) increased while phosphorus-containing PFAS (e.g., di-substituted polyfluoroalkyl phosphate esters) and fluorotelomer carboxylic acids decreased. Shorter-chain PFAAs were enriched during ATAD, whereas most PFAS increased during SNDR except diPAPs and FTCAs, reflecting treatment conditions' impact. Overall, minor decreases in total PFAS concentrations during ATAD as well as SNDR were observed and hypothesized to be due to enhanced biotransformation to ultra-short PFAS that were not quantified. Even with up to 60 PFAS quantified in the samples, PFAS accounted for <1% of the total fluorine with <2% of that total fluorine being fluoride prompting interest in additional exploration.

Integrated design of flame retardancy, smoke suppression and structure of carbon fiber reinforced vinyl ester resin composites through intercalation of nanofiber membranes

A novel flame-retardant method based on the intercalation of nanofiber flame-retardant membrane has been studied for composite laminates. Compared to traditional additive flame-retardant method, this method is more efficient, does not affect the composite forming process, and can improve the mechanical properties of composite. Nanofiber flame-retardant membranes (FPm) are prepared from polyether sulfone (PES) and pentaerythritol phosphate ester (PEPA) by electrospinning technique and inserted in the interlayer of carbon fiber reinforced vinyl ester resin (CF/VER) composites. The FPm can improve the flame-retardancy and smoke suppression of the CF/VER composites by promoting the charring of interlayer structure and form a barrier layer. The thickness of the FPm and the flame-retardant performance of the composites are positive correlation. At a FPm’s thickness of 50 μm, the limiting oxygen index (LOI) and UL-94 ratings of the CF/VER composites reached 33.5 % and V-1, respectively. The total heat release (THR) and total smoke release (TSP) are reduced by 26.4 % and 30.4 %, respectively. Due to the interlayer enhancement effect of FPm, the mechanical strength and interlaminar fracture toughness of CF/VER composites are also improved. Especially, when the thickness of FPm is 30 μm, the mode I interlaminar fracture toughness (GIC) of the CF/VER composite increased by 17.4 %. while the flexural strength, interlayer shear strength (ILSS), mode II interlaminar fracture toughness (GIIC) and storage modulus (E’) are all enhanced.

Rhizosphere microbial roles in phosphorus cycling during successive plantings of Chinese fir plantations

The rhizosphere, a critical interface involving soil, plant roots, and microorganisms, plays a vital role in the feedback processes between plants and soil, especially under phosphorus (P) limiting conditions typical of subtropical forests. This study used a chronosequence design to investigate first-fourth successive planting rotations of Chinese fir (Cunninghamia lanceolata) plantations in Fujian Province, China, with stands around 17 years old. We employed a modified P fractionation assay and metagenomic sequencing to explore P cycling in the rhizosphere across different plantation rotations. Rhizosphere labile P concentrations increased significantly in the fourth rotation, alongside a consistent upward trend in moderately labile P throughout successive plantings. Conversely, stable P and residual P concentrations declined during successive plantings, signaling a shift toward more accessible P forms. From metagenomic analyses, the proportion of P transport processes (transportation of phosphonate, phosphate, and inorganic phosphate) gradually increased. Notably, abundances were significantly higher in the rhizosphere soil of the fourth Chinese fir planting rotation of the K01126 gene (involved in phosphate ester mineralization), the phnD gene (associated with phosphonate transport), functional genes related to the solubilization of inorganic phosphate, such as pqqB, pqqC, pqqE, and ppa, and the phoB gene (linked to P-starvation response regulation). The results indicate that functional microbes of the rhizosphere, dominated by Proteobacteria and Acidobacteria, are instrumental in changing P cycling processes during successive plantings. The successive planting rotations of Chinese fir plantations significantly and positively impacted on the gene abundance related to the activation and uptake of P in the rhizosphere. Based on these insights, specific strategies, such as regular monitoring and application of phosphate fertilizer and adjusting rotation timing based on the soil rhizosphere P status, and incorporating native broad-leaved tree species are suggested to promote efficient P cycling, thus supporting sustainable forest management practices.

Crucial role of extracellular polymeric substances from anammox sludge in wastewater phosphorus recovery via magnesium phosphate crystallization

The magnesium phosphate (Mg-P) crystallization based on anaerobic ammonia oxidation is of interest for simultaneous nitrogen and phosphorus removal in wastewater treatment due to cost-effectiveness. Understanding the role of extracellular polymeric substances (EPS) in crystal growth is pivotal for bio-induced Mg-P crystallization. In this work, the effects of EPS in Mg-P crystallization were thoroughly investigated. Results indicated that EPS decreased the initial crystallization rate but slightly improved the final crystallization yield. The maximum removal efficiencies of Mg and P ions increased by 2.8 % and 3.1 %, respectively, when EPS concentration was 80 mg/L. Additionally, the presence of EPS enhanced Mg3(PO4)2·10 H2O production and facilitated the formation of larger rhombic plate-like structures crystals (maximum particle size increased by 215 %). Analysis of EPS composition changes during the crystallization process and characterization of the final crystals suggested that tryptophan-like proteins preferentially involved in the Mg-P crystallization process, while β-sheet proteins potentially influencing crystal morphology. Furthermore, the formation of phosphate ester groups, hydrogen bonding, and COOH-Mg2+ complexes were considered triggering factors for the interaction between EPS and Mg-P crystals. This study elucidated the underlying mechanism of EPS on Mg-P crystallization, further enhancing the understanding of the interaction between inorganic mineralization processes and microorganisms.