RESUMEN
The trichothecenes produced by solid and liquid cultures of Fusarium sporotrichioides were evaluated with high performance liquid chromatography-tandem mass spectrometry (LC-MS/MS). Along with the expected T-2 toxin HT-2 toxin and neosolaniol, two additional compounds were detected, which had ions 162 m/z higher than those in the mass spectra of T-2 toxin or HT-2 toxin. Fragmentation behavior of these two compounds was similar to that of T-2 toxin and HT-2 toxin. Based on LC-MS/MS behavior, it is proposed that the two compounds are T-2 toxin 3-O-glucoside and HT-2 toxin 3-O-glucoside. Production of the two glucosides was measured in kernels from wheat and oat inoculated with F. sporotrichiodes, as well as in cultures grown in liquid media and on cracked corn or rice. Production of glucosides in wheat and oats suggest that they may also be present in naturally contaminated cereals.
Asunto(s)
Cromatografía Líquida de Alta Presión/métodos , Fusarium/metabolismo , Glucósidos/análisis , Toxina T-2/análogos & derivados , Toxina T-2/análisis , Espectrometría de Masas en Tándem/métodos , Grano Comestible/microbiología , Glucósidos/biosíntesis , Toxina T-2/biosíntesisRESUMEN
The presence of deoxynivalenol (DON) in cereal-based baby food, a primary source of the first solid food for infants, was studied in order to develop a method to detect its presence at low concentrations. DON, produced primarily by Fusarium graminearum, is commonly isolated from grains and feed around the world and affects both animal and human health, producing diarrhea, vomiting, gastrointestinal inflammation, and immunomodulation. An aqueous extract of infant cereal was cleaned by means of an immunoaffinity chromatography column. After the eluate was evaporated and redissolved, DON was determined by high-pressure liquid chromatography-UV. The level of quantification for DON was 10 ppb for three types of infant cereal (mixed, barley, and oatmeal); the level of detection was 5 ppb. The protocol we have developed can measure DON between 10 to 500 ppb. An advisory level of 1 ppm for wheat products has been established by the U.S. Food and Drug Administration; however, the European Communities (EC) regulations have been set at 200 ppb for cereal-based foods for infants. Only 1 of 52 samples of barley-, mixed-, or oat-based infant cereal purchased in 2008 and 2009 in the United States exceeded the European standard.
Asunto(s)
Grano Comestible/química , Contaminación de Alimentos/análisis , Alimentos Infantiles/análisis , Tricotecenos/aislamiento & purificación , Cromatografía Líquida de Alta Presión , Seguridad de Productos para el Consumidor , Grano Comestible/microbiología , Microbiología de Alimentos , Humanos , Lactante , Medición de Riesgo , Tricotecenos/análisisRESUMEN
Acremonium zeae produces pyrrocidines A and B, which are polyketide-amino acid-derived antibiotics, and is recognized as a seedborne protective endophyte of maize which augments host defenses against microbial pathogens causing seedling blights and stalk rots. Pyrrocidine A displayed significant in vitro activity against Aspergillus flavus and Fusarium verticillioides in assays performed using conidia as inoculum, with pyrrocidine A being more active than B. In equivalent assays performed with conidia or hyphal cells as inoculum, pyrrocidine A revealed potent activity against major stalk and ear rot pathogens of maize, including F. graminearum, Nigrospora oryzae, Stenocarpella (Diplodia) maydis, and Rhizoctonia zeae. Pyrrocidine A displayed significant activity against seed-rotting saprophytes A. flavus and Eupenicillium ochrosalmoneum, as well as seed-infecting colonists of the phylloplane Alternaria alternata, Cladosporium cladosporioides, and Curvularia lunata, which produces a damaging leaf spot disease. Protective endophytes, including mycoparasites which grow asymptomatically within healthy maize tissues, show little sensitivity to pyrrocidines. Pyrrocidine A also exhibited potent activity against Clavibacter michiganense subsp. nebraskense, causal agent of Goss's bacterial wilt of maize, and Bacillus mojaviense and Pseudomonas fluorescens, maize endophytes applied as biocontrol agents, but were ineffective against the wilt-producing bacterium Pantoea stewartii.
Asunto(s)
Acremonium/metabolismo , Antiinfecciosos/farmacología , Enfermedades de las Plantas/microbiología , Pirrolidinonas/farmacología , Zea mays/microbiología , Bacterias/efectos de los fármacos , Hongos/efectos de los fármacos , Pruebas de Sensibilidad Microbiana , Estructura Molecular , Pirrolidinonas/química , Pirrolidinonas/metabolismoRESUMEN
Acremonium zeae has been characterized as a protective endophyte of maize and displays antifungal activity against other fungi. Pyrrocidines A and B were discovered to be the metabolites accounting for this activity. During a population survey of A. zeae isolates from maize seeds produced in nine states to determine their ability to produce pyrrocidines, another metabolite of A. zeae, unrelated to the pyrrocidines, was found to have widespread occurrence (105 of 154 isolates) and to be produced in amounts comparable to the pyrrocidines. Further chemical studies of fermentation extracts of an A. zeae isolate (NRRL 45893) from maize led to the identification of a new compound, dihydroresorcylide, the saturated analogue of cis-resorcylide. Also identified were the two diastereomers of 7-hydroxydihydroresorcylide. Dihydroresorcylide and pyrrocidines A and B were detected by LC-APCI-MS in symptomatic maize kernels from ears that were wound-inoculated in the milk stage with A. zeae NRRL 34559.
Asunto(s)
Acremonium/metabolismo , Macrólidos/metabolismo , Semillas/microbiología , Zea mays/microbiología , Hidrocarburos Aromáticos con Puentes/análisis , Hidrocarburos Aromáticos con Puentes/metabolismo , Fungicidas Industriales/farmacología , Macrólidos/análisis , Macrólidos/química , Macrólidos/farmacología , Pirrolidinonas/análisis , Pirrolidinonas/metabolismo , EstereoisomerismoRESUMEN
Incubation of fumonisin B(1) and D-glucose in aqueous solutions resulted in the formation of N-(1-deoxy-D-fructos-1-yl) fumonisin B(1) in addition to the previously reported N-(carboxymethyl) fumonisin B(1). N-(1-Deoxy-D-fructos-1-yl) fumonisin B(1) is the first stable product formed after the Amadori rearrangement of the Schiff base formed by the reaction of the primary amine of fumonisin B(1) and the aldehyde group of D-glucose. N-(1-Deoxy-D-fructos-1-yl) fumonisin B(1) was synthesized by reacting fumonisin B(1) with an excess of D-glucose in methanol and heating for 6 h at 64 degrees C. It was purified using C(18) and strong cation exchange solid-phase extraction cartridges and characterized by nuclear magnetic resonance and liquid chromatography-mass spectrometry. Subsequently, N,N-dimethylformamide was found to be a better reaction solvent, requiring reaction for only 2-3 h at 64 degrees C and eliminating the formation of methyl esters. Alkaline hydrolysis of N-(1-deoxy-D-fructos-1-yl) fumonisin B(1) gave a mixture of hydrolyzed fumonisin B(1) and hydrolyzed N-(carboxymethyl) fumonisin B(1).