Organophosphorus Compounds Research Articles

Combined effect of polystyrene nanoparticles and chlorpyrifos to Daphnia magna

Microplastics and nanoplastics (MPs/NPs) are emerging contaminants ubiquitous in the environment. These particles can act as carriers of hydrophobic organic compounds (HOCs), such as chlorpyrifos (CPF), an organophosphorus insecticide. This study investigates the acute toxicity of CPF combined with model polystyrene nanoplastics (PS-NPs) using Daphnia magna as a model organism. The uptake and accumulation of luminescence-labelled 240 nm PS-NPs were visualized and quantified during co-exposure tests. Heart rates were measured using a video-based method, and IC50 values for heart rate were calculated to assess the acute toxicity of CPF. The results demonstrate that PS-NPs alone have no acute toxicity, while CPF exhibits high toxicity, with an IC50 of 50.8 μg/L. However, in the presence of 50 μg/L PS-NPs, the IC50 increased to approximately 400 μg/L, indicating an antagonistic effect of PS-NPs on CPF toxicity. The adsorption of CPF onto PS-NPs can reduce the concentration of free CPF, leading to aggregation and sedimentation of CPF-PS-NP clusters, thereby decreasing the uptake of CPF by D. magna. This interaction between CPF and PS-NPs in D. magna exemplifies the toxicity-attenuating effects and potential load capacity of nanoplastics for HOCs.

Catalytic strategies for detoxifying phosphorus(V) biocides.

Organophosphorus substances are employed in several industrial segments, albeit they may feature high toxicity levels depending on their structures. Based on previous extensive investigations of structure-reactivity patterns, researchers have been working on the development of catalysts as a means to detoxify phosphorus(V) organic compounds rapidly and safely through specific reaction pathways. This highlight reviews some recent advances in the utilization of catalytic systems for the decomposition of organophosphorus(V) compounds, in most cases using simulants of nerve agents. The nature of the catalysts is wide, including heterogeneous, colloidal and supramolecular systems, and although not all cases may be practical for the detoxification of phosphorus(V) organic structures, they are certainly useful for future research on this theme.

Epidemiology of Fatal Poisonings from Organophosphorus Compounds in Rangpur District, Bangladesh

Background: Organophosphorus compound (OPC) poisoning represents a significant public health issue in low- and middle-income countries. Globally, the WHO estimates three million annual cases of pesticide poisoning, resulting in 220,000 deaths, predominantly in international settings. In Bangladesh, OPCs are frequently used for suicide in rural areas due to their affordability, toxicity, and accessibility. Objective: This study aimed to determine the prevalence, incidence by age and sex, and marital status of victims in cases of fatal organophosphorus poisoning in Rangpur District. Methods: This retrospective study analyzed all medicolegal autopsies conducted between October 2005 and January 2007 at the mortuary of Rangpur Medical College based on the history and preliminary findings of the deceased. Results: Of the 282 medicolegal autopsies performed during the study period, 60 (21%) resulted from organophosphorus poisoning. Females accounted for the majority of victims (31, 52%) compared to males (29, 48%). The highest prevalence of organophosphorus poisoning occurred in the Mithapukur area (17, 28%), with the age group 21-30 years showing the highest incidence (38%). Acute poisoning was more prevalent among married individuals (80%) compared to unmarried individuals (20%). Conclusion: Organophosphorus poisoning remains a significant healthcare challenge in Bangladesh. Enhanced awareness, restricted availability, and preventive measures are crucial for reducing mortality and morbidity associated with OPC poisoning.

Rapid and efficient removal of organophosphorus pollutant and recovery of valuable elements: A boosted strategy for eliminating organophosphorus from wastewater

Considering the significant hazards of organophosphorus compounds (OPs) and the potential crisis of phosphorus (P) resource shortage, there is a great necessity to develop economically feasible, highly effective, and sustainable strategies to remove OPs and recover P resources. In this study, low-cost microscale zero-valent iron (mZVI) was used to activate hydrogen peroxide for the rapid and efficient elimination of Tetrakis(hydroxymethyl)phosphonium sulfate (THPS) from the aquatic environment. Compared to the conventional Fenton reaction and commercial mZVI, mZVI/H2O2-based Fenton-like reaction exhibited superior removal performance for THPS. The removal mechanism of the mZVI/H2O2 system for THPS was thoroughly elucidated through the identification of reactive oxygen species, characterization analysis, and theoretical calculation. Furthermore, the valuable components of the degradation products were successfully recovered through thermally induced precipitation of the sample followed by high-temperature calcination. The mZVI/H2O2 system has demonstrated significant advantages in removing organic compounds from various types of actual wastewater and improving the biodegradability of the wastewater. This study presented an environmentally friendly and highly efficient strategy to eliminate OPs pollution and recover P resources. It also provided an easy-to-operate method for remediating actual industrial wastewater.

Phosphorus Heterocycles and Their Biological Applications

AbstractLife of the living organism is based on phosphorous, and it is involved in almost all important biological and biochemical processes such as energy transfer, bone development and storing genetic information. Many of the therapeutic agents having C─P bond, isolated naturally as well and widely used in daily clinical practices are phosphorus‐containing drugs (e.g: phosphotriesters, phosphonates, phosphinates, phosphine oxides, phosphoric amides, bisphosphonates, phosphoric anhydrides, etc.) and growing further. The phosphorus heterocycles (PHs) integrate the merits of both phosphorus atom and heterocyclic scaffolds representing an important class of organophosphorus compounds, which are constantly drawing the attention among both industrial and scientific society as these compounds have shown varieties of related applications. Owing to its seminal biological importance PHs have inspired a whole generation of medicinal chemists to come up with novel scaffolds containing phosphorous atom. This review is focused mainly on the compilation of different classes of bioactive phosphorus containing heterocyclic skeletons (which includes phosphorus atom within the heterocyclic ring system or as substituted phosphorus atom attached with another heterocyclic ring system) having both therapeutic and other material chemistry applications since the year 2000 onwards barring their synthetic routes.

First Evidence of Novel Organothiophosphate Esters as Prevalent New Pollutants in Dust from Automotive Repair Shops Discovered by High-Resolution Mass Spectrometry.

The occurrence of organophosphorus compounds has garnered global concern due to their widespread production and potential environmental risks. Limited structural information has hindered a comprehensive understanding of their composition. By characteristic fragmentation-based nontarget analysis, the occurrence and composition of organothiophosphate esters (OTPEs), which are antiwear additives in lubricant oils that have received little attention previously, were investigated in dust from automotive repair shops and surrounding buildings. Fourteen OTPEs were tentatively identified, including four triarylphosphorothionates, six O,O-dialkyl phosphorothioates, and four O-alkyl O-alkyl sulfone phosphorothioates, among which four OTPEs were further confirmed by authentic standards or an industrial product. Triphenyl phosphorothioate (TPhPt) and tris(2,4-di-tert-butylphenyl) phosphorothioate (AO168=S) were prevalently detected in automotive repair shops with median concentrations of 230 and 246 ng/g, respectively, closely comparable to triphenyl phosphate (TPhP, median concentration: 302 ng/g). O,O-Dihexyl phosphorothioate (DHPt), O,O-dioctyl phosphorothioate (DOPt), O-hexyl O-hexyl sulfone phosphorothioate (DHSPt), and O-octyl O-octyl sulfone phosphorothioate (DOSPt) were the abundant analogues in automotive repair shops with semiquantitative median concentrations in the range of 119-1.05 × 103 ng/g. Hierarchical cluster analysis showed that OTPEs exhibited similar distribution patterns across automotive repair shops, indicating that these chemicals had similar sources. Moreover, the concentrations of OTPEs were usually higher in automotive repair shops than that in surrounding buildings, suggesting a motor vehicle related emission source. To our knowledge, 12 out of the 14 detected OPTEs were reported in the environment for the first time. The discovery of these OTPEs expanded the scope of known organophosphorus pollutants, highlighting the potential contaminants of OTPEs from lubricant oils for automotive and industrial applications.

Synthetic versatility: the C-P bond odyssey.

C-P bond formation reactions have garnered significant attention due to the widespread presence of organophosphorus compounds in pharmaceuticals, phosphine-containing ligands, pesticides, and materials science. Consequently, various efficient methodologies have been established in recent decades for constructing C-P bonds. This review article traces the historical evolution of C-P bond research and explores the prospects of C-P bond formation. It contrasts biotechnological approaches with chemical synthesis, emphasizing the critical importance of precision and innovation in developing novel C-P structures. A forward-looking perspective is provided on the role of computational tools and machine learning in optimizing C-P bond synthesis and discovering new compounds. The article explores prospective avenues for reactions that form C-P bonds and advocates for enhanced interdisciplinary collaboration to propel scientific and technological advancements.

Entomopathogenic fungi raise the effectiveness of organophosphorus insecticides against Trogodermagranarium

Treatment of wheat grains with three organophosphorus insecticides (OPs), chlorpyrifos-methyl (CH), malathion (MA) and pirimiphos-methyl (PI) alone and in combination with three entomopathogenic fungi (EPF) (Trichoderma harzianum (TH), T. citrinoviride (TC), and Metarhizium anisopliae (MA)) was carried in the current study to examine their control potential of Trogoderma granarium Everts. The application rates of OPs were: CH (2.5 and 5.0 ppm), MA (4.0 and 8.0 ppm) and PI: (5.0 and 10.0 ppm). The three EPF were tested at 1.0 × 105, 1.0 × 107 and 1.0 × 109 spores/kg. The impact of treatments on mortality of larvae after 7 and 14 days, F1 progeny after 30 days, F2 progeny, and grain weight loss after 80 days was examined. Generally, the binary mixtures of OPs and EPF were significantly more effective in the controlling T. granarium larvae than OPs alone or EPF alone after 7 and 14 days of exposure. Also, the mixtures of OPs (CH, MA and PI) and EPF achieved full mortality (100%) 14 days post-exposure and at the highest tested concentrations. Furthermore, mixtures of OPs and EPF significantly reduced the progeny production of khapra beetle and full progeny suppression was resulted in almost combined mixtures of OPs particularly (CH or PI) and EPF. Likewise, all mixtures of OPs and EPF induced a full protection of grains (wheat weight loss = 0.0 %) 80 days post treatment. Our findings indicate that the combinations of OPs and EPF could be a suitable protective tool of stored commodities against T. granarium.

Introduction of Phosphinine Ring into Aromatic Systems via Alkyne Cyclization

AbstractRecently developed synthetic protocols for the preparation of λ3‐phosphanaphthalenes have broadened the general scope of organophosphorus chemistry, but a versatile protocol is still missing. Here, we describe a scalable synthetic approach for the construction of various substituted phosphanaphthalenes. We have obtained 11 derivatives through rigorous study and have demonstrated the robustness of this method. The optical properties of these phosphorus compounds and their aza and carbo analogues have been experimentally compared. Here, we show the power of the method in extending the synthesis to even larger polycyclic aromatic systems with embedded phosphine rings toward its potential applicability to materials science.

Recent Advances in Visible‐Light‐Mediated Synthesis of Phosphorylated Heterocycles

AbstractOrganophosphorus compounds, especially phosphorylated heterocycles, are gaining increasing attention in the fields of materials science, pharmaceuticals, and agrochemistry due to their excellent biological activities. Consequently, the exploration of green and efficient methods for the synthesis of phosphorylated heterocycles has garnered significant interest from organic chemists. In recent years, visible light‐induced photoredox‐catalyzed organic synthesis has made substantial progress in the field of phosphorylation reaction since its eco‐friendly and mild conditions. This review summarizes the advances of the past five years in the visible‐light‐mediated synthesis of phosphorylated heterocycles using phosphine oxides as precursors through P‐centered radical addition, cross‐coupling, and cyclization reactions.

Assessing agricultural practices and insecticides resistance for effective malaria vector control in northwestern Iran

BackgroundAfter three years with no local transmission of malaria, an outbreak occurred in Iran in 2022. Key malaria control methods in Iran are including indoor residual spraying (IRS), long-lasting insecticide-treated nets (LLINs), and prompt diagnosis and treatment of malaria cases. Anopheles sacharovi is one of the main malaria vectors in Iran. This study aimed to determine the insecticides resistance status of An. sacharovi in northwestern Iran, to inform effective vector control programs in this region.MethodsLarval stages of An. sacharovi were collected from various larval habitats located in the villages along the Aras River. Adult susceptibility tests were performed on An. sacharovi using diagnostic doses of insecticides accordance to World Health Organization (WHO) guidelines. The study also evaluated agricultural insecticide and fertilizer usage alongside the presence of natural mosquito predators in breeding sites in the study area.ResultsAlongside various chemicals such as silica, humic acid, superphosphate, sulfur, urea, and solupotasse at different dose levels, organophosphorus and pyrethroid insecticides are commonly used in rice fields and orchards. Anopheles sacharovi displayed diverse reactions to insecticides, demonstrating resistance to DDT but sensitivity to malathion, and showing similar reactions to carbamate and pyrethroid insecticides.ConclusionsThese results provide significant insights into agricultural practices and the presence of mosquito larvae in the study area. The extensive use of a specific herbicide illustrates its popularity among farmers for weed control, while other agricultural products focus on enhancing soil fertility and productivity. The absence of mosquito larvae in habitats with predators indicates the usefulness of these predators in controlling the population of mosquitoes. The resistance of mosquitoes to certain insecticides highlights the need for careful selection and intermittent use of insecticides in vector control programs. These findings can inform the development of targeted strategies to reduce malaria transmission risks. Further research is essential for assessing the effectiveness of these interventions.

31P Nuclear Magnetic Resonance Spectroscopy for Monitoring Organic Reactions and Organic Compounds.

31P NMR spectroscopy is a consolidated tool for the characterization of organophosphorus compounds and, more recently, for reaction monitoring. The evolution of organic synthesis, mainly due to the combination of elaborated building blocks with enabling technologies, generated great challenges to understand and to optimize the synthetic methodologies. In this sense, 31P NMR experiments also became a routine technique for reaction monitoring, accessing products and side products yields, chiral recognition, kinetic data, intermediates, as well as basic organic parameters, such as acid-base and hydrogen-bonding. This review deals with these aspects demonstrating the essential role of the 31P NMR spectroscopy. The recent publications (the last ten years) will be explored, discussing the experiments of 31P NMR and the strategies accomplished to detect and/or quantify distinct organophosphorus molecules, approaching reaction mechanism, stability, stereochemistry, and the utility as a probe.

Continuous Flow Optimisation of the Pudovik Reaction and Phospha-Brook Rearrangement Using DBN

Flow chemistry has shown significant versatility over the last two decades, offering advantages in efficiency, scalability, and sustainability. In this study, the continuous stirred tank reactor (CSTR) was used to optimise the synthesis of α-hydroxyphosphonates via the Pudovik reaction and their subsequent conversion to phosphates through the phospha-Brook rearrangement. The study highlights that using CSTRs allows for better control over reaction parameters, leading to reduced reaction times and improved yields compared to traditional batch methods. The optimised conditions successfully facilitated a range of organophosphates, including electron-rich and electron-poor derivatives, with high efficiency. Additionally, a one-pot tandem process combining the Pudovik reaction and the phospha-Brook rearrangement was developed, reducing reaction times to two hours while maintaining comparable yields. This work demonstrates the potential of CSTRs in flow chemistry for synthesising complex organophosphorus compounds, achieving higher reaction yields and shorter reaction times, highlighting the effectiveness of continuous flow methodologies.

Selective Functionalization of White Phosphorus with Alkyl Bromides under Photocatalytic Conditions: A Chlorine-Free Protocol to Dialkyl and Trialkyl Phosphine Oxides.

A novel and efficient method for the direct selective alkylation of white phosphorus (P4) with alkyl bromides has been developed, utilizing 4DPAIPN as the photocatalyst and Hantzsch ester as the reductant. This method facilitates the synthesis of structurally diverse dialkyl phosphine oxides in good yields, offering a streamlined alternative to the traditional stepwise approach of chlorinating P4 with Cl2 and subsequently displacing the chlorine atom. Noteworthy features of this reaction include excellent product selectivity, remarkable functional group tolerance, and a broad substrate scope. Additionally, this method is effective for the synthesis of trialkyl phosphine oxides.

Interrupted Michael Reaction: Sulfophosphinoylation of α,β-Unsaturated Ketones Catalyzed by Phosphine.

An efficient method for phosphine-catalyzed sulfophosphinoylation of α,β-unsaturated ketones for synthesis allylic organophosphorus compounds has been reported, in which α,β-unsaturated compounds acting as zwitterions react with electrophiles and nucleophiles to form a C-P bond and a C-O bond and obtain allylic organophosphorus with high regio- and stereoselectivity in moderate to excellent yields.

White rot fungi to decompose organophosphorus insecticides and their relation to soil microbial load and ligninolytic enzymes

The functional and structural features of microbial load in soil are influenced by the presence of insecticides. This study examined the impact of two organophosphorus insecticides, dimethoate and parathion on the microbial load of soil. The colony count of fungi, actinomycetes, bacteria, and nitrogen fixing bacteria was reduced after insecticides application at 7 and 14 days, but at 28 days the colony count began to increase. The growth of two white rot fungi including Pleurotus sajor-caju and Phanerochaete chrysosporium was affected by parathion, which was reflected by a decrease in colony radius to 1.85±0.05 and 0.75±0.06 cm, respectively, and by dimethoate, reflected by a decrease in colony radius to 3.33±0.12 and 1.85±0.05 cm, respectively at 40 mg/L compared to colony radius at control 7.90±0.12 and 7.50±0.06 cm, respectively. The applied low concentration (10 mg/L) encouraged P. sajor-caju and P. chrysosporium to remove up to 87.7% and 81.8% of dimethoate, respectively, and 69.20 and 68.30% of parathion, respectively compared with the decomposition at high dose (40 mg/L) at 28 days. The presence of insecticides induced the production of ligninolytic enzymes lignin peroxidase, laccase, and manganase peroxidase.

Phosphonates of Pectobacterium atrosepticum: Discovery and Role in Plant-Pathogen Interactions.

Many phytopathogens' gene products that contribute to plant-pathogen interactions remain unexplored. In one of the most harmful phytopathogenic bacterium Pectobacterium atrosepticum (Pba), phosphonate-related genes have been previously shown to be among the most upregulated following host plant colonization. However, phosphonates, compounds characterized by a carbon-phosphorus bond in their composition, have not been described in Pectobacterium species and other phytopathogenic bacteria, with the exception of Pseudomonas syringae and Pantoea ananatis. Our study aimed to determine whether Pba synthesizes extracellular phosphonates and, if so, to analyze their physiological functions. We demonstrated that Pba produces two types of extracellular phosphonates: 2-diethoxyphosphorylethanamine and phenylphosphonic acid. Notably, such structures have not been previously described among natural phosphonates. The production of Pba phosphonates was shown to be positively regulated by quorum sensing and in the presence of pectic compounds. Pba phosphonates were found to have a positive effect on Pba stress resistance and a negative effect on Pba virulence. The discovered Pba phosphonates are discussed as metabolites that enable Pba to control its "harmful properties", thereby maintaining its ecological niche (the host plant) in a relatively functional state for an extended period.

Copper-Catalysed Synthesis of (E)-Allylic Organophosphorus Derivatives: A Low Toxic, Mild, Economical, and Ligand-Free Method.

Organophosphorus compounds are fundamental for the chemical industry due to their broad applications across multiple sectors, including pharmaceuticals, agrochemicals, and materials science. Despite their high importance, the sustainable and cost-effective synthesis of organophoshoryl derivatives remains very challenging. Here, we report the first successful regio- and stereoselective hydrophosphorylation of terminal allenamides using an affordable copper catalyst system. This reaction offers an efficient protocol for the synthesis of (E)-allylic organophosphorus derivatives from various types of P-nucleophiles, such as H-phosphonates, H-phosphinates, and secondary phosphine oxides. Key advantages of this ligand-free and atom-economic strategy include low toxicity of the Cu-based catalyst, cost effectiveness, mild reaction conditions, and experimental simplicity, making it competitive with methods that use toxic and expensive Pd-based catalysts. In an effort to comprehend this process, we conducted extensive DFT calculations on this system to uncover the mechanistic insights of this process.

Improvement of chlorpyrifos-induced cognitive impairment by mountain grape anthocyanins based on PI3K/Akt signaling pathway

The organophosphorus insecticide Chlorpyrifos (CPF) is widely used worldwide due to its high effectiveness. However, when ingested through the mouth and nose, it can cause severe neurotoxic effects and cognitive impairment. Natural anthocyanins show great potential in improving cognitive impairment. In this paper, we will delve into the protective effect of anthocyanins on CPF-induced cognitive impairment and its mechanism through the PI3K/Akt signaling pathway. Morris water maze, histopathological, ELISA and western blot analyses showed that anthocyanins effectively ameliorated CPF-induced spatial learning memory impairment in mice by ameliorating CPF-induced AChE inhibition, oxidative stress, and neuroinflammation and by modulating the levels of apoptosis (Caspase-3, Caspase-9) and autophagy (LC3II/ LC3I, Beclin1, p62, mTOR) biomarkers, in order to restore damaged hippocampal tissue morphology, neuron and synapse structures. To identify the action pathway of anthocyanins, we used KEGG and GO pathway enrichment analysis for screening prediction and western blot and molecular docking to verify that anthocyanins improve CPF-induced cognitive impairment by activating the PI3K/Akt pathway.

Highly enhanced fluoride removal from aqueous systems via solvent extraction utilizing trialkyl phosphine oxide as an efficient extractant

Solvent extraction (SX) has been recognized as an efficient approach for the large-scale removal of impurities, demonstrating considerable potential for fluoride extraction in industrial applications. However, existing fluoride extraction methods typically require the incorporation of additives to form complexes with fluoride for its removal. Due to the excessive additive requirements for efficient fluoride removal, these methods inevitably result in secondary contamination of feed solution, necessitating additional purification efforts to remove them. In this study, four extractants (trioctyl amine, tributyl phosphate, trioctyl phosphate, and trialkyl phosphine oxide (TRPO)) were investigated for fluoride removal via hydrogen bonding with hydrofluoric acid (HF). Various parameters, including the concentrations of extractants and stripping agents, pH values, extraction time, and temperature were initially optimized. It was found that TRPO exhibits the highest extraction efficiency for HF, with a single-stage extraction rate exceeding 70 %. Complete fluoride removal (> 99.9 %) was achieved through a consecutive four-stage extraction process. Further experiments, including maximum loading and slope analysis, combined with FT-IR and 19F NMR characterization, and DFT calculations elucidate the mechanism of the extraction. The transfer of HF into the organic phase is accomplished by the formation of a 1:1 hydrogen-bonded complex with TRPO. The loaded fluoride in the organic phase can be easily stripped by a base to get a fluoride salt. This study paves the way for the construction of novel SX systems to remove fluoride as HF.