Organophosphorus Research Articles

Visible light photocatalytic reduction of Toxic Chemical Organophosphate Monocrotophos using reduced Graphene Oxide derived from bamboo leaves

In this study, graphene oxide (GO) was synthesized from waste bamboo leaves using a pyrolysis and ultra-sonication technique. UV-visible spectroscopy revealed a prominent absorption peak at 230nm, while Raman spectroscopy confirmed the presence of characteristic D-band (1340cm⁻¹) and G-band (1596cm⁻¹). XRD analysis showed a peak at 11.5°, corresponding to a lattice spacing of 3nm, and SEM/TEM imaging demonstrated the formation of multi-layered graphene sheets. The synthesized GO was evaluated for the photocatalytic degradation of the organophosphate pesticide monocrotophos under visible light. At a concentration of 25mg/L, graphene exhibited a removal efficiency of 98% with a degradation rate of 0.036 ppm/min, following a Langmuir isotherm and pseudo-first-order kinetic model. The significance of this study lies in the potential environmental application, offering an economical and sustainable solution for the decontamination of pesticide-contaminated water sources. The method could contribute significantly for reducing environmental pollution and addressing global water safety challenges.

Enhanced Nanobody-Driven Bioluminescent Immunoassay for Rapid Parathion Detection Using Engineered Split-Nanoluciferase

In this work, with parathion, a typical forbidden organophosphate pesticide as target drug, an enhanced nanobody-driven bioluminescent immunoassay based on the engineered split-nanoluciferase (NanoLuc) was proposed. Concretely, through labeling 11S and β10, two split-NanoLuc units onto the anti-parathion nanobody (Nb) VHH9 and the artificial antigen H1 coupled with carrier protein ovalbumin (H1-OVA) respectively, an NanoLuc Binary Technology (NanoBiT) system was firstly developed in the form of homogeneous immunoassay, in which the luminescence signal was produced by the reassembled NanoLuc after the combination of the 11S-fused VHH9 and β10-labeled H1-OVA. Subsequently, in order to enhance the signal-to-noise (S/N) ratio, a novel strategy of splitting 11S into two smaller subunits Δ11S and β9 was adopted so then an NanoLuc Ternary Technology (NanoTeT) system based on tri-part components of β9-fused VHH9, β10-labeled H1-OVA and Δ11S was successfully established. The results showed that the maximum half inhibition concentration (IC50) for parathion can be as low as 2.04 ng/mL, 3.2-fold and 4.2-fold improved than that of the NanoBiT system and indirect competitive enzyme-linked immunosorbent assay (ic-ELISA). Meanwhile, the detection range was from 0.19 ng/mL to 22.11 ng/mL. More importantly, this method required simply a one-step incubation with all reagents mixed together, and the total time used in detection was only 10 min, 7-fold faster than ic-ELISA. Finally, the average recoveries for vegetable samples were from 84.8% to 122% with the coefficient of variance (CV) below 15%. Overall, this study provides a new platform for homogeneous immunoassay of the small-molecule contaminants.

Affecting factors and health risks of organophosphate esters in urban soil and surface dust in a typical river valley city based on local bivariate Moran's I and Monte-Carlo simulation

Affecting factors and health risks of organophosphate esters in urban soil and surface dust in a typical river valley city based on local bivariate Moran's I and Monte-Carlo simulation

Organophosphate esters and their metabolites in eggs from Vietnam

ABSTRACT Data on the occurrence of organophosphate tri-esters (tri-OPEs) and their metabolites (di-OPEs) in hen’s eggs are scarce. Therefore, 200 egg samples were gathered in 2023 in Hanoi, Vietnam and analysed by UHPLC-Q-Exactive HRMS. The majority of these compounds were detected, with tris(2-ethylhexyl) phosphate (0.10–2.7 ng/g wet weight (ww)) and trihexyl phosphate (0.08–2.3 ng/g ww) being the most prevalent tri-OPEs. Significant differences in tri-OPE profiles were observed in egg samples from battery-cage and free-range farming (p < .05). Despite egg levels ranging from 0.05 to 11.2 ng/g ww, Σdi-OPE accumulation in yolk and egg white was not significantly different in (p > .05). Among di-OPEs, dibutyl phosphate was found at the highest levels in the egg white, while bis(2-ethylhexyl) phosphate had the highest levels in yolk. There was no carcinogenic human health risk associated with OPEs in eggs (HQs <1).

Managing atropine-induced psychosis in organophosphate poisoning: A case report

Atropine-induced psychosis, though rare, is a critical adverse effect that can arise during the treatment of organophosphate (OP) poisoning, necessitating swift recognition for optimal patient care. This case report describes the presentation of a 45-year-old male with a history of chronic alcoholism and smoking, admitted for OP intoxication, who developed acute psychosis after atropine administration. The symptoms included hallucinations, agitation, and delirium, with diagnostic evaluation confirming atropine-induced psychosis according to DSM-IV-TR criteria. The treatment approach involved discontinuing atropine and providing supportive care, which resulted in symptom resolution within several days. In addition, benzodiazepines were administered to manage agitation and anxiety. This case highlights the need for careful monitoring of drug reactions, particularly in patients with risk factors, such as chronic alcoholism. It underscores the importance of individualized treatment strategies and the critical role of healthcare professionals in recognizing and addressing atropine-induced psychosis. Further research is warranted to better understand the underlying mechanisms and risk factors associated with this complication.

Metal‐Organic Framework (Cu@ZIF) for Photocatalytic Reduction of p‐Nitrophenol and its Toxicological Evaluation using Zebrafish (Danio Rerio)

AbstractGlobal food security depends on agricultural development, yet excessive fertilizer and pesticide usage is harmful to the environment. These substances have a role in human health problems, environmental changes, and erosion of the soil. Although p‐nitrophenol, an organic pollutant and other organophosphorous compounds are utilised in agriculture, their usage raises major health and environmental issues. These synthetic pesticides are quite effective at getting rid of pests, but they have also been linked to serious health problems for people and animals, degraded soil, and contaminated water. One typical persistent pollutant present in industrial wastewater is the organic pollutant, which is produced by organophosphorous compounds. The primary objective of this work is to use Cu@ZIF for photoreduction of p‐nitrophenol (PNP). A UV‐visible spectrophotometer test revealed that the deterioration peak after 60 mins. An analyzer for total organic carbon (TOC) was utilised to assess the PNP mineralization. The catalyst remained same and continued in the same behaviour even after four cycles. This study evaluated the acute toxicity of PNP on the development of early‐stage zebrafish, paying particular attention to the embryonic developmental deformities. The technique of photocatalytic decontamination is safe for the environment, financially practical, and technically achievable.

Mad Honey Poisoning: Another Substance causing Muscarinic Overactivity

Mad honey syndrome is the poisoning by Grayanotoxin, produced by plants of genus Rhododendron of Ericacea family. Grayanotoxin poisoning is relatively uncommon and is encountered mostly in Nepal and Turkey, where the plants are found in abundance. The similarity between the symptoms of Grayanotoxin toxicity and organophosphate compounds (OPC) poisoning poses the challenge of differentiating between the two, and a possibility of atropine poisoning while treating as OPC poisoning. Here we report the first ever case of “Mad Honey Syndrome” in Bangladesh, where meticulous history taking helped us in proper diagnosis and appropriate management. J Bangladesh Coll Phys Surg 2024; 42: 383-386

Gestational organophosphate esters (OPEs) and executive function in adolescence: The HOME Study

BackgroundEvidence from toxicological studies indicate organophosphate esters (OPEs) are neurotoxic, but few epidemiological studies investigated associations between gestational OPEs and executive function. ObjectiveTo examine the associations between gestational concentrations of OPE urinary metabolites and executive function at 12 years MethodsWe used data from 223 mother-adolescent dyads from the Health Outcomes of Measures of the Environment (HOME) Study. Women provided spot urine samples at 16 weeks gestation, 26 weeks gestation, and at delivery for quantification of bis(1,3-dichloro-2-propyl) phosphate, bis-2-chloroethyl phosphate (BCEP), diphenyl phosphate (DPHP), and di-n-butyl phosphate (DNBP). Executive function was assessed at age 12 years using the parent- and self-report Behavior Rating Inventory of Executive Function (BRIEF2). Covariate-adjusted associations between specific gravity-corrected OPEs and BRIEF2 scores were estimated using multiple informant models. Bayesian Kernel Machine Regression (BKMR) was used to assess the impact of all OPEs simultaneously. ResultsParent- and self-report BRIEF2 indices and composite scores were weakly to moderately correlated (rs=0.32-0.41). A natural-log unit increase in BCEP at 26 weeks was associated with approximately a 1-point increase on the self-report Cognitive Regulation Index [CRI] (95% CI 0.4, 2.3), the Emotion Regulation Index [ERI] (95% CI 0.3, 2.2), and the Global Executive Composite [GEC] (95% CI 0.4, 2.2), indicating poorer performance. Higher DPHP at 16 weeks was associated with lower parent-report GEC score (β=-1.1, 95% CI -2.3, -0.003). BKMR identified BCEP and DNBP at 26 weeks as important contributors to CRI and ERI, respectively. ConclusionOPE metabolites during gestational development, particularly BCEP, may influence adolescent executive function. However, since the FDR p-values failed to reach statistical significance, additional studies would benefit from using larger cohorts.

Impact of organic contaminants in soils from Important Bird and Biodiversity areas.

Soils act as sinks for many organic contaminants, posing a threat to biodiversity and essential ecosystem services. In this study, we assessed the contamination status of soils in 140 Important Bird and Biodiversity Areas (IBAs) in Spain. Fifty-two organic contaminants including organochlorine pesticides (OCPs), organophosphorus pesticides (OPPs), polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), and plasticizers or plastic related such as phthalates, bisphenol A, nonylphenol, and organophosphate esters (OPEs) were analyzed by gas chromatography coupled to tandem mass spectrometry (GC-MS/MS). The mean soil concentration ranged from 1.41 to917ng/g and plasticizer and PAHs were detected at the highest concentrations, while OCPs were the most frequently detected. Hierarchical clustering on principal components (HCPC) and land use data associated PCBs with artificial land, phthalates with industrial sites and incineration plants and PAHs with burned areas, and in a lesser extent pesticides with agricultural activities. A tier I environmental risk assessment (ERA) was performed to identify the most impacted natural areas and the most concerning compounds. Out of the 140 IBAs, 95 presented at least one compound at high-risk concentrations (RQ > 1) for soil organisms. The OPPs chlorpyrifos and malathion, together with the PAH benzo[b]fluoranthene, were detected at high-risk concentrations. Overall, this study highlights the widespread presence of organic contaminants in areas of high natural value and the importance of implementing monitoring studies to identify potential contaminated sites that require conservation and remediation actions for the protection of biodiversity.

A novel portable in situ analyzer for highly sensitive monitoring of organophosphorus and carbamate pesticides in food and environment

The presence of excessive residues of organophosphorus (OPs) and carbamate (CPs) pesticides in food and the environment poses a significant threat to human health and ecological sustainability. Herein, we reported a dual-readout, portable, and highly sensitive photoelectric analyzer (DPHP-analyzer) to achieve rapid and accurate monitoring of OPs and CPs. The dual signal strategy is mainly achieved by controlling the activity of acetylcholinesterase (AChE) in the presence of OPs to catalyze acetylthiocholine (ATCh) and generate thiocholine (TCh), which specifically induced the conversion of colorless Ellman's reagent (DTNB) into yellow 5-thio-2-nitrobenzoic acid (TNB). Simultaneously, the utilization of positively charged TNB as an absorber can induce a dynamic fluorescence quenching effect based on energy transfer mechanism. Fully cooperating with the above mechanism, a CD like, disposable array-based chip manufactured by 3D printing (CD-AN-chip) was designed and integrated to deliver reagents. By use of this dual-output strategy, the analyzer and chip can provide good sensitivity and selectivity for the monitoring of diazinon and carbendazim (case analysis) with a LOD 0.38 ng/mL for carbendazim. And the reproducibility, stability and practicability analysis of real sample have been thoroughly validated simultaneously. Importantly, with the features of fluorescence fingerprint map, the detector could be employed for the distinction of various analytes and further be used for monitoring the nutritional environment within residential and public settings.

Gestational organophosphate pesticide exposure and childhood cardiovascular outcomes

IntroductionThe general population is chronically exposed to organophosphate pesticides through various routes including ingestion, hand-to-mouth contact, inhalation, and dermal contact. Exposure to organophosphate pesticides during pregnancy impairs fetal development, but the potential long-term effects of gestational organophosphate pesticide exposure are less well understood. MethodsWe investigated associations between gestational organophosphate pesticide exposure and cardiovascular outcomes in 643 children in the Generation R Study, a prospective pregnancy cohort based in Rotterdam, The Netherlands. Urinary organophosphate pesticide metabolites (dimethyl [∑DMAP], diethyl [∑DEAP], and total dialkyl phosphate [∑DAP] metabolites) were quantified in three urine samples collected from pregnant participants, and their children were followed until age 10 years at which time cardiac magnetic resonance imaging, ultrasonography, blood pressure, and serum biomarkers assessed cardiovascular health. Linear regression models estimated associations (β and 95 % confidence interval [CI]) between a one-interquartile range (IQR) increase in averaged gestational exposure biomarker concentrations and z-scored pediatric cardiovascular outcomes. We investigated effect modification of associations by PON1 genotype. ResultsCarotid intima-media thickness z-score was lower (β: -0.14 [95 % CI: −0.25, −0.02]) and HDL cholesterol z-score was higher (β: 0.14 [95 % CI: 0.02, 0.25]) for increases in ∑DEAP concentrations. Carotid intima-media distensibility z-score was lower (β: -0.08 [95 % CI: −0.19, 0.03]) for increases in ∑DMAP concentrations, and systolic blood pressure z-score was higher (β: 0.10 [95 % CI: −0.01, 0.21]) for increases in ∑DMAP and ∑DAP. Among those with PON1-161CC and PON1-L55MTT genotypes, higher organophosphate pesticide concentrations conferred an excess risk of adverse vascular and glycemic outcomes, respectively. ConclusionsWe observed heterogenous associations between gestational organophosphate pesticide exposure and pediatric cardiovascular health: an anti-atherogenic profile was observed for increases in ∑DEAP concentrations, and impairments in multiple aspects of cardiovascular health was observed for increases in ∑DMAP concentrations. PON1-161 and PON1-L55M single nucleotide polymorphisms modified associations for vascular and glycemic outcomes, respectively.

Simultaneous analysis of several plasticizer classes in different matrices by on-line turbulent flow chromatography-LC-MS/MS.

The development of methodologies for the determination of plasticizers is essential for assessing the environmental and human impact resulting from the use of plastics. A fast analytical method with on-line purification based on turbulent flow chromatography (TFC) coupled to tandem mass spectrometry (MS-MS) has been developed for the analysis of ten phthalates, four alternative plasticizers (including adipates and citrates), and 20 organophosphate esters (OPEs). The method has been validated for the determination of plasticizers across different matrices. Analytical parameters showed acceptable recoveries ranging between 50 and 125%, RSDs lower than 20%, and mLODs of 0.001-2.08ngg-1 wet weight (ww), 0.002-0.30ngg-1, and 0.001-0.93ngm-3 for foodstuffs, face masks, and ambient air, respectively. These methodologies were applied to foodstuff samples purchased in grocery stores, reusable and self-filtering masks, and indoor air measured in different locations. Plasticizers were detected in all the analyzed samples, with values up to 22.0μgg-1 ww, 6.78μgg-1, and 572ngm-3 for foodstuffs, face masks, and indoor air, respectively. The contribution of each family to the total plasticizer content varied between 1.3 and 87%, 0.5 and 98%, and 0.5 and 65% for phthalates, alternative plasticizers, and OPEs, respectively. These findings highlighted the need for analytical methodologies capable of simultaneously assessing a wide number of plasticizers with minimal extractionsteps. This capability is crucial in order to obtain more conclusive insights into the impact of these pollutants on both the environment and human health, arising from different sources of exposure such as foodstuffs, plastic materials, and atmospheric air.

Accidental Organophosphate Poisoning in a Child: A Case Report Highlighting the Importance of Early Recognition and Treatment

Background: Organophosphate (OP) poisoning is a significant global health concern, especially in developing countries where these chemicals are widely used in agriculture and household pest control. Children are particularly susceptible to accidental OP poisoning due to their inquisitive nature and immature physiology. This case report presents a child with acute muscarinic symptoms following accidental ingestion of an OP insecticide, emphasizing the importance of early recognition and treatment. Case presentation: A 9-year-old boy presented to the emergency department with vomiting, decreased consciousness, and respiratory distress 6 hours after accidentally ingesting an OP insecticide (Baygon) stored in a drinking bottle at home. He exhibited classic muscarinic symptoms, including miosis, hypersalivation, hyperlacrimation, stridor, and wheezing. The patient was treated with atropine and supportive care, resulting in the complete resolution of his symptoms. Conclusion: This case highlights the importance of early recognition and prompt management of OP poisoning in children. Atropine remains the cornerstone of treatment for muscarinic symptoms, and supportive care is crucial to prevent complications. Public health interventions aimed at educating parents and caregivers about the safe storage and handling of OP insecticides are essential to prevent accidental poisoning in children.

Visual signal transduction for environmental stewardship: A novel biosensing approach to identify and quantify chlorpyrifos-related residues in aquatic environments

The pervasive presence of organophosphate pesticides (OPs), such as chlorpyrifos (CPF), in aquatic ecosystems underscores the urgent need for sensitive and reliable detection methods to safeguard environmental and public health. This study addressed the critical need for a novel biosensor capable of detecting CPF and its toxic metabolite, 3,5,6-trichloro-2-pyridinol (TCP), with high sensitivity and selectivity, suitable for field applications in environmental monitoring. The study engineered a whole-cell biosensor based on E. coli strains that utilize the ChpR transcriptional regulator and the vioABCE gene cluster, providing a distinct visual and colorimetric response to CPF and TCP. The biosensor's performance was optimized and evaluated across various water matrices, including freshwater, seawater, and soil leachate. The biosensor demonstrated high sensitivity with a broad linear detection range, achieving limits of detection (LODs) at 0.8 μM for CPF and 7.813 nM for TCP. The linear regression concentration ranges were 1.6–12.5 μM for CPF and 15.6–125 nM for TCP, aligning with environmental standard limits and ensuring the biosensor's effectiveness in real-world scenarios. This innovative biosensing approach offers a robust, user-friendly tool for on-site environmental monitoring, significantly mitigating OPs contamination and advancing current detection technologies to meet environmental protection standards.

Development of a Photothermal Regenerative Plasmonic Platform as a Light-Controlled Interface.

This study introduces a novel plasmonic nanocomposite platform, where gold nanoparticles (AuNPs) are synthesized in situ within a polydimethylsiloxane (PDMS) film. The innovative fabrication process leverages ethyl acetate swelling to achieve a uniform distribution of AuNPs, eliminating the need for additional reagents. The resulting nanocomposite film exhibits exceptional photothermal conversion capabilities, efficiently converting absorbed light into heat and rapidly reaching high temperatures. Furthermore, the platform is biofunctionalized with the phosphotriesterase enzyme, not only enabling the degradation of organophosphate pesticides but also showcasing the potential for multifunctional applications. The platform's ability to be regenerated after use underscores its sustainability for repeated applications.

MOF-mediated cascade reaction system for ultrasensitive detection of alkaline phosphatase activity and organophosphorus pesticides.

Ametal-organic-framework (MOF) fluorescent sensor is reportedbased on NH2-MIL-101(Fe) propelled pesticide and alkaline phosphatase (ALP) catalytic reaction. Different from previous reports, a cascade reaction system combined with MOF structural changes to generate fluorescence was employed. The rationale is that ALP can hydrolyze L-ascorbic acid 2-phosphate (AAP) into L-ascorbic acid (AA), which can reduce Fe3+ to decompose structurally NH2-MIL-101(Fe), resulting in 2-aminoterephthalic acid (NH2-BDC) with intense fluorescence. The fluorescence can be decreased to different degrees due to inhibition of organophosphate pesticides (OPPs) on the activity of ALP. By taking chlorpyrifos (CPY) as the model compoundof anOPP pesticide and adding ALP and CPY into the NH2-MIL-101(Fe) framework, the resulting cascade reaction fluorescence sensors exhibit a good sensitivity for CPY and ALP sensing. The working ranges are 0.02-2 μg/L and 0.2-20 mU/mL with detection limits (LOD) of 5.31 ng/L and 0.05 mU/mL, respectively. The proposed sensor has been actually applied tosatisfactory detection of CPY and ALP in food and serum samples. This fluorescence-based assay may extend the application of MOF-based biosensors.

Ubiquitous occurrence of organophosphate esters in plastic-made and paper-made food contact materials and their implication for human exposure

Ubiquitous occurrence of organophosphate esters in plastic-made and paper-made food contact materials and their implication for human exposure

Enhancing Sensitivity and Selectivity: Current Trends in Electrochemical Immunosensors for Organophosphate Analysis.

This review examines recent advancements in electrochemical immunosensors for the detection of organophosphate pesticides, focusing on strategies to enhance sensitivity and selectivity. The widespread use of these pesticides has necessitated the development of rapid, accurate, and field-deployable detection methods. We discuss the fundamental principles of electrochemical immunosensors and explore innovative approaches to improve their performance. These include the utilization of nanomaterials such as metal nanoparticles, carbon nanotubes, and graphene for signal amplification; enzyme-based amplification strategies; and the design of three-dimensional electrode architectures. The integration of these sensors into microfluidic and lab-on-a-chip devices has enabled miniaturization and automation, while screen-printed and disposable electrodes have facilitated on-site testing. We analyze the challenges faced in real sample analysis, including matrix effects and the stability of biological recognition elements. Emerging trends such as the application of artificial intelligence for data interpretation and the development of aptamer-based sensors are highlighted. The review also considers the potential for commercialization and the hurdles that must be overcome for widespread adoption. Future research directions are identified, including the development of multi-analyte detection platforms and the integration of sensors with emerging technologies like the Internet of Things. This comprehensive overview provides insights into the current state of the field and outlines promising avenues for future development in organophosphate pesticide detection.

Machine Learning Models for Predicting Bioavailability of Traditional and Emerging Aromatic Contaminants in Plant Roots.

To predict the behavior of aromatic contaminants (ACs) in complex soil-plant systems, this study developed machine learning (ML) models to estimate the root concentration factor (RCF) of both traditional (e.g., polycyclic aromatic hydrocarbons, polychlorinated biphenyls) and emerging ACs (e.g., phthalate acid esters, aryl organophosphate esters). Four ML algorithms were employed, trained on a unified RCF dataset comprising 878 data points, covering 6 features of soil-plant cultivation systems and 98 molecular descriptors of 55 chemicals, including 29 emerging ACs. The gradient-boosted regression tree (GBRT) model demonstrated strong predictive performance, with a coefficient of determination (R2) of 0.75, a mean absolute error (MAE) of 0.11, and a root mean square error (RMSE) of 0.22, as validated by five-fold cross-validation. Multiple explanatory analyses highlighted the significance of soil organic matter (SOM), plant protein and lipid content, exposure time, and molecular descriptors related to electronegativity distribution pattern (GATS8e) and double-ring structure (fr_bicyclic). An increase in SOM was found to decrease the overall RCF, while other variables showed strong correlations within specific ranges. This GBRT model provides an important tool for assessing the environmental behaviors of ACs in soil-plant systems, thereby supporting further investigations into their ecological and human exposure risks.

Organophosphate esters (OPEs) in the air and dust of new vehicle cabins: Concentrations, sources and contributions

Vehicles cabin represents unique indoor environment characterized by its limited space and multiple interior materials. For the first time, OPEs levels in vehicles and OPEs content in cabin materials were measured, and the material contributions were also analyzed. Between May and July in 2023, air, dust and materials samples were collected from 32 new vehicles. The detection rates were as high as 71%–100 % in dust and 100 % in selected cabin materials. The median of ∑OPEs in air-phase (both gas and particles) was significantly higher at 589.26 ng/m3 compared to those in other vehicle investigations. Material content analysis revealed that the top three were cushion textile, mat and lubricant, with ∑OPEs ranging from 85.94 μg/g to 1406.04 μg/g, which were three orders of magnitude higher than those in toys. Chlorinated forms such as TCIPP and TDCIPP were predominant among all air, dust and material samples analyzed. Particle-phase OPEs provided statistic diversity on manufactures and seat materials. Positive Matrix Factorization (PMF) analysis found that the combination of cushion textile, seat leather, and carpet substrate textile contributed significantly, accounting for 68 % of cabin OPEs.