Search Results (165)

A triphenylphosphine-functionalized silica gel material, optimized for lead adsorption, was synthesized via a one-pot sol–gel reaction and characterized using FTIR and solid-state ¹³C and ²⁹Si NMR and XPS spectroscopy. The interaction between lead cations and phosphine groups was evaluated using the ³¹P NMR chemical shift tensor as a sensor. Two distinct types of phosphine groups, exhibiting different rotational mobility behaviors, were identified, with their ratio influenced by the presence of lead cations. These results suggest that the adsorption behavior of lead on this functionalized silica gel adsorbent can be directly evaluated by its lead–phosphorus interaction. This association was corroborated by the shifting of the binding energies of phosphorus functional groups after lead uptake in the XPS analysis. Full article

A series of new isatin hydrazones bearing phosphorus-containing moiety was synthesized through a simple, high-yield and easy work-up reaction of phosphine oxide (Phosenazide) or phosphinate (2-chloroethyl (4-(dimethylamino)phenyl)(2-hydrazinyl-2-oxoethyl)phosphinate, CAPAH) hydrazides with aryl-substituted isatins. The ³¹P NMR technique showed that, in most cases, out of 12 examples in solution, the ratio of the two spatial isomers varied from 1:1 to 1:3. Quantum chemical calculations confirmed the predominance of Z,syn form both in the gas phase and in solution. According to X-ray analysis data in crystals, they exist only in Z,syn form too. Most of the phosphine oxide derivatives and 5-methoxy- and 5-bromoaryl phosphinate analogs exhibit anti-aggregant activity at the level of acetylsalicylic acid but inhibit platelet activation processes more effectively. The 5-chloro type phosphinate derivative exhibits anti-aggregant properties more effectively than acetylsalicylic acid under the conditions of the tissue factor (TF)-activated thromboelastography (TEG) model, the ex vivo thrombosis model. Thus, all the obtained results can become the basis for future pharmaceutical developments to create effective anti-aggregation drugs with broad antithrombotic potential. Full article

With the increasing urgency of petroleum resource scarcity and environmental challenges, the development of degradable bio-based flame retardants has become crucial for enhancing the fire safety of organic materials. In this work, a phosphorus-containing chitosan derivative (CS-PPOA) was synthesized via a one-step protonation reaction between chitosan (CS) and phenylphosphinic acid (PPOA) under mild conditions. The resulting multifunctional flame-retardant coating was applied to polyester (PET) fabrics. Comprehensive characterization using FT-IR, XPS, and NMR confirmed the successful protonation of chitosan amino groups through electrostatic interactions, forming a stable ionic complex. The CS-PPOA solution exhibited excellent rheological properties and film-forming ability, producing films with over 80% optical transmittance and flexibility. Thermogravimetric analysis (TGA) revealed that CS-PPOA achieved char residue yields of 76.8% and 40.2% under nitrogen and air atmospheres, respectively, significantly surpassing those of acetic acid-protonated chitosan (CS-HAc). The limiting oxygen index (LOI) of CS-PPOA increased to 48.3%, and vertical burning tests demonstrated rapid self-extinguishing behavior. When applied to PET fabrics at a 15% loading, the LOI value improved from 20.3% (untreated fabric) to 27.8%, forming a dense char layer during combustion while completely suppressing melt dripping. Additionally, the coated fabric exhibited broad-spectrum antibacterial activity, achieving a 99.99% inhibition rate against Escherichia coli and Staphylococcus aureus. This study provides a novel strategy for the green and efficient preparation of multifunctional bio-based flame-retardant coatings. Full article

Developing a new efficient separation ligand based on the “CHON” principle to address the limitations of phosphorus containing extractants in nuclear fuel reprocessing can help further simplify the process flow and reduce the amount of secondary waste. Building upon this critical need, a novel ligand was developed through a strategic application of the Hard and Soft Acids and Bases (HSAB) theory, integrating a soft donor nitrogen atom into the linear architecture of bis-diglycolamide. This groundbreaking ligand, named N,N′-bis[2-(2-(N,N-dioctylcarbamoyl)ethoxy)ethylacetamido]-N″-diethylenetriamine (TOMDEA-BisDGA), has demonstrated remarkable potential in the extraction of Pu(IV). The study unveils that the ligand demonstrates remarkable selectivity and separation efficiency towards Pu(IV) ions while maintaining an exceptionally low extraction capacity for U(VI) across a wide acidity spectrum of 0.1~6 mol/L. To explain the structure properties of complex formed by the ligand and Pu(IV), a systematic analysis was performed, including slope analysis, proton nuclear magnetic resonance (NMR) titration, and Fourier-transform infrared (FT-IR) spectroscopy. This study explores the coordination and separation behavior of diglycolamide ligands with actinide. This work is expected to provide important information and theoretical bases upon which advanced design and optimization of ligands for high-performance processes for the separation of plutonium might be carried out. Such findings will contribute to the understanding of actinide chemistry and further the design of improved separation methods for nuclear applications. Full article

In this study, the synthesis and properties of β-cyclodextrin-functionalized silver nanoparticles and their loading with a drug component are considered. β-Cyclodextrin was used as a reducing agent and stabilizer in the preparation of silver nanoparticles. The use of β-CD-AgNPs in loading molecules of the alkaloid cytisine (Cz) and its O,O-dimethyl-N-cytisinilphosphate (CzP) derivative, which have pronounced antiviral properties, was studied. The formation of β-CD-Cz-AgNPs and β-CD-CzP-AgNPs was confirmed by UV spectroscopy and X-ray diffraction spectroscopy. Scanning electron microscopy and transmission electron microscopy showed that the obtained β-CD-Cz-AgNP and β-CD-CzP-AgNP nanocomposites were well dispersed with particle sizes in the range of 3–20 nm. ¹H-, ¹³C-NMR and COSY, HMQC, HMBC and Fourier transform infrared spectroscopy revealed the reduction and encapsulation of AgNPs by β-Cz, and the TEM imaging results showed an increase in the size of nanoparticles after the introduction of cytisine and its phosphorus derivative. The kinetic parameters of the thermal degradation process of β-CD, Cz, CzP and their inclusion complexes Cz(CzP)-β-CD-AgNPs under isothermal conditions, which ensure the preservation of the kinetic triplet, were determined. The differences in the mechanism of thermal decomposition of the studied materials are described by the parameters of the Šesták–Berggren model (m and n), which demonstrated differences for different compounds: for β-CD, the values of the parameters m and n are 0.47 and 0.53, respectively, while for CzP-β-CD-AgNPs they reach values of 0.66 and 1.34. These results indicate differences in the mechanism of thermal decomposition of the studied materials. Full article

ATP analogues are essential tools in enzymology and structural biology, but the structural and functional implications of their chemical modifications on nucleotide-binding proteins are often underappreciated. To address this, we evaluated a panel of ATP analogues, focusing on thiosubstituted and fluorinated molecules, using the AAA+ ATPase p97 as a benchmark system. Hydrolysis stability and impact on protein conformation, binding modes, and kinetics of enzymatic catalysis were assessed by protein-detected methyl NMR and ligand-detected ¹⁹F NMR in solution, as well as ³¹P solid-state NMR of nucleotides within protein sediments. ATPγS and AMP-PNP emerged as the most suitable analogues for preserving pre-hydrolysis states over extended periods, despite undergoing gradual hydrolysis. In contrast, both AMP-PCP and α/β-thiosubstituted analogues failed to induce native protein conformations in p97. Notably, we demonstrate a novel real-time NMR setup to explore the effect of nucleotide mixtures on cooperativity and the regulation of enzymes. Additionally, aromatic fluorine TROSY-based ¹⁹F NMR shows promise for direct ligand detection in solution, even in the context of large macromolecular complexes. These findings provide critical guidance for selecting ATP analogues in functional and structural studies of nucleotide-binding proteins. Full article

There are few examples of covalent organic frameworks (COFs) based on phosphorus as the building element, probably because the structure of most phosphorus derivatives is pyramidal, which may prevent the stacking expected for classical 2-dimensional COFs. In addition, they are generally associated with linear difunctional derivatives. In this paper is reported the original association of a trifunctional 3-D compound with a trifunctional 2-D compound in an attempt to get a new COF. The condensation reaction between a thiophosphate derivative bearing three aldehydes and the trihydrazinotriazine has been carried out with the aim of obtaining either a COF or simply a porous organic polymer (POP), consisting in both cases of associated macrocycles, affording a new covalent triazine framework (CTF). The material resulting from this condensation has been characterized by multinuclear MAS NMR (³¹P, ¹H, and ¹³C), IR, and thermogravimetric analysis (TGA). All these data confirmed the condensation reactions. However, BET (Brunauer–Emmett–Teller) measurements indicated that the porosity of this material is low. Trapping dyes in solution, as a model of pollutants, by the insoluble porous material 3 has been attempted. Full article

Phosphorus is essential to environmental systems because it affects both agricultural productivity and ecological balance. Since it contributes to eutrophication and pollution problems, its existence in a variety of environmental matrices, including soil, water, and air, necessitates precise and effective determination methods for monitoring and managing its levels. This review paper provides an extensive overview of the latest advancements in analytical techniques for measuring phosphorus in environmental samples. We investigate sophisticated spectroscopic, chromatographic, and electrochemical techniques in addition to conventional approaches like colorimetric analysis. Innovative techniques such as mass spectrometry (MS), X-ray fluorescence (XRF) spectrometry, and nuclear magnetic resonance (NMR) spectroscopy are also highlighted in this study, along with newly developed technologies such as biosensors, lab-on-a-chip devices, and nanotechnology-based techniques. Real-time and field-deployable monitoring technologies are also covered, with a focus on their advantages and usefulness. Among the techniques reviewed, XRF and colorimetry methods have proven to be the most reliable due to their precision, cost-effectiveness, and adaptability for different sample matrices. While emerging spectroscopic and electrochemical techniques offer promising alternatives, further validation and standardization are needed for routine environmental monitoring. Future research should focus on integrating automated and high-throughput techniques to enhance monitoring capabilities further. Full article

The phosphorus-31 (³¹P) spectral modulus (PSM) is a measure of the metabolic status of cells, tissues, and organs. The PSM can be calculated from ³¹P nuclear magnetic resonance (³¹P NMR) spectra obtained from cell, tissue, or organ preparations. These ³¹P NMR spectra can be a measure of intact living cells, tissues, or organs, or appropriate biochemical extracts of such preparations. The ³¹P NMR spectrum is comprised of signals derived from organophosphate metabolites that resonate from 10 δ to −25 δ on the phosphorus chemical shift δ scale. The PSM is the ratio of the high-energy phosphate to that of the low-energy phosphate spectral integrals. These integrals may be conveniently grouped into high-energy and low-energy spectral regions, respectively, into ³¹P chemical shifts located between −0.13 δ to −25 δ and between 10 δ to −0.13 δ. High-energy phosphates are typically described as providing the energy necessary for the activity of cellular metabolism; chemically, they contain one or more phosphate anhydride bonds. This study demonstrates that, (1) in general, the higher the metabolic activity, the higher the PSM, and (2) the modulus calculation does not require a highly resolved ³¹P spectrum and can be calculated solely from the integral. The PSM was calculated among cells, tissues, and organs considered normal, diseased, and stressed. In diseased (mean 1.29 ± 0.73) and stressed (mean 1.23 ± 0.75) cells, tissues, and organs, PSM values are typically low or low relative to normal cells, tissues, or organs (mean 1.65 ± 0.90), following time-course measurements, in dynamic decline. The PSM is useful in determining the metabolic status of cells, tissues, or organs and can be employed as a calculable numeric assay for determining health status statically or over time. Calculation of the PSM can be carried out with spectra of low signal-to-noise; it relies on the minimal resolution required to detect an integral curve having a clear spectral integral inflection point at ca. −0.13 δ. Detection of an integral curve alone enables the calculation of a PSM even at levels of phosphorus concentration so low as to prevent detection of the individual or groups of metabolites, such as with in vivo or ex vivo cell, tissue, or organ determinations. This study (1) presents the foundations and fundamentals of the PSM, a living index of tissue metabolic health, and (2) demonstrates the use of spectral scan analysis in opening new vistas of biology and medicine for measuring the metabolic status of stressed and diseased tissues at a range of detectable levels for monitoring therapeutic interventions. Full article

Nuclear magnetic resonance (NMR) spectroscopy is gaining prominence as a vital quantitative method for sample analysis, with significant progress being made in the investigation of heteronuclei like phosphorus, a key element in numerous physiological functions. This paper provides a comprehensive review of the principles, methodologies, and applications of quantitative ³¹P nuclear magnetic resonance (qNMR) spectroscopy. It begins with an introduction to the fundamental principles of NMR spectroscopy, highlighting the specific advantages of qNMR and the unique properties of the ³¹P nucleus, including its high natural abundance and broad chemical shift range. While ¹H qNMR is widely used, signal overlap in complex mixtures can limit its accuracy. Additionally, this work explores diverse applications of ³¹P qNMR across fields such as food analysis, pharmaceuticals, and biology, emphasizing its contributions to real-time drug quantification, metabolomics, and environmental analysis. A key advantage of ³¹P NMR is its ability to provide exclusive detection and direct quantification of phosphorus in phosphorus-containing compounds. The internal standard method is favored for its simplicity, as it avoids the need for calibration curves, while the external standard method is better suited for natural products with established reference materials. This review aims to consolidate the applied prospects of ³¹P qNMR, emphasizing its potential to expand the horizons of quantitative detection technologies and facilitate advancements in future research and practical applications. Full article

In this paper, we investigated the efficient metal-free phosphorus–nitrogen (PN) catalyst and used the PN catalyst to degrade waste PU with two-component binary mixed alcohols as the alcohol solvent. We examined the effects of reaction temperature, time, and other factors on the hydroxyl value and viscosity of the degradation products; focused on the changing rules of the hydroxyl value, viscosity, and molecular weight of polyols recovered from degradation products with different dosages of the metal-free PN catalyst; and determined the optimal experimental conditions of reaction temperature 180 °C, reaction time 3 h, and PN dosage 0.08%. The optimal experimental conditions were 180 °C, 3 h reaction time, and 0.08% PN dosage, the obtained polyol viscosity was 3716 mPa·s, the hydroxyl value was 409.2 mgKOH/g, and the number average molecular weight was 2616. The FTIR, ¹H, NMR, and other tests showed that the waste urethanes were degraded into oligomers successfully, the recycled polyether polyols were obtained, and a series of recycled polyurethanes with different substitution ratios were then prepared. A series of recycled polyurethane materials with different substitution rates were then prepared and characterized by FTIR, SEM, compression strength, and thermal conductivity tests, which showed that the recycled polyurethane foams had good physical properties such as compression strength and apparent density, and the SEM test at a 20% substitution rate showed that the recycled polyol helped to improve the structure of the blisters. Full article

This study explored the effect of the combined application of chemical and organic fertilizers on phosphorus morphology and its conversion to an active state. A long-term field positioning experiment comprising five treatments was conducted in black soil. The results concluded that the soil total phosphorus (TP), available phosphorus (AP), inorganic phosphorus, and organic phosphorus contents of all treatments ranked as follows: 1.5M1NPK > M2NPK > M1NPK > NPK > CK. The long-term application of chemical and organic fertilizers increased the proportion of soil reactive phosphorus and moderately reactive phosphorus but decreased the proportion of mildly active phosphorus and residual phosphorus. A phosphorus-31 nuclear magnetic resonance (³¹P NMR) spectral analysis showed that the contents of orthophosphate, pyrophosphate, phosphoric acid diesters, and orthophosphate acid monoesters increased with the application of chemical and organic fertilizers, of which 1.5M1NPK usually resulted in the highest increases. In conclusion, the long-term application of chemical fertilizers could promote the conversion of soil phosphorus into active phosphorus and improve the effectiveness of soil phosphorus, and the long-term use of organic and chemical fertilizers was more effective than the use of chemical fertilizers only, with 1.5M1NPK providing the best effects. Full article

Amino acid analogues with a phosphorus-containing moiety replacing the carboxylic group are promising sources of biologically active compounds. The H-phosphinic group, with hydrogen–phosphorus–carbon (H-P-C) bonds and a flattened tetrahedral configuration, is a bioisostere of the carboxylic group. Consequently, amino-H-phosphinic acids undergo substrate-like enzymatic transformations, leading to new biologically active metabolites. Previous studies employing NMR-based metabolomic and proteomic analyses show that in Escherichia coli, α-KG-γ-P_H (the distal H-phosphinic analogue of α-ketoglutarate) can be converted into L-Glu-γ-P_H. Notably, α-KG-γ-P_H and L-Glu-γ-P_H are antibacterial compounds, but their intracellular targets only partially overlap. L-Glu-γ-P_H is known to be a substrate of aspartate transaminase and glutamate decarboxylase, but its substrate properties with NAD⁺-dependent glutamate dehydrogenase (GDH) have never been investigated. Compounds containing P-H bonds are strong reducing agents; therefore, enzymatic NAD⁺-dependent oxidation is not self-evident. Herein, we demonstrate that L-Glu-γ-P_H is a substrate of eukaryotic GDH and that the pH optimum of L-Glu-γ-P_H NAD⁺-dependent oxidative deamination is shifted to a slightly alkaline pH range compared to L-glutamate. By ³¹P NMR, we observe that α-KG-γ-P_H exists in a pH-dependent equilibrium of keto and germinal diol forms. Furthermore, the stereospecific enzymatic synthesis of α-KG-γ-P_H from L-Glu-γ-P_H using GDH is a possible route for its bio-based synthesis. Full article

Phosphorus (P) is an essential macronutrient for plants. The focus of this work is to recover P from biosolids and their derived biochar. The effect of three different pyrolysis temperatures (400 °C, 500 °C, and 600 °C) and two carrier gases (CO₂ and N₂) on P fractionation and the speciation of P on biochars produced from two biosolids were investigated. The Hedley chemical sequential extraction method and ³¹P liquid NMR were used for P characterization and quantification. Higher pyrolysis temperatures increased P fixation and decreased short-term P bioavailability. Carrier gas had also significant effects on P fractionation in the biochars. Biochar produced in a CO₂ environment had slightly higher water-soluble P, NaHCO₃-P_i, NaOH-P_i, and residual P than in biochar prepared in a N₂ environment, while HCl-P showed the opposite trend. Additionally, the predominant molecular configuration of P was present in the inorganic form identified by ³¹P liquid NMR spectra, while organic P transformed into inorganic P with increasing pyrolysis temperature. Full article

New cyclotriphosphazene derivatives featuring amide–Schiff base linkages with a hydrazine bridge and different terminal ends, such as decyl alkyl chains and hydroxy groups, were successfully synthesized and characterized. Fourier-transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR), and CHN elemental analysis were used to characterize the structures of these compounds. The formation of hydrazine-bridged cyclotriphosphazene derivatives with amide–Schiff base linkages was confirmed by the FTIR spectra, showing a primary amine band for the amide linkage around ~3300 cm⁻¹ and a band for the Schiff base linkage near ~1595 cm⁻¹. This was further supported by NMR analysis, which displayed an amide proton (H-N-C=O) at ~δ 10.00 ppm and an azomethine proton (H-C=N) within the δ 8.40–8.70 ppm range. The ³¹P NMR spectra of cyclotriphosphazene compounds display a singlet at ~δ 8.20 ppm, indicating an upfield shift that suggests the complete substitution of all phosphorus atoms with identical side chains. Furthermore, CHN analysis verified the purity of the synthesized compounds, with a percentage error below 2%. The introduction of hydrazine bridges and amide–Schiff base linkages into the cyclotriphosphazene core significantly enriches the molecular structure with diverse functional groups. These modifications not only improve the compound’s stability and reactivity, but also expand its potential for a wide range of applications. Full article