An Au(<scp>iii</scp>)–amino alcohol complex for degradation of organophosphorus pesticides

Ferri, Daniel; Barba‐Bon, Andrea; Costero, Ana M.; Gaviña, Pablo; Parra, Margarita; Gil, Salvador

doi:10.1039/c5ra20645f

Cited by 7 publications

(5 citation statements)

References 27 publications

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“…The major metabolite for malathion was observed at δ P 97.64 ppm, corresponding to O, O-dimethyl dithiophosphate [37]. However, this observation is in contrast to previous studies of malathion 4, where malaoxon (signal around 28.31 ppm) [38], a more toxic and potent inhibitor of AChE or dimethyl thiophosphate (expected at around δ P 27 ppm) [39], were shown to be the major metabolites of malathion but were absent after three days of HLM incubation (Figure S2). Several published biotransformation studies of malathion have shown that the formation of malaoxon is dependent on the concentration of the CYP2C P450 family in the HLMs [38,40,41].…”

Section: Resultscontrasting

confidence: 73%

Targeted Metabolomics of Organophosphate Pesticides and Chemical Warfare Nerve Agent Simulants Using High- and Low-Dose Exposure in Human Liver Microsomes

et al. 2023

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Our current understanding of organophosphorus agent (pesticides and chemical warfare nerve agents) metabolism in humans is limited to the general transformation by cytochrome P450 enzymes and, to some extent, by esterases and paraoxonases. The role of compound concentrations on the rate of clearance is not well established and is further explored in the current study. We discuss the metabolism of 56 diverse organophosphorus compounds (both pesticides and chemical warfare nerve agent simulants), many of which were explored at two variable dose regimens (high and low), determining their clearance rates (Clint) in human liver microsomes. For compounds that were soluble at high concentrations, 1D-NMR, 31P, and MRM LC-MS/MS were used to calculate the Clint and the identity of certain metabolites. The determined Clint rates ranged from 0.001 to 2245.52 µL/min/mg of protein in the lower dose regimen and from 0.002 to 98.57 µL/min/mg of protein in the high dose regimen. Though direct equivalency between the two regimens was absent, we observed (1) both mono- and bi-phasic metabolism of the OPs and simulants in the microsomes. Compounds such as aspon and formothion exhibited biphasic decay at both high and low doses, suggesting either the involvement of multiple enzymes with different KM or substrate/metabolite effects on the metabolism. (2) A second observation was that while some compounds, such as dibrom and merphos, demonstrated a biphasic decay curve at the lower concentrations, they exhibited only monophasic metabolism at the higher concentration, likely indicative of saturation of some metabolic enzymes. (3) Isomeric differences in metabolism (between Z- and E- isomers) were also observed. (4) Lastly, structural comparisons using examples of the oxon group over the original phosphorothioate OP are also discussed, along with the identification of some metabolites. This study provides initial data for the development of in silico metabolism models for OPs with broad applications.

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Section: Resultscontrasting

confidence: 73%

Targeted Metabolomics of Organophosphate Pesticides and Chemical Warfare Nerve Agent Simulants Using High- and Low-Dose Exposure in Human Liver Microsomes

et al. 2023

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“…Organophosphates at high concentrations can be efficiently degraded by catalytic materials. − In nature, a series of enzymes such as phosphatase and phosphodiesterase are used as catalysts for the hydrolytic decomposition of organophosphates. − Many enzymes hold metal ions at active sites. In this context, metal ions such as zinc, copper, cobalt, and mercury ions have been used as homogeneous catalysts for the hydrolysis of organophosphates. − Lanthanoid (Ln) ions are also available as the hydrolysis catalysts due to their strong Lewis acidity in aqueous solutions. − Recently, the higher catalytic activity of cerium(IV) ions than 3d-metal ions has been reported for organophosphates hydrolysis because 4f orbitals of Ce IV ion readily interact with the orbitals of the phosphate group in an organophosphate. − …”

Section: Introductionmentioning

confidence: 99%

Heterogeneous Catalysis of Lanthanoid Ions for the Hydrolysis of p-Nitrophenyl Phosphate Enhanced by Incorporation to Cyano-Bridged Heterometallic Coordination Polymers

2022

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Solid materials containing lanthanoid ions (LnIII = TbIII or EuIII), i.e., lanthanoid oxide (LnIII 2O3), lanthanoid ions immobilized on silica–alumina by cation exchange (LnIII/Al-SiO2), and lanthanoid ions incorporated into cyano-bridged heterometallic coordination polymers ([LnIII(H2O) x ] y [MC(CN)6], LnIII = TbIII or EuIII; MC = FeIII or RuII; x ≥ 2), were examined as heterogeneous catalysts for hydrolysis of p-nitrophenyl phosphate (p-NPP). LnIII 2O3 and LnIII/Al-SiO2 exhibit lower catalytic activity (∼50% and ∼55% for 72 h, respectively) than LnIII ions used as homogeneous catalysts (∼65%) for the hydrolysis of p-NPP. Ex situ IR measurements after the hydrolysis of p-NPP indicated that active sites of the heterogeneous catalysts were inhibited by a product of dihydrogen phosphate. On the other hand, [LnIII(H2O) x ] y [MC(CN)6] exhibited higher activity (≥81%) for the hydrolysis of p-NPP compared with not only the homogeneous LnIII-ion catalysts but also cyano-bridged heterometallic coordination polymers containing 3d-metal ions such as FeIII ions (38%) previously reported as active catalysts. The high activity of [LnIII(H2O) x ] y [MC(CN)6] resulted from suitable interaction among LnIII ions in the coordination polymers, p-NPP, and water as evidenced by the ex situ IR measurements.

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“…Because of their highly efficient catalytic activity, Schiff bases have been extensively studied, [9][10][11][12][13][14][15] with catalytic degradation of Schiff base complexes gaining popularity in recent years. [17] Yet, metal organic complexes have unlimited research value in the field of degradation because of their potential catalytic activity. They lose electrons to form unfilled electronic orbits, which typically act as "Lewis acids."…”

Section: Introductionmentioning

confidence: 99%

“…However, metal ions are known to direct the movement of numerous groups during catalysis due to which the activation energy of the catalytic reaction is diminished. [17] Yet, metal organic complexes have unlimited research value in the field of degradation because of their potential catalytic activity. In this work, phosphorus-based Schiff base complexes were synthesized and characterized by ( 1 H and 3 C) nuclear magnetic resonance (NMR), Fourier transforminfrared (FT-IR), and UV-Vis spectroscopy.…”

Section: Introductionmentioning

confidence: 99%

Phosphorus‐based Schiff bases and their complexes as nontoxic antioxidants: Structure–activity relationship and mechanism of action

Zoubi

Kim

Al‐Hamdani

et al. 2019

Applied Organom Chemis

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Phosphorus-based Schiff base were synthesized by treating bis{3-[2-(4-amino-1.5-dimethyl-2-phenyl-pyrazol-3-ylideneamino)ethyl]-indol-1-ylmethyl}phosphinic acid with paraformaldehyde and characterized as a novel antioxidant. Its corresponding complexes [(VO) 2 L(SO 4 ) 2 ], [Ni 2 LCl 4 ], [Co 2 LCl 4 ], [Cu 2 LCl 4 ], [Zn 2 LCl 4 ], [Cd 2 LCl 4 ], [Hg 2 LCl 4 ], [Pd 2 LCl 4 ], and [PtLCl]Cl 2 were analyzed by Fourier transform-infrared, ( 1 H and 13 C) nuclear magnetic resonance, and mass and UV-Vis spectroscopy. Experimental data showed that the ligand coordinated with the metal ions via donor atoms such as nitrogen to form an octahedral arrangement of the Schiff base around the central transition-metal atom. The nature of these complexes was identified using the molar ratio and Job's methods, with the results agreeing with a metal-toligand (M:L) molar ratio of 2:1, expect for Pt, whose M:L was 1:1. Thermodynamic activation parameters such as ΔE*, ΔH*, ΔS*, ΔG*, and K were determined from the thermogravimetric analysis curve using the Coats-Redfern method. The antioxidant activities of the prepared compounds were assessed by using 1.1-diphenyl-2-picrylhydrazyl as the free radical, and the results show that the complex Schiff bases were found to possess potent antioxidant activity. The structure-activity relationship of the ligand and its complexes indicates that the presence of electron-donating moieties, such as Co(II) and Ni(II), in the chemical structure increases the antioxidant activity, whereas the Pt(IV) and Pd(II) complexes diminished the antioxidant activity, indicating the superior activity of the hydroxyl radical (OH · ) over the superoxide radical.

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An Au(iii)–amino alcohol complex for degradation of organophosphorus pesticides

Abstract: A gold(iii)–amino alcohol complex induces the P–S bond cleavage in organophosphorous pesticides giving rise to less toxic compounds.

Cited by 7 publications

References 27 publications

Targeted Metabolomics of Organophosphate Pesticides and Chemical Warfare Nerve Agent Simulants Using High- and Low-Dose Exposure in Human Liver Microsomes

Targeted Metabolomics of Organophosphate Pesticides and Chemical Warfare Nerve Agent Simulants Using High- and Low-Dose Exposure in Human Liver Microsomes

Heterogeneous Catalysis of Lanthanoid Ions for the Hydrolysis of p-Nitrophenyl Phosphate Enhanced by Incorporation to Cyano-Bridged Heterometallic Coordination Polymers

Phosphorus‐based Schiff bases and their complexes as nontoxic antioxidants: Structure–activity relationship and mechanism of action

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