-
Food and Chemical Toxicology : An... Sep 2020Data on the bioactivation of Phosmet (Pho), a phthalimide-derived organophosphate pesticide (OPT), to the neurotoxic metabolite Phosmet-oxon (PhOx) in human are not...
Data on the bioactivation of Phosmet (Pho), a phthalimide-derived organophosphate pesticide (OPT), to the neurotoxic metabolite Phosmet-oxon (PhOx) in human are not available. The characterization of the reaction in single human recombinant CYPs evidenced that the ranking of the intrinsic clearances was: 2C18>2C19>2B6>2C9>1A1>1A2>2D6>3A4>2A6. Considering the average human hepatic content, CYP2C19 contributed for the great majority (60%) at relevant exposure concentrations, while CYP2C9 (33%) and CYP3A4 (31%) were relevant at high substrate concentration. The dose-dependent role of the active isoforms was confirmed in human liver microsomes by using selective CYP inhibitors. This prominent role of CYP2C in oxon formation was not shared by other OPTs. The pre-systemic Pho bioactivation measured in human intestinal microsomes was relevant accounting for ¼ of that measured in the liver showing two reaction phases catalysed by CYP2C and CYP3A4. Phosmet efficiently inhibited CPF bioactivation and detoxication, with Ki values (≈30 μM) relevant to pesticide concentrations achievable in the human liver, while the opposite is unlikely (Ki ≈ 160 μM) at the actual exposure levels, depending on the peculiar isoform-specific Pho bioactivation. Kinetic information in humans can support the development of quantitative in vitro/in vivo extrapolation and in silico models for risk assessment refinement for single and multiple pesticides.
Topics: Chlorpyrifos; Cytochrome P-450 Enzyme System; Drug Interactions; Gene Expression Regulation, Enzymologic; Humans; Insecticides; Isoenzymes; Liver; Molecular Structure; Phosmet; Risk Assessment
PubMed: 32590074
DOI: 10.1016/j.fct.2020.111514 -
Acta Biomaterialia Apr 2022Much debate still revolves around bone architecture, especially at the nano- and microscale. Bone is a remarkable material where high strength and toughness coexist... (Review)
Review
Much debate still revolves around bone architecture, especially at the nano- and microscale. Bone is a remarkable material where high strength and toughness coexist thanks to an optimized composition of mineral and protein and their hierarchical organization across several distinct length scales. At the nanoscale, mineralized collagen fibrils act as building block units. Despite their key role in biological and mechanical functions, the mechanisms of collagen mineralization and the precise arrangement of the organic and inorganic constituents in the fibrils remains not fully elucidated. Advances in three-dimensional (3D) characterization of mineralized bone tissue by focused ion beam-scanning electron microscopy (FIB-SEM) revealed mineral-rich regions geometrically approximated as prolate ellipsoids, much larger than single collagen fibrils. These structures have yet to become prominently recognized, studied, or adopted into biomechanical models of bone. However, they closely resemble the circular to elliptical features previously identified by scanning transmission electron microscopy (STEM) in two-dimensions (2D). Herein, we review the presence of mineral ellipsoids in bone as observed with electron-based imaging techniques in both 2D and 3D with particular focus on different species, anatomical locations, and in proximity to natural and synthetic biomaterial interfaces. This review reveals that mineral ellipsoids are a ubiquitous structure in all the bones and bone-implant interfaces analyzed. This largely overlooked hierarchical level is expected to bring different perspectives to our understanding of bone mineralization and mechanical properties, in turn shedding light on structure-function relationships in bone. STATEMENT OF SIGNIFICANCE: In bone, the hierarchical organization of organic (mainly collagen type I) and inorganic (calcium-phosphate mineral) components across several length scales contributes to a unique combination of strength and toughness. However, aspects related to the collagen-mineral organization and to mineralization mechanisms remain unclear. Here, we review the presence of mineral prolate ellipsoids across a variety of species, anatomical locations, and interfaces, both natural and with synthetic biomaterials. These mineral ellipsoids represent a largely unstudied feature in the organization of bone at the mesoscale, i.e., at a level connecting nano- and microscale. Thorough understanding of their origin, development, and structure can provide valuable insights into bone architecture and mineralization, assisting the treatment of bone diseases and the design of bio-inspired materials.
Topics: Bone and Bones; Calcification, Physiologic; Calcinosis; Collagen; Humans; Minerals; Phosmet
PubMed: 35202855
DOI: 10.1016/j.actbio.2022.02.024 -
Environmental Science. Processes &... Dec 2023Phosmet is an organophosphorus insecticide widely used in agriculture to control a range of insects; recently, it was banned by the European Union in 2022 due to its...
Phosmet is an organophosphorus insecticide widely used in agriculture to control a range of insects; recently, it was banned by the European Union in 2022 due to its harmful effects. However, its environmental degradation and fate have not yet been evident. Thus, phosmet oxidation by HO˙ radicals was theoretically studied in this work using the DFT approach at the M06-2X/6-311++G(3df,3pd)//M06-2X/6-31+G(d,p) level of theory. Three different mechanisms were considered, including formal hydrogen transfer (FHT), radical adduct formation (RAF), and single electron transfer (SET). The mechanisms, kinetics, and lifetime were studied in the gas and aqueous phases, in addition to its ecotoxicity evaluation. The results show that FHT reactions were dominant in the gas phase, while RAF was more favourable in the aqueous phase at 298 K, while SET was negligible. The branching ratio indicated that H-abstractions at the methyl and the methylene groups were the most predominant, while the most favourable HO˙-addition was observed at the phosphorus atom of the dithiophosphate group. The overall rate constant values varied from 1.2 × 10 (at 283 K) to 1.40 × 10 M s (at 323 K) in the aqueous phase and from 6.29 × 10 (at 253 K) to 1.32 × 10 M s (at 323 K) in the gas phase. The atmospheric lifetime of phosmet is about 6 hours at 287 K, while it can persist from a few seconds to several years depending on the temperature and [HO˙] concentration in the aqueous environment. The QSAR-based ecotoxicity evaluation indicates that phosmet and its degradation products are all dangerous to aquatic organisms, although the products are less toxic than phosmet. However, they are generally developmental toxicants and mutagenicity-negative compounds.
Topics: Insecticides; Phosmet; Water; Organophosphorus Compounds; Oxidation-Reduction; Kinetics; Models, Theoretical; Hydroxyl Radical
PubMed: 37850503
DOI: 10.1039/d3em00325f -
Spectrochimica Acta. Part A, Molecular... Nov 2023Pesticide active ingredients (AIs) are often applied with adjuvants to facilitate the stability and functionality of AIs in agricultural practice. The objective of this...
Pesticide active ingredients (AIs) are often applied with adjuvants to facilitate the stability and functionality of AIs in agricultural practice. The objective of this study is to investigate the role of a common non-ionic surfactant, alkylphenol ethoxylate (APEO), on the surface-enhanced Raman spectroscopic (SERS) analysis of pesticides as well as its impact on pesticide persistence on apple surfaces, as a model fresh produce surface. The wetted areas of two AIs (thiabendazole and phosmet) mixed with APEO were determined respectively to correct the unit concentration applied on apple surfaces for a fair comparison. SERS with gold nanoparticle (AuNP) mirror substrates was applied to measure the signal intensity of AIs with and without APEO on apple surfaces after a short-term (45 min) and a long-term (5 days) exposure. The limit of detection (LOD) of thiabendazole and phosmet using this SERS-based method were 0.861 ppm and 2.883 ppm, respectively. The result showed that APEO decreased the SERS signal for non-systemic phosmet, while increased SERS intensity of systemic thiabendazole on apple surfaces after 45 min pesticide exposure. After 5 days, the SERS intensity of thiabendazole with APEO was higher than thiabendazole alone, and there was no significant difference between phosmet with and without APEO. Possible mechanisms were discussed. Furthermore, a 1% sodium bicarbonate (NaHCO) washing method was applied to test the impact of APEO on the persistence of the residues on apple surfaces after short-term and long-term exposures. The results indicated that APEO significantly enhanced the persistence of thiabendazole on plant surfaces after a 5-day exposure, while there was no significant impact on phosmet. The information obtained facilitates a better understanding of the impact of the non-ionic surfactant on SERS analysis of pesticide behavior on and in plants and helps further develop the SERS method for studying complex pesticide formulations in plant systems.
Topics: Pesticides; Malus; Phosmet; Surface-Active Agents; Gold; Thiabendazole; Metal Nanoparticles; Lipoproteins
PubMed: 37270975
DOI: 10.1016/j.saa.2023.122954 -
Neotropical Entomology Feb 2019The lethal and sublethal effects of 11 insecticides on the predator Ceraeochrysa cubana (Hagen) were assessed under laboratory conditions. First-instar larvae and adults...
The lethal and sublethal effects of 11 insecticides on the predator Ceraeochrysa cubana (Hagen) were assessed under laboratory conditions. First-instar larvae and adults ≤ 48 h old were sprayed with the highest insecticides doses allowed to control Diaphorina citri Kuwayama in the citrus crop. The survival and duration rates of the different development stages, sex ratio, pre-oviposition period, fecundity, and fertility of the insects were evaluated. In the larval bioassay, chlorpyrifos and malathion had lethal effect which none larvae survived. Azadirachtin, lambda-cyhalothrin + chlorantraniliprole, lambda-cyhalothrin + thiamethoxam, and thiamethoxam had lethal and sublethal effects that did not allow to estimate the life table parameters because the low number of couples formed. Esfenvalerate, imidacloprid WG and SC, phosmet, and pyriproxyfen had sublethal effects which were reflected in the net reproductive rate and in the intrinsic rate of natural increase. In bioassay using adults, none of the individuals survived in the chlorpyrifos, lambda-cyhalothrin + chlorantraniliprole, lambda-cyhalothrin + thiamethoxam, malathion, or thiamethoxam treatments, and the azadirachtin, esfenvalerate, imidacloprid WG and SC, phosmet, and pyriproxyfen treatments were significantly lower compared to the control. None of the insecticides was harmless to first-instar larvae and adults of C. cubana under laboratory conditions showing their potential to reduce the efficiency of this predator.
Topics: Animals; Chlorpyrifos; Hemiptera; Insecticides; Larva; Limonins; Malathion; Neonicotinoids; Nitriles; Nitro Compounds; Pyrethrins; Pyridines; Random Allocation; Thiamethoxam; Toxicity Tests
PubMed: 30168012
DOI: 10.1007/s13744-018-0626-3 -
Contact Lens & Anterior Eye : the... Aug 2022This prospective study assessed the influence of wearing and then discontinuing orthokeratology (OK) lenses on retinal shape and peripheral refraction in myopic children.
PURPOSE
This prospective study assessed the influence of wearing and then discontinuing orthokeratology (OK) lenses on retinal shape and peripheral refraction in myopic children.
METHODS
Fifty-eight myopic children (age 8-12 years) were equally divided into an OK group and a single vision spectacles (SVS) group. After 12 months of OK, it was discontinued for 1 month. Peripheral eye length (PEL), relative peripheral refraction (RPR), and corneal parameters were measured in the right eye on the nasal and temporal retinal sides at baseline, 6 months, and 12 months (13 months in OK group) visits.
RESULTS
In the SVS group, faster elongation of the temporal side PEL made the eyes more asymmetric and prolate, developing a temporal pointed shape. In the OK group, the nasal retinal side PEL grew faster, the nasal RPR developed less hyperopic defocus, and the eye shape became more symmetric and less prolate. The central cornea became thinner and flattened, while the peripheral cornea became steeper. Changes in corneal thickness, relative peripheral corneal power, and K-values were no significant differences for the OK and SVS groups at 12 months.
CONCLUSIONS
The cornea reverted to be no difference with myopic children with SVS after 1 month discontinuation of OK. The retinal shape of SVS eyes became more asymmetric and prolate with myopia progression. OK remodelled retinal shape to be less asymmetric and less prolate.
Topics: Axial Length, Eye; Child; Corneal Topography; Humans; Myopia; Orthokeratologic Procedures; Phosmet; Prospective Studies; Refraction, Ocular
PubMed: 34736858
DOI: 10.1016/j.clae.2021.101532 -
Scientific Reports Nov 2022While MRI and CT are the gold standards for assessments of splenic size in clinical settings, ultrasonography is particularly suited due to its portability, cost...
While MRI and CT are the gold standards for assessments of splenic size in clinical settings, ultrasonography is particularly suited due to its portability, cost efficiency and easy utilization. However, ultrasonography is associated with subjective assessment, potentially resulting in increased variation. We used a test-retest design aiming to determine the reliability of splenic measurements assessed by ultrasonography during apnea. In addition, we compared reliability between different equations for volume calculations: Koga, Prolate ellipsoid and Pilström. Twelve healthy participants (6 women) performed two tests separated by 15 min, comprising a maximal voluntary apnea in a seated position. Splenic dimensions were measured via ultrasonography for 5 min before and immediately following apnea. Resting splenic volume displayed high test-retest reliability between tests (Pilström: 157 ± 39 mL vs 156 ± 34 mL, p = .651, ICC = .970, p < .001, CV = 2.98 ± 0.1%; Prolate ellipsoid: 154 ± 37 mL vs 144 ± 43 mL, p = .122, ICC = .942, p < .001, CV = 5.47 ± 0.3%; Koga: 142 ± 37 mL vs 140 ± 59 mL, p = .845, ICC = .859, p < .001, CV = 9.72 ± 1.4%). Apnea-induced volumes displayed similar reliability (127 ± 29 mL vs 129 ± 28 mL, p = .359, ICC = .967, p < .001, CV = 3.14 ± 3.1%). Reliability was also high between equations (Pilström vs Prolate ellipsoid: ICC = .818, p < .001, CV = 7.33 ± 0.3%, bias = - 3.1 mL, LoA = - 46.9 to 40.7 mL; Pilström vs Koga: ICC = .618, p < .01, CV = 11.83 ± 1.1%, bias = - 14.8 mL, LoA = - 76.9 to 47.3 mL). We conclude that splenic ultrasonographic measurements have practical applications during laboratory and field-based research as a reliable method detecting splenic volume change consistently between repeated tests. The Pilström equation displayed similar reliability compared to the prolate ellipsoid formula and slightly higher compared to the Koga formula and may be particularly useful to account for individual differences in splenic dimensions.
Topics: Humans; Female; Reproducibility of Results; Apnea; Phosmet; Ultrasonography; Spleen
PubMed: 36347952
DOI: 10.1038/s41598-022-23384-6 -
Nature Communications Sep 2022Escherichia coli phage SU10 belongs to the genus Kuravirus from the class Caudoviricetes of phages with short non-contractile tails. In contrast to other short-tailed...
Escherichia coli phage SU10 belongs to the genus Kuravirus from the class Caudoviricetes of phages with short non-contractile tails. In contrast to other short-tailed phages, the tails of Kuraviruses elongate upon cell attachment. Here we show that the virion of SU10 has a prolate head, containing genome and ejection proteins, and a tail, which is formed of portal, adaptor, nozzle, and tail needle proteins and decorated with long and short fibers. The binding of the long tail fibers to the receptors in the outer bacterial membrane induces the straightening of nozzle proteins and rotation of short tail fibers. After the re-arrangement, the nozzle proteins and short tail fibers alternate to form a nozzle that extends the tail by 28 nm. Subsequently, the tail needle detaches from the nozzle proteins and five types of ejection proteins are released from the SU10 head. The nozzle with the putative extension formed by the ejection proteins enables the delivery of the SU10 genome into the bacterial cytoplasm. It is likely that this mechanism of genome delivery, involving the formation of the tail nozzle, is employed by all Kuraviruses.
Topics: Bacteriophages; DNA, Viral; Genome, Viral; Phosmet; Podoviridae
PubMed: 36153309
DOI: 10.1038/s41467-022-33305-w -
Micromachines Mar 2023Here, a molecular imprinting technique was employed to create an SPR-based nanosensor for the selective and sensitive detection of organophosphate-based coumaphos, a...
Here, a molecular imprinting technique was employed to create an SPR-based nanosensor for the selective and sensitive detection of organophosphate-based coumaphos, a toxic insecticide/veterinary drug often used. To achieve this, UV polymerization was used to create polymeric nanofilms using -methacryloyl-l-cysteine methyl ester, ethylene glycol dimethacrylate, and 2-hydroxyethyl methacrylate, which are functional monomers, cross-linkers, and hydrophilicity enabling agents, respectively. Several methods, including scanning electron microscopy (SEM), atomic force microscopy (AFM), and contact angle (CA) analyses, were used to characterize the nanofilms. Using coumaphos-imprinted SPR (CIP-SPR) and non-imprinted SPR (NIP-SPR) nanosensor chips, the kinetic evaluations of coumaphos sensing were investigated. The created CIP-SPR nanosensor demonstrated high selectivity to the coumaphos molecule compared to similar competitor molecules, including diazinon, pirimiphos-methyl, pyridaphenthion, phosalone, -2,4(dimethylphenyl) formamide, 2,4-dimethylaniline, dimethoate, and phosmet. Additionally, there is a magnificent linear relationship for the concentration range of 0.1-250 ppb, with a low limit of detection (LOD) and limit of quantification (LOQ) of 0.001 and 0.003 ppb, respectively, and a high imprinting factor (I.F.4.4) for coumaphos. The Langmuir adsorption model is the best appropriate thermodynamic approach for the nanosensor. Intraday trials were performed three times with five repetitions to statistically evaluate the CIP-SPR nanosensor's reusability. Reusability investigations for the two weeks of interday analyses also indicated the three-dimensional stability of the CIP-SPR nanosensor. The remarkable reusability and reproducibility of the procedure are indicated by an RSD% result of less than 1.5. Therefore, it has been determined that the generated CIP-SPR nanosensors are highly selective, rapidly responsive, simple to use, reusable, and sensitive for coumaphos detection in an aqueous solution. An amino acid, which was used to detect coumaphos, included a CIP-SPR nanosensor manufactured without complicated coupling methods and labelling processes. Liquid chromatography with tandem mass spectrometry (LC/MS-MS) studies was performed for the validation studies of the SPR.
PubMed: 37420940
DOI: 10.3390/mi14040707 -
Food Chemistry Jun 2021This study was undertaken to assess the potential of Tribolium castaneum (Red flour beetle) acetylcholinesterase (Tc-AChE) based electrochemical biosensor integrating...
This study was undertaken to assess the potential of Tribolium castaneum (Red flour beetle) acetylcholinesterase (Tc-AChE) based electrochemical biosensor integrating WO/g-CN nanocomposite modified Pencil graphite electrode to detect an organophosphate insecticide, Phosmet. The WO/g-CN nanocomposite provides a non-toxic, biocompatible surface for binding the enzyme on the electrode surface, attributed to its large surface area, high conductivity, and low ohmic resistance. The proposed biosensor shows a very good analytical performance with LOD 3.6 nM for Phosmet and effectively determined Phosmet in wheat with a 99% recovery rate. Furthermore, molecular docking deciphers the binding interactions of Phosmet with Tc-AChE using a modified AutoDock LGA algorithm and an AMBER03 force field in YASARA. The kinetic parameters strongly suggest the high potency of inhibitor with the enzyme. This study presents an adaptable, rapid, and straightforward approach that opens ways towards real progress in developing commercial biosensors for pesticide detection.
Topics: Acetylcholinesterase; Animals; Biosensing Techniques; Coleoptera; Edible Grain; Electrodes; Food Storage; Graphite; Molecular Docking Simulation; Nanocomposites; Nitriles; Oxides; Pesticides; Phosmet; Tungsten
PubMed: 33422918
DOI: 10.1016/j.foodchem.2020.128894