RESUMEN
The introduction of invasive fish species to aquatic ecosystems has been demonstrated to cause disastrous ecological effects. Current conservation strategies regard rotenone-containing piscicide formulations, such as commercial product CFT Legumine, as a potentially viable alternative to the cumbersome traditional approaches to fish eradication. This consideration relies on the fast degradation of rotenone and its relatively rapid dissipation from the environment. Piscicide treatments in fragile aquatic ecosystems should thus monitor not only rotenone concentrations following application, but also other byproducts and degradation products. We present a methodology for the analysis of rotenoids in fresh and brackish waters that addresses two main challenges: the accurate determination of applied concentrations in different salinity concentrations by performing a simplified on-site solid-phase extraction, overcoming the fast degradation of rotenone in sample storage conditions, and the selective analysis of rotenoid byproducts and degradation products by gas chromatography coupled to mass spectrometry. Limits of quantification were below the ecological no-effect concentration of rotenone (2 µg/L) and average recoveries exceeded 80%. Accuracy (compared to expected values) and precision (deviation of replicates) ranged from 78 to 103% and 3 to 14%, respectively, across various rotenoid concentrations. These metrics are more than satisfactory for the intended application of this simplified procedure. The method was applied to piscicide-treated samples, revealing significant and fast degradation of parent rotenoids in storage conditions, as well as a non-negligible accumulation of rotenone in the particulate fraction of water that could impact the effectivity of eradication efforts.
Asunto(s)
Peces , Cromatografía de Gases y Espectrometría de Masas , Rotenona , Extracción en Fase Sólida , Contaminantes Químicos del Agua , Rotenona/análisis , Rotenona/química , Animales , Cromatografía de Gases y Espectrometría de Masas/métodos , Contaminantes Químicos del Agua/análisis , Contaminantes Químicos del Agua/química , Extracción en Fase Sólida/métodos , Aguas Salinas/química , Agua Dulce/química , Límite de Detección , Monitoreo del Ambiente/métodos , Reproducibilidad de los ResultadosRESUMEN
In neurodegenerative diseases, particularly in Parkinson's disease (PD), antinociceptive centers are often implicated in neurodegeneration, leading to persistent pain unresponsive to narcotic substances. This study investigated the periaqueductal gray matter (PAG) and the nucleus raphe magnus (NRM), components of the brain's antinociceptive system. In conditions of rotenone intoxication (an experimental PD model), morphological changes in intracellular structures were observed in PAG and NRM neurons, indicating metabolic disorders characteristic of PD (alterations in the shape and size of neuronal bodies and processes, disruption of acid phosphatase activity in neuron cytoplasm). Under the influence of bacterial melanin and in combination with synoestrol, positive changes in structural properties were observed in PAG and NRM neurons compared to the rotenone model of PD. This included the preservation of the morphological characteristics typical of these brain regions, with cells exhibiting shapes and sizes close to normal. Furthermore, under the influence of these therapeutic agents, an increase in phosphatase activity in cell cytoplasm was detected, indicating an acceleration of metabolic processes (metabolic activation) disrupted by rotenone intoxication. The data obtained suggests that bacterial melanin and synoestrol may act as potential neuroprotective agents against PAG and NRM neurons in the rat brain in the rotenone model of PD. Further research is needed to elucidate the mechanisms of action of therapeutic doses and propose their use in the treatment of PD, either in isolation or combination therapy.
Asunto(s)
Enfermedad de Parkinson , Núcleos del Rafe , Animales , Núcleos del Rafe/fisiología , Enfermedad de Parkinson/tratamiento farmacológico , Rotenona/farmacología , Rotenona/análisis , Melaninas/análisis , AnalgésicosRESUMEN
A 64-year-old woman presented with coma, seizure, and lactic acidosis after ingesting 80 yam bean seeds. This rotenone-containing seeds cause cellular asphyxia via blockage of the mitochondrial electron transport. Subsequent oxidative stress results in the formation of lipid peroxidation (LPO). Rotenone analysis via liquid chromatography mass spectrometry revealed the following: 31,590 ng/mL in cooked yam bean seed and 100 ng/mL in the blood. We attempted to use N-acetylcysteine to alleviate oxidative stress and documented the continuous decline in the plasma concentration of LPO.
Asunto(s)
Pachyrhizus/efectos adversos , Rotenona/análisis , Acidosis Láctica/complicaciones , Acidosis Láctica/etiología , Coma/etiología , Femenino , Humanos , Persona de Mediana Edad , Estrés Oxidativo/efectos de los fármacos , Rotenona/efectos adversos , Rotenona/sangre , Convulsiones/etiologíaRESUMEN
Tephrosia vogelii Hook was excellent insecticidal plant, it was introduced into China and planted over a large area in Guangdong province. The main active components of T. vogelii was rotenone and it widely found in leaves and pods of T. vogelii. This paper study of the safety assessment of T. vogelii flowers to worker bees. In this paper, the content of rotenone in T. vogelii petal, nectar, pollen, pistil, and stamen samples were investigated by HPLC, and tested the toxicity of T. vogelii flowers for Apis cerana cerana during 24â¯h. The dissipation and dynamic of rotenone in A. c. cerana different biological compartments were investigated under indoor conditions during 24â¯h. The results showed, The LT50 of T. vogelii flowers to worker bees were collected from the eastern, western, southern, northern and top were 13.95, 24.17, 12.55, 26.48, and 18.84â¯h, the haemolymph of worker bees have the highest content of rotenone, the least accumulation of rotenone in workers bee's thorax, and the rate of dissipation was slowly during the whole study. In conclusion, the results showed the T. vogelii create security risks to worker bees under some ecosystems.
Asunto(s)
Abejas/efectos de los fármacos , Insecticidas/toxicidad , Rotenona/toxicidad , Tephrosia/química , Animales , China , Ecosistema , Flores/química , Flores/crecimiento & desarrollo , Insecticidas/análisis , Control Biológico de Vectores , Hojas de la Planta/química , Hojas de la Planta/crecimiento & desarrollo , Néctar de las Plantas/química , Polen/química , Rotenona/análisis , Tephrosia/crecimiento & desarrolloRESUMEN
Tephrosia purpurea (L.) Pers., commonly known as "sarpunkha" and "wild indigo", is being used in traditional systems of medicine to treat liver disorders, spleen and kidney. In the present study, a validated High Performance Thin Layer Chromatography (HPTLC) method was established for the estimation of lupeol, ß-sitosterol and rotenone in various extracts of T. purpurea with the aim to see the effect of seasons on the quantity of aforesaid phytoconstituents. The plant material was collected in summer (April), rainy (August) and winter (December) during 2013-2014 from Lucknow, India. The method was validated in terms of precision, repeatability, specificity, sensitivity linearity and robustness. The method permits reliable quantification and showed good resolution on silica gel with toluene-ethyl acetate-formic acid (9:1:1 v/v/v) as mobile phase, and characteristic bands of ß-sitosterol, rotenone and lupeol were observed at Rf 0.38, 0.45 and 0.52, respectively. The content of aforesaid phytoconstituents varies from season to season and extract to extract. Our finding indicated that winter season (December) may not be appropriate for collection of T. purpurea for the preparation of therapeutic formulations because of the high content of rotenone, a known insecticide that is responsible for Parkinson's disease and associated with heart failure, fatty liver and liver necrosis.
Asunto(s)
Cromatografía en Capa Delgada/métodos , Triterpenos Pentacíclicos/análisis , Extractos Vegetales/análisis , Rotenona/análisis , Sitoesteroles/análisis , Tephrosia/química , India , Estaciones del AñoRESUMEN
The total syntheses of (-)-rotenone and (-)-dalpanol have been achieved by a group-selective, stereospecific 1,2-shift of an epoxy alcohol and SN Ar cyclizations. Three oxacycles are constructed, thus illustrating a versatile synthetic route to various rotenoids.
Asunto(s)
Productos Biológicos/síntesis química , Compuestos Heterocíclicos de 4 o más Anillos/síntesis química , Rotenona/síntesis química , Productos Biológicos/química , Técnicas de Química Sintética/métodos , Ciclización , Derris/química , Compuestos Heterocíclicos de 4 o más Anillos/química , Rotenona/análisis , EstereoisomerismoRESUMEN
This work describes the isolation and quantification of rotenoids from crude organic extracts of different parts of Clitoria fairchildiana R. A. Howard (Leguminosae) by HPLC-DAD. The lipid composition and the Artemia salina cytotoxic activities of the isolates were also conducted. Clitoriacetal (1), 6-deoxyclitoriacetal (2), stemonal and stemonone were isolated by chromatographic procedures and identified by usual spectroscopic and spectrometric techniques. Clitoriacetal and 6-deoxyclitoriacetal were not found in all parts of the plant, such as leaves and petals, but in the roots they occur in higher concentration. The activity against brine shrimp revealed that the root extract (LD50 = 158 ppm) was the more active.
Asunto(s)
Clitoria/química , Rotenona/análogos & derivados , Animales , Artemia , Clitoria/toxicidad , Lípidos/análisis , Rotenona/análisisRESUMEN
The species Deguelia utilis and Deguelia rufescens var. urucu, popularly known as "timbó," have been used for many years as rotenone sources in insecticide formulations. In this work, a method was developed and validated using a high-performance liquid chromatography-photodiode array (HPLC-PDA) system, and results were analyzed using hierarchical cluster analysis (HCA). By quantifying the major rotenoids of these species, it was possible to establish a linear relation between them. The ratio between the concentrations of rotenone and deguelin for D. utilis is approximately 1:0.8, respectively, while for D. rufescens var. urucu it is 2:1. These results may help to distinguish these species contributing to their taxonomic identification.
Asunto(s)
Cromatografía Líquida de Alta Presión/métodos , Fabaceae/química , Insecticidas , Rotenona/análisis , Análisis por Conglomerados , Fabaceae/clasificación , Insecticidas/análisis , Raíces de Plantas/química , Rotenona/análogos & derivados , Especificidad de la EspecieRESUMEN
Following the use of rotenone to eradicate invasive pest fish, a dynamic first-order kinetic model is usually used to determine the half-life and rate at which rotenone dissipated from the treated waterbody. In this study, we investigate the use of a stochastic gamma model for determining the half-life and rate at which rotenone dissipates from waterbodies. The first-order kinetic and gamma models produced similar values for the half-life (4.45 days and 5.33 days respectively) and days to complete dissipation (51.2 days and 52.48 days respectively). However, the gamma model fitted the data better and was more flexible than the first-order kinetic model, allowing us to use covariates and to predict a possible range for the half-life of rotenone. These benefits are particularly important when examining the influence that different environmental factors have on rotenone dissipation and when trying to predict the rate at which rotenone will dissipate during future operations. We therefore recommend that in future the gamma distribution model is used when calculating the half-life of rotenone in preference to the dynamic first-order kinetics model.
Asunto(s)
Monitoreo del Ambiente/métodos , Insecticidas/análisis , Rotenona/análisis , Contaminantes Químicos del Agua/análisis , Contaminación Química del Agua/estadística & datos numéricos , Agua Dulce , Semivida , Residuos de Plaguicidas/análisisRESUMEN
In September 2006, Diamond Lake (OR, USA) was treated by the Oregon Department of Fish and Wildlife with a mixture of powdered and liquid rotenone in the successful eradication of invasive tui chub Gila bicolor. During treatment, the lake was in the middle of a phytoplankton (including cyanobacteria Anabaena sp.) bloom, resulting in an elevated pH of 9.7. Dissipation of rotenone and its major metabolite rotenolone from water, sediment, and macrophytes was monitored. Rotenone dissipated quickly from Diamond Lake water; approximately 75% was gone within 2 d, and the average half-life (t½) value, estimated by using first-order kinetics, was 4.5 d. Rotenolone persisted longer (>46 d) with a short-term t½ value of 16.2 d. Neither compound was found in groundwater, sediments, or macrophytes. The dissipation of rotenone and rotenolone appeared to occur in 2 stages, which was possibly the result of a release of both compounds from decaying phytoplankton following their initial dissipation. Fisheries managers applying rotenone for fish eradication in lentic environments should consider the following to maximize efficacy and regulatory compliance: 1) treat at a minimum of twice the minimum dose demonstrated for complete mortality of the target species and possibly higher depending on the site's water pH and algae abundance, and 2) implement a program that closely monitors rotenone concentrations in the posttreatment management of a treated water body.
Asunto(s)
Cyprinidae/fisiología , Monitoreo del Ambiente , Insecticidas/análisis , Lagos/análisis , Rotenona/análogos & derivados , Contaminantes Químicos del Agua/análisis , Animales , Cianobacterias/metabolismo , Monitoreo del Ambiente/métodos , Semivida , Insecticidas/metabolismo , Insecticidas/toxicidad , Especies Introducidas , Oregon , Fitoplancton/metabolismo , Rotenona/análisis , Rotenona/metabolismo , Rotenona/toxicidad , Contaminantes Químicos del Agua/metabolismo , Contaminantes Químicos del Agua/toxicidadRESUMEN
The dissipation and residue levels of rotenone with suspension concentrate (SC) as well as water dispersible granule (WDG) formulations in cabbage and soil were investigated under field conditions. The decline curves of rotenone residues in cabbage and soil corresponded with first-order kinetics. The dissipation rate of rotenone in cabbage was faster than that in soil. The half-lives of the SC formulations in cabbage and soil were 1.14d to 1.85d and 2.26d to 3.98d, respectively. For the WDG formulation, the values were 1.33d to 1.96d and 2.41d to 3.38d. Less spraying, lower dosage, and longer pre-harvest intervals could reduce terminal residue levels. Terminal residues below the MRL (0.5mg kg(-1)) were achieved after pre-harvest intervals of 3d at either once (45g a.i. ha(-1)) or twice (90g a.i. ha(-1)) the recommended dosage. The different dissipation processes of rotenone in cabbage and soil under field conditions could be attributed to the different climate and soil properties, and the types of formulation had no apparent effect on half-life. Formulation type affected the initial concentrations and finally led to different terminal residues. Prolonged pre-harvest intervals are necessary to ensure that the products are sufficiently safe for consumption.
Asunto(s)
Brassica/química , Residuos de Plaguicidas/análisis , Rotenona/análisis , Contaminantes del Suelo/análisis , Suelo/química , Clima , Monitoreo del Ambiente , SemividaRESUMEN
In this paper, different supervised pattern recognition methods have been applied to detect the manually additive methamidophos in rotenone preparation. The aim of this paper was to examine the performances of different supervised pattern recognition techniques: soft independent modeling of class analogy (SIMCA), partial least squares discriminant analysis (PLS-DA), artificial neutral networks (ANN), and support vector machine (SVM). The results obtained show that SVM is the most effective techniques with 100.0% classification accuracy followed by ANN, PLS-DA and with the accuracy of 97.5% and 93.3% respectively while SIMCA yields the poorest result of 85.8%. We hope that the results obtained in this study will help both further chemometric investigations and investigations in the sphere of applied vibrational spectroscopy of sophisticated multicomponent systems. Furthermore, the use of portable instrument and satisfactory classification also indicated the possibility of detecting illicit-addition at scene by near-infrared (NIR) spectroscopy which makes a great sense in pesticide quality control.
Asunto(s)
Compuestos Organotiofosforados/análisis , Reconocimiento de Normas Patrones Automatizadas/métodos , Rotenona/análisis , Espectroscopía Infrarroja Corta , Algoritmos , Método de Montecarlo , Análisis de Componente PrincipalRESUMEN
The purpose of the research was to develop and validate a rapid quantification method able to screen many samples of yam bean seeds to determine the content of two toxic polyphenols, namely pachyrrhizine and rotenone. The analytical procedure described is based on the use of an internal standard (dihydrorotenone) and is divided in three steps: microwave assisted extraction, purification by solid phase extraction and assay by ultra high performance liquid chromatography (UHPLC). Each step was included in the validation protocol and the accuracy profiles methodology was used to fully validate the method. The method was fully validated between 0.25 mg and 5 mg pachyrrhizin per gram of seeds and between 0.58 mg/g and 4 mg/g for rotenone. More than one hundred samples from different accessions, locations of growth and harvest dates were screened. Pachyrrhizine concentrations ranged from 3.29 mg/g to lower than 0.25 mg/g while rotenone concentrations ranged from 3.53 mg/g to lower than 0.58 mg/g. This screening along with principal component analysis (PCA) and discriminant analysis (DA) analyses allowed the selection of the more interesting genotypes in terms of low concentrations of these two toxic polyphenols.
Asunto(s)
Pachyrhizus/química , Polifenoles/análisis , Rotenona/análisis , Semillas/química , Cromatografía Líquida de Alta Presión/métodos , Análisis Discriminante , Genotipo , Límite de Detección , Microondas , Pachyrhizus/genética , Análisis de Componente Principal , Estándares de Referencia , Rotenona/análogos & derivados , Semillas/genética , Extracción en Fase Sólida , Factores de TiempoRESUMEN
Rotenone dissipation and terminal residue in cabbage and soil under field conditions were determined by high-performance liquid chromatography. The dissipation rates of rotenone were described using first-order kinetics. The half-lives ranged from 0.89 to 1.55 days in cabbage and 1.98 to 2.76 days in soil. Prolonged pre-harvest interval times ensure that the cabbage is safe for consumption. Temperature and the physico-chemical properties of the soil were identified as the key factors affecting rotenone degradation in cabbage and soil under field conditions.
Asunto(s)
Brassica/química , Insecticidas/análisis , Residuos de Plaguicidas/análisis , Rotenona/análisis , Contaminantes del Suelo/análisis , Biodegradación Ambiental , Fenómenos Químicos , Cromatografía Líquida de Alta Presión , Seguridad de Productos para el Consumidor , Monitoreo del Ambiente , Contaminación de Alimentos/análisis , SemividaRESUMEN
The aim of this study was to find if fast microwave-assisted extraction could be an alternative to the conventional Soxhlet extraction for the quantification of rotenone in yam bean seeds by SPE and HPLC-UV. For this purpose, an experimental design was used to determine the optimal conditions of the microwave extraction. Then the values of the quantification on three accessions from two different species of yam bean seeds were compared using the two different kinds of extraction. A microwave extraction of 11 min at 55°C using methanol/dichloromethane (50:50) allowed rotenone extraction either equivalently or more efficiently than the 8-h-Soxhlet extraction method and was less sensitive to moisture content. The selectivity, precision, trueness, accuracy, and limit of quantification of the method with microwave extraction were also demonstrated.
Asunto(s)
Fraccionamiento Químico/métodos , Cromatografía Líquida de Alta Presión/métodos , Pachyrhizus/química , Extractos Vegetales/análisis , Extractos Vegetales/aislamiento & purificación , Rotenona/análisis , Rotenona/aislamiento & purificación , Fraccionamiento Químico/instrumentación , Cromatografía Líquida de Alta Presión/instrumentación , Microondas , Semillas/químicaRESUMEN
Tephrosia vogelii has been used for generations as a pest control material in Africa. Recently, two chemotypes have been reported based on the occurrence (chemotype 1) or absence (chemotype 2) of rotenoids. This could have an impact on the efficacy and reliability of this material for pest control. We report that chemotype 2 has no pesticidal activity against Callosobruchus maculatus Fabricius (family Chrysomelidae) and that this is associated with the absence of rotenoids. We present a first report of the comparative biological activity of deguelin, tephrosin, α-toxicarol, and sarcolobine and show that not all rotenoids are equally effective. Tephrosin was less toxic than deguelin which was less active than rotenone, while obovatin 5-methyl ether, the major flavonoid in chemotype 2 was inactive. We also report that in chemotype 1 the occurrence of rotenoids shows substantial seasonal variation.
Asunto(s)
Control de Insectos , Insecticidas/análisis , Tephrosia/química , Tephrosia/clasificación , África , Animales , Escarabajos , Flavonoides/análisis , Hojas de la Planta/química , Rotenona/análogos & derivados , Rotenona/análisis , GorgojosRESUMEN
A new approach for the assay of rotenone (1) by isotope dilution mass spectrometry is presented. The extreme toxicity of rotenone, a natural phytodrug with insecticidal and piscicidal activity, recently banned by national and international environmental protection agencies, calls for the development of sensitive and accurate methods of analyses. Accordingly, the proposed protocol is based on the availability of the labeled internal standard rotenone-d3 (3) which can be conveniently prepared by consecutive and specific mono-O-demethylation, and remethylation with methyl iodide-d3. The sensitivity of the method is confirmed by the very low limit of detection (LOD) and quantitation (LOQ) values achieved in the assay of 1 in two distinct fortified matrices, and is further supported by the observed accuracy values.
Asunto(s)
Cromatografía Liquida/métodos , Aceites de Plantas/química , Ríos/química , Rotenona/análisis , Espectrometría de Masas en Tándem/métodos , Aceite de Oliva , Reproducibilidad de los Resultados , Sensibilidad y EspecificidadRESUMEN
Rotenone, azadirachtin, pyrethrins and copper fungicide decay curves were determined in olives and olive oil samples after experimental trials, consisting of one, two and three applications of each active ingredient, were carried out twice in 2005 and 2006. Rotenone, azadiracthin and pyrethrins were analyzed by extraction with acetonitrile and determined by liquid chromatography; copper was extracted into aqueous HCl and determined by chemical stripping. Pyrethrins were always found but in levels below the acceptable limits, whereas rotenone and copper residues always exceeded, after the pre-harvest interval, the maximum threshold allowed for olives. As regards residues in olive oil, rotenone was found in concentrations higher than those detected in olives. Copper accumulated in olives according to the number of applications, whereas, in oil, the residue was always lower than the maximum residue limit. The sensitivity of the method applied did not allow detection of azadirachtin.
Asunto(s)
Cobre/análisis , Limoninas/análisis , Olea , Residuos de Plaguicidas/análisis , Aceites de Plantas , Piretrinas/análisis , Rotenona/análisis , Tephritidae , Animales , Cromatografía Liquida , Límite de Detección , Aceite de OlivaRESUMEN
A new method for the analysis of three ecological insecticides, namely azadyrachtin, spinosad (sum of spinosyn A and spinosyn D) and rotenone, in produce and soil samples is presented. Investigated compounds are one of the most significant insecticides authorized for organic farming crop protection in many countries. Extraction of the pesticides from plant and soil matrices was performed by using a modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) method. The method entailed a single extraction of the investigated compounds with acidified acetonitrile followed by a dispersive solid-phase extraction cleanup step prior to the final determination by reverse-phase ultra-performance liquid chromatography/tandem quadrupole mass spectrometry (UPLC-MS/MS). Validation studies were carried out on cabbage, tomato and soil samples. Recoveries of the spiked samples were in the range between 67% and 108%, depending on the matrix and the spiking level. Relative standard deviations for all matrix-compound combinations did not exceed 12%. The limits of quantification were < or = 0.01 mg kg(-1) in all cases, except for azadirachtin. The developed method was applied to the analysis of real samples originating from organic farming production.
Asunto(s)
Cromatografía Liquida/métodos , Contaminación de Alimentos/análisis , Insecticidas/análisis , Suelo/análisis , Espectrometría de Masas en Tándem/métodos , Cromatografía Liquida/economía , Productos Agrícolas/química , Combinación de Medicamentos , Limoninas/análisis , Macrólidos/análisis , Rotenona/análisis , Sensibilidad y Especificidad , Extracción en Fase Sólida/métodos , Espectrometría de Masas en Tándem/economía , Factores de Tiempo , Verduras/químicaRESUMEN
Three slow release experimental rotenone formulations were tested to evaluate their effectiveness against Varroa destructor Anderson & Trueman in colonies with sealed brood and to determine whether they left residues in honey and bees wax: we evaluated cardboard strip containing 1 g rotenone and two types of polyvinyl chloride (PVC) strips containing 1 (high-dose) and 0.5 (low-dose) g of rotenone, respectively. In general, the efficacy of the treatments, expressed as percentage of mite mortality, was highly variable in all treatment groups (range, 0-96.8%). The highest effectiveness was obtained with the high-dose-PVC strips, which caused an average percentage of mortality ranging between 47 and 69% in the adult bees and sealed brood, respectively. At the end of the treatment, rotenone residues ranged between 0.03 and 0.06 and 1.5-144.0 mg/kg in honey and wax, respectively. Rotenone residues in wax were still detectable 4 mo after the treatment period, whereas no residues were found in honey. The higher residues content and persistence recorded in wax samples, was probably due to the lipophilic nature of rotenone. A reduction in the amount of adults was recorded for the group treated with high-dose-PVC strips compared with the untreated colonies. Toxicological risks connected with the use of rotenone and the low maximum level recently fixed by European legislation (0.01 mg/kg) suggest that rotenone is not a good candidate for reducing varroa populations in honey bee colonies.