Phosphate Anions Research Articles

Coassembly of a Hybrid Synthetic-Biological Chitosan-g-Poly(N-isopropylacrylamide) Copolymer with DNAs of Different Lengths.

Natural polysaccharides can serve as carriers of genes owing to their intrinsic biocompatibility, biodegradability, and low toxicity. Additionally, they can be easily chemically modified, e.g., through grafting, leading to hybrid synthetic-biological copolymers with additional functionalities. In this work we report on the electrostatic interaction between a chitosan-g-poly(N-isopropylacrylamide) (Chit-g-PNIPAM) copolymer and DNA macromolecules of different lengths (i.e., 50 and 2000 bp), towards the construction of polyplexes that can serve as potential gene delivery systems. At the basic science level, the work aims to elucidate the effects of DNA length on the structural and physicochemical properties of the thermoresponsive hybrid macromolecular assemblies. The protonated amino groups on the chitosan backbone enable electrostatic binding with the anionic phosphate groups of the DNA molecules, while the PNIPAM side chains are expected to impart thermoresponsive properties to the formed polyplexes. Different amino to phosphate group (N/P) mixing ratios were examined, aiming to produce stable dispersions. The physicochemical properties of the resulting polyplexes were investigated by dynamic and electrophoretic light scattering (DLS and ELS), while their morphology was studied by scanning-transmission electron microscopy (STEM). Moreover, their response to changes in temperature and ionic strength, as well as their stability against biological media, was also examined. Finally, the binding affinity of the copolymer towards DNA was evaluated through fluorescence spectroscopy, using ethidium bromide quenching assays, while infrared spectroscopy was used to investigate the structure of the incorporated DNA chains.

Surface Coating of ZIF-8 Nanoparticles with Polyacrylic Acid: A Facile Approach to Enhance Chemical Stability for Biomedical Applications.

Nanoparticles of zeolitic imidazole framework-8 (ZIF-8 NPs), which are the subclass of metal-organic frameworks consisting of Zn ion and 2-methylimidazole, have been identified as promising drug carriers since their large microporous structure is suited for encapsulating hydrophobic drug molecules. However, one of the limitations of ZIF-8 NPs is their low stability in physiological solutions, especially in the presence of water and phosphate anions. These molecules can interact with the coordinatively unsaturated Zn sites at the external surface to induce the degradation of ZIF-8 NPs. In this study, herein a facile approach is reported to enhance the chemical stability of ZIF-8 NPs by surface coating with polyacrylic acid (PAA). The PAA-coated ZIF-8 (PAA-ZIF-8) NPs are prepared by mixing ZIF-8 NPs and PAA in water. PAA coating inhibits the degradation of ZIF-8 NPs in water as well as phosphate-buffered saline over 6 days, which seems to be due to the coordination of carboxyl groups of PAA to the reactive Zn sites. Furthermore, the PAA-ZIF-8 NPs loaded with the anticancer drug doxorubicin (Dox) show cytotoxicity in human colon cancer cells. These results clearly show the feasibility of the PAA coating approach to improve the chemical stability of ZIF-8 NPs without impairing their drug delivery capability.

The role of iron(II) excess and phosphate to synthesize hydroxychloride green rust

Green rust (GR) is a chemically reactive mineral of interest for environmental remediation. However, the lack of stability of this compound is a major drawback for practical applications. In this study, the precipitation of hydroxychloride green rust type 1 (GR1Cl) from soluble FeII and FeIII species was studied by analyzing pH titration curves and employing XRD, Raman and Mössbauer spectroscopies to find optimal conditions for synthesizing GR1Cl. Using the stoichiometric condition for FeII-FeIII corresponding to the [FeII3FeIII(OH)8]Cl compound, FeIIIO(OH)2.9Cl0.1 was formed in a first step during the addition of NaOH and then transformed into a mixture of GR1Cl and Fe3O4. The addition of phosphate anions (PO4) at a molar ratio PO4: Fe = 1: 10 in the initial solution was shown to avoid the formation of undesired magnetite. Interestingly, GR1Cl was also the only product without adding PO4 using an excess of FeII species in solution, i.e. for an initial ferric molar fraction x = FeIII: Fetot of 0.2. First experimental evidences of a hydroxyphosphate green rust type 2 GR2PO4 were also provided by XRD and Raman spectroscopy. Therefore, this work may attract interest for a better understanding of the geochemical cycle of iron and phosphate in natural environments such as hydromorphic soils or hydrothermal chimneys where fougerite, the mineral homologue of synthetic GR, is supposed to play a significant role.

Unexpected nanoscale CeO2 structural transformations induced by ecologically relevant phosphate species

In the present study, the dissolution and microstructural transformation of CeO2 nanoparticles (NPs) in a phosphate-containing milieu were investigated. The dissolution behaviour of 2 nm and 5 nm CeO2 NPs in phosphate buffer solutions was found to differ markedly from that observed in 0.01 M NaClO4. Through synchrotron X-ray diffraction analysis and X-ray absorption spectroscopy, the interaction between CeO2 NPs and phosphate species was examined, revealing the transformation of the oxide into sodium-cerium double phosphate, with cerium predominantly existing in the Ce(IV) state. According to scanning and transmission electron microscopy observations, thus formed Na-Ce(IV) phosphate consists of spindle-like aggregates of nanocrystalline rods, presumably formed during phosphate anions sorption on the initial CeO2 surface. Pair distribution function analysis revealed that Na-Ce(IV) phosphate has a three-dimensional framework crystal structure, similar to NaTh2(PO4)3, as reported earlier, with large channels along the c-axis containing disordered sodium atoms. This study represents the first detailed analysis of phosphate-induced speciation and microstructural transformation of CeO2 NPs, resulting in the formation of Ce(IV) phosphate. Similar processes may occur in natural ecosystems upon the introduction of CeO2 NPs.

Ion-chromatographic determination of common anions in drinking water in some regions of the Republic of Armenia

The present study investigated the anion composition of drinking water from various cities and villages in Armenia, including spring water and tap water samples. The simultaneous separation was achieved for fluoride, chloride, bromide, nitrite, nitrate, sulfate, and phosphate anions with the correlation coefficients >0.998. Validation of the method was carried out in accordance with the requirements of guidelines in terms of selectivity, specificity, system suitability, linearity, accuracy, precision, lower limits of detection and quantitation, robustness, and stability. The method was suitable for routine drinking water quality assessment in line with the national or World Health Organization (WHO) regulations. The validated method was further used to analyze drinking water samples from different regions of Armenia. The observed concentrations for the anions in drinking water complied with the WHO limits for drinking water with some exceptions. The test method can be submitted to quality control laboratories as a convenient and practical tool for routine analysis and monitoring studies.

Co-Delivery of Renal Clearable Cerium Complex and Synergistic Antioxidant Iron Complex for Treating Sepsis.

The mononuclear phagocytic system clears the circulating inorganic nanomaterials from the bloodstream, which raises concerns about the chronic toxicity of the accumulated metal species. A better understanding of the behavior of each metal after systemic injection is thus required for clinical translations. This study investigates the significance of the metal-ligand interaction on the accumulation of cerium and demonstrates that only the form in which cerium is coordinated to a multidentate chelator with a strong binding affinity does not accumulate in major organs. Specifically, cerium complexed with diethylenetriamine pentaacetic acid (DTPA) forms renally excretable nanoparticles in vivo to circumvent the leaching of cerium ions, whereas weakly coordinated cerium-based nanomaterials produce insoluble precipitates upon encountering physiological phosphate anions. Ceria-based renally clearable nanoparticles (CRNs) derived from cerium-DTPA are utilized as the antioxidant pair with iron-DTPA, in which their combination leverages the Fenton reaction to synergistically scavenge hydrogen peroxide. This reduces the gene expression of pro-inflammatory factors in the macrophages activated with lipopolysaccharide as well as improves the survival rate of septic mice by alleviating the systemic inflammatory response and its downstream tissue injury in the liver, spleen, and kidneys. This study demonstrates that CRNs combined with iron-DTPA can be utilized as nonaccumulative nanomedicines for treating systemic inflammation, thereby overcoming the limitations of conventional ceria nanoparticle-based treatments.

Cellular Phosphate Sensing and Anion Binding by an Azacrown-Calixpyrrole Hybrid.

A hybrid receptor-sensor for anions originating from the merging of positively charged ammonium moieties for electrostatic attraction/stronger binding of azacrowns with directionality of calixpyrrole hydrogen bond donors for selectivity is investigated. As demonstrated this hybrid receptor-sensor shows a remarkable selectivity for orthophosphate even in the presence of other phosphates and anions found in cellular materials (Kassoc H2PO4 ->H2P2O7 2->AMP-≫ADP2- or ATP3- over halides, nitrate, or hydrogen sulfate; all Na+ salts in water) but also cellular polyphosphate or phospholipids. This selectivity is harnessed in a real-time monitoring of cell lysis by lysozyme, which releases orthophosphate and other phosphates and anions from the cells. This sensitive (LOD 0.4 μM) fluorescence-based microscale method compares favorably with the state-of-the-art techniques but can easily be practiced in a high-throughput screening (HTS) manner. The anion binding and selectivity in aqueous solutions were investigated by NMR and put in context with phosphate binding of the parent calix[4]pyrrole. The microscopic understanding of anion binding by the hybrid receptor was then obtained from a combination of density functional theory (DFT), classical molecular dynamics (MD) with explicit water solvation, and ab initio MD (AIMD) simulations. Correlating the NMR and fluorescence binding data with studies of solvation of the receptor, phosphate anion, and the resulting complex confirms the binding is largely driven by entropic component (TΔS) associated with receptor and anion desolvation.

Neodymium-Facilitated Visualization of Extreme Phosphate Accumulation in Fibroblast Filopodia: Implications for Intercellular and Cell–Matrix Interactions

A comprehensive understanding of intercellular and cell–matrix interactions is essential for advancing our knowledge of cell biology. Existing techniques, such as fluorescence microscopy and electron microscopy, face limitations in resolution and sample preparation. Supravital lanthanoid staining provides new opportunities for detailed visualization of cellular metabolism and intercellular interactions. This study aims to describe the structure, elemental chemical, and probable origin of zones of extreme lanthanoid (neodymium) accumulation that form during preparation for scanning electron microscopy (SEM) analysis in corneal fibroblasts filopodia. The results identified three morphological patterns of neodymium staining in fibroblast filopodia, each exhibiting asymmetric staining within a thin, sharp, and extremely bright barrier zone, located perpendicular to the filopodia axis. Semi-quantitative chemical analyses showed neodymium-labeled non-linear phosphorus distribution within filopodia, potentially indicating varying phosphate anion concentrations and extreme phosphate accumulation at a physical or physicochemical barrier. Phosphorus zones labeled with neodymium did not correspond to mitochondrial clusters. During apoptosis, the number of filopodia with extreme and asymmetric phosphorus accumulation increases. Supravital lanthanoid staining coupled with SEM allows detailed visualization of intercellular and cell–matrix interactions with high contrast and resolution. These results enhance our understanding of phosphate anion accumulation and transfer mechanisms in cells under normal conditions and during apoptosis.

Adsorption of Cr(VI) and phosphate anions by amino-functionalized palm oil fibers.

This work developed a novel sustainable adsorbent (PF-Aq) prepared by the amino-functionalization of palm oil fibers (PF). XPS, SEM/EDS, TGA/DSC, and FT-IR techniques proved the successful functionalization of the PF with the amino group. The PF-Aq adsorbent presents a high adsorption capacity for phosphate and Cr(VI) ions. Adsorption kinetics of the ions onto the PF-Aq followed the general-order models, with 240- and 300-min equilibrium times for phosphate and Cr(VI), respectively. The Freundlich equilibrium model can explain the adsorption of phosphate and Cr(VI) on the PF-Aq. Besides, the maximum adsorption capacities were 151.07mgg-1 for phosphate and 206.08mgg-1 for Cr(VI). The best pH for the adsorption of both ions on PF-Aq was 4.0. Interestingly, adsorption was exothermic for phosphate and endothermic for Cr(VI). The adsorption capacities were reduced by 16% for phosphate and 10% for Cr(VI) after 5 adsorption-desorption cycles, demonstrating the good recyclability of the PF-Aq. It can be concluded that PF-Aq is a relevant adsorbent to uptake phosphate and Cr(VI) from water due to its high adsorption capacity, low cost, recyclability, availability, and fast kinetics. Finally, the excellent adsorption potential results from inserting amino groups in the PF, allowing electrostatic interactions between adsorbent and adsorbate.

Molecular insight into the dissolution-degradation process of cellulose bunch in ionic liquids

Ionic liquids (ILs) as green solvents have been utilized in dissolving cellulose and fabricating regenerated cellulose fibers. Imidazolium-based ILs with acetate or phosphate anions present advantage, due to the low viscosity and melting point, as well as its excellent ability to form hydrogen bonds (H-bonds) with the hydroxyl groups of cellulose chains. In this work, the microscopic dissolution processes of a cellulose bunch in four ILs were reproduced via molecular dynamics (MD) simulations. The cellulose bunch dissolution capabilities of these four ILs are [Emim][OAc] > [Emim][DMP] > [Emim][DEP] > [Bmim][DMP], as verified through in-situ polarized optical microscope. It is important to note that cellulose may degrade in some ILs during dissolution, affecting the performance of regenerated cellulose, while the underlying mechanism is unclear, and the strength of H-bonds formed between ILs and cellulose chains can reflect their degradation strength Combined with density functional theory (DFT) calculations, the H-bonds formed between different anions and cellulose hydroxyl groups were analyzed in depth and the order of H-bond strength is [OAc]− > [DEP]− > [DMP]−, which is different from the dissolution order of cellulose bunch in [Emim][DEP] and [Emim][DMP]. Further analysis revealed that the difference in diffusion coefficients leads to faster dissolution of cellulose in [Emim][DMP]. This study elucidates the dissolution and degradation processes of cellulose in ILs at the molecular level, offering theoretical insights crucial for the development of novel ILs that are efficient in the process of cellulose spinning.

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.

Enhanced phosphate anion flux through single-ion, reverse-selective mixed-matrix cation exchange membrane

Phosphate recovery from wastewater is vital for both environmental sustainability and resource conservation, offering the dual benefit of reducing phosphate pollution while providing a valuable source of this essential nutrient. We previously reported an approach for synthesizing hydrous manganese oxide (HMO) nanoparticles within a polymeric cation-exchange membrane (CEM) to achieve a phosphate-selective mixed-matrix membrane (PhSMMM); however, the phosphate flux was lower than desired. Herein, we demonstrate a next-generation PhSMMM membrane with enhanced phosphate flux and selectivity. Experimental results confirm the successful incorporation of up to 28 wt% HMO nanoparticles into the polymeric CEM. The new PhSMMM exhibits a phosphate flux of 1.57 mmol∙m–2.hr–1 (an 8.5X enhancement), with selectivity over chloride, nitrate, and sulfate ions of 9, 11, and 104, respectively. This significant enhancement in phosphate flux marks a promising advancement in a sustainable solution for phosphate removal and recovery from wastewater.

Effect of Inorganic Anions on the Structure of Alkali-Activated Blast Furnace Slag

Analyzing the effect of anions on the structure of geopolymers is crucial because anions can significantly influence the material’s chemical stability, mechanical properties, and long-term durability. Understanding these effects helps optimize geopolymer compositions for various applications, such as construction materials and waste encapsulation. This research report describes the effects of nitrate, sulfate, and phosphate anions on alkali-activated blast furnace slag’s structural integrity and properties. Advanced techniques like XRD, FT-IR, Raman spectroscopy, and XPS have been employed to analyze structural modifications caused by anions, providing insights into their interactions and effects. These anions generally decrease compressive strength by disrupting geopolymerization and altering microstructure. For example, sulfate ions lead to the formation of ettringite, while phosphate ions bind calcium into separate phases. We can also observe microstructural changes, such as increased porosity with phosphate, which significantly reduces strength. Nitrate’s effect is less detrimental but still influences the overall structural dynamics.

Alternative lipid synthesis in response to phosphate limitation promotes antibiotic tolerance in Gram-negative ESKAPE pathogens.

Gram-negative ESKAPE pathogens, including A cinetobacter baumannii , are responsible for a dramatic increase in the morbidity and mortality of patients in healthcare settings over the past two decades. Infections are difficult to treat due to antibiotic resistance and tolerance; however, broadly conserved mechanisms that promote antibiotic treatment failure have not been extensively studied. Herein, we identify an alternative lipid biosynthesis pathway that is induced in phosphate starvation that enables Gram-negative ESKAPE pathogens, including A. baumannii , Klebsiella pneumoniae , and Enterobacter cloacae to build lipid bilayers in the absence of glycerophospholipids, which are the canonical bilayers lipid. Replacement of the anionic phosphate in the lipid headgroup with zwitterionic ornithine and lysine promote survival against colistin, a last resort antimicrobial used against Gram-negative infections. These studies suggest that ESKAPE pathogens can remodel their bilayers with phosphate free lipids to overcome colistin treatment and that aminolipid biosynthesis could be targeted to improve antimicrobial treatment.

Stable Magnetite@La-Fe Oxide Core-Shell Nanostructures Prepared via Lattice Lock for Reusable Extraction of Phosphate Anions.

Stable magnetic core-shell nanostructures are developed by lattice locking lanthanide-iron (La-Fe) oxide shells with magnetite cores to prevent the release of La from the surfaces of the magnetite nanostructures. The resulting core-shell nanostructures demonstrate excellent outstanding regeneration performance and high adsorption capacity for phosphate (115 mg P·g-1). These nanostructures release minimal La from the magnetite core surfaces after adsorbent regeneration, with a La loss of only 20% compared to the control sample, Mag@La(OH)3. La3+ ions were released at concentrations ranging from 1 to 2.3 μg·L-1 at pH levels of 4 to 8, which is within the metal content range found in natural aquatic environments. These results demonstrate the high stability of the nanostructures after regeneration. Furthermore, the adsorbent exhibits high extraction capacity across a wide pH range of 4 to 10 and performs well even in the presence of interfering anions at phosphate-to-anion molar ratios of 1:5, 1:25, and 1:100. Microscopic and spectroscopic analyses reveal that the primary extraction mechanism of phosphate in the La-containing shells is surface precipitation. This approach not only improves the use of magnetic core-shell nanostructures as adsorbents but also demonstrates the creation of a broad range of stable magnetic functional materials for diverse applications.

МИКРОВОДОРОСЛИ ХЛОРЕЛЛА ДЛЯ ОЧИСТКИ СТОКОВ В СЕЛЬСКОМ ХОЗЯЙСТВЕ

A promising way to solve current problems of energy saving and reducing environmental pollution may be the use of microalgae. These simple microorganisms are capable of purifying contaminated wastewater in agriculture. Wastewater contains nitrogen, phosphorus, sulfate and other contaminants. In order to optimize the technology of obtaining biodiesel fuel from lipid components in the conditions of small agricultural producers, the possibility of using Chlorella vulgaris in cleaning from ammonium ions and phosphate ions was studied. Chlorella was cultivated in a photobioreactor on a standard Tamiya medium and wastewater for 10 days at a temperature of 30 ° C and an illumination of 14 kLx in the red (620-740 nm), blue (430-500 nm) and green (500-565 nm) wavelength ranges. The filtrate of the microalgae suspension was collected over several days and assessed for the content of phosphate and nitrate ions using a photometric method. The greatest increase was observed with illumination in the red range (2 times higher), the minimum value in the green. The studies found that cell growth occurs both in synthetic, standard nutrient media and in wastewater, the latter being more costeffective. It was found that when adding chlorella to wastewater, the maximum decrease in the content of ammonium ions and phosphate anions is observed on the 6-7th day (by 19-59% and 5-29%, respectively), which is most likely due to the use of these elements by microalgae for nutrition and maintenance of life. A scheme for growing Chlorella vulgaris on wastewater for further production of lipid components of biodiesel fuel is proposed.

Efficient removal of fluoride from water by CaO/Ca12Al14O33/Ca5Al6O14 composites: Performance and mechanism

CaO/Ca12Al14O33/Ca5Al6O14 composites were synthesized through calcination of Ca-Al layered double hydroxides (CaAl-LDHs). The structures of the CaAl-LDHs and the composites were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and nitrogen adsorption–desorption isotherms. Batch experiments were carried out to study the influence of various experimental parameters such as initial fluoride concentration, contact time, pH and the coexisting anions on the adsorption of fluoride. The fluoride adsorption follows the Freundlich isotherm model. With the World Health Organization (WHO) guideline of 1.5 mg L−1, the adsorption capacity was 52.78 mg g−1. The kinetic data were fitted to the pseudo-second-order model. The change of pH (3–10) has almost no influence on the fluoride removal. High concentration of the coexisted sulfate, carbonate and phosphate anions slightly inhibited the fluoride removal. The fluoride removal mechanism study suggested that CaO transformed into CaF2 after fluoride adsorption, which play key roles in fluoride removal. The hydrolysis of Ca12Al14O33 and Ca5Al6O14 resulted the formation of Ca3Al2(OH)12. Fluoride anions participated in this hydrolysis process and resulted in the formation of Ca3Al2(OH)12-xFx, which was revealed by XRD, X-ray photoelectron spectroscopy analysis (XPS) and SEM elemental mapping images.

Bilayer-favored intercalation induced low-voltage electrochemical production of nano-graphene oxide in neutral phosphate

Graphene oxide (GO) exhibits great potential in various fields such as catalysis, wastewater treatment, and energy storage. However, traditional top-down GO preparation methods based on graphite exfoliation often suffer from high energy consumption and inevitably environmental pollution. In this work, an environmentally benign and low-voltage electrochemical exfoliation approach to fabricate nanoscale GO employing carbon fiber-based materials as the precursor using phosphate was proposed. Under neutral phosphate electrolyte, bilayer graphene oxide with a lateral size of ∼500 nm, thickness of ∼1.5 nm, and C/O ratio of 2.96 could be obtained via a constant potential process. By adjusting the pH to 12 to intensify the exfoliation reaction, the lateral size of the graphene oxide was controllable, decreasing to ∼50 nm, while the C/O ratio decreased to 0.9. Due to the further decrease in C/O ratio, the thickness increased slightly to 2–3 nm. The exfoliation potential (1.6–2.5 V vs. Ag/AgCl) and electrolyte concentration (50–500 mM) had an obvious impact on the yield of graphene oxide. Through electrochemical analysis such as linear sweep voltammetry, as well as density functional theory calculations, the exfoliation mechanism of phosphate is elucidated in detail, demonstrating that the stepwise ionized phosphate anions possess more robust intercalation capability than sulfate, thus enabling efficient exfoliation to the intertwined nanocrystalline graphite structure of carbon fibers. The DFT results revealed the bilayer-favored intercalation of phosphate, which accords well with experiments. This work provides a new controllable and green approach for GO synthesis, demonstrated by life cycle assessment. It could assist subsequent studies exploring the size effects of GO and its applications in environmental remediation and energy storage.

Syntheses, structures and magnetisms of dimethyl phosphate-bridged dinuclear lanthanide complexes with pentadentate macrocyclic ligand

A series of air-stable dinuclear complexes, [HNEt3]2[Ln2(L)2((CH3O)2PO2)4](BPh4)4 (L = 2,14-dimethyl-3,6,10,13,19-pentaazabicyclo[13.3.1]nonadeca1(19), 2,13,15,17-pentene, Ln = Dy, 1-Dy; Tb, 2-Tb; Gd, 3-Gd), has been synthesized and characterized using single-crystal X-ray crystallography and magnetic measurements. The crystal structures disclose that two dimethyl phosphate anions act as bridging ligands, linking two Ln(III) ions. Each Ln(III) ion is eight-coordinated by five nitrogen atoms from a pentadentate Schiff based ligand L and three oxygen atoms from three dimethyl phosphates, forming a triangular dodecahedral coordination geometry. Direct-current magnetic susceptibility measurements indicate an extremely weak antiferromagnetic exchange between Gd(III) ions in 3-Gd. Complex 1-Dy exhibits slow magnetic relaxation with an effective energy barrier (Ueff) of 13 K under an applied field of 1000 Oe, whereas 2-Tb does not exhibit single-molecule magnet behavior. This work presents a novel strategy for constructing polynuclear single-molecular magnets by using a pentadetate macrocycle as magnetic building blocks integrated with replaceable axial ligands.

Highly selective and efficient Pb2+ capture using PO4-loaded 3D-NiFe layer double hydroxides derived from MIL-88A

Lead (Pb) contamination in water requires improved decontamination technologies. The addition of phosphate to precipitate Pb2+ is a widely used method for remediating Pb in soil and water, though it has certain limitations. This study focuses on novel 3D mesoporous layered double hydroxide (LDH) sorbents functionalized with phosphate anions for Pb2+ removal from contaminated waters. Our innovative strategy involves converting a sacrificial template metal-organic frameworks (MOFs) structure (MIL-88A(Fe)) into NixFe LDH, followed by an anion exchange reaction with phosphate anions. This process preserves the 3D microrod architecture of MIL-88A and prevents deleterious LDH particle aggregation. The synthesis results in stable microrod crystals, 1–2 μm long, composed of 3D assemblies of NixFe-PO4 LDH nanoplatelets with a specific surface area exceeding 110 m2/g. The novel LDH materials display fast adsorption kinetics (pseudo-second order model) and remarkably high Pb2+ removal performances (Langmuir isotherm model) with a capacity of 538 mg/g, surpassing other reported adsorbents. LDH-PO4 exhibits high selectivity for Pb2+ over competing ions like Ni2+ and Cd2+ (selectivity order is: Pb2+ > Ni2+ > Cd2+). Removal of Pb2+ from NixFeLDH/88A-PO4 involves various mechanisms, including surface complexation and surface precipitation of lead phosphate or lead hydroxide phases as revealed by structural characterization techniques.