Bioactive natural products from fungicolous Hawaiian isolates: secondary metabolites from a Phialemoniopsis sp.

Chemical investigations of two fungal isolates initially identified as members of the genus Phialemonium are described. Both isolates were obtained as colonists of other fungi collected on the island of Hawaii and were later assigned as P. curvatum. However, P. curvatum has recently been reclassified as a member of a new genus (Phialemoniopsis) and renamed as Phialemoniopsis curvata. Studies of solid-substrate fermentation cultures of one of these isolates afforded an oxirapentyn analogue and destruxin A4 as major components, while analysis of the second strain led to the isolation of several simple aromatic metabolites and a compound of mixed biogenetic origin called gabusectin that had previously been reported only in a patent. Structures were assigned mainly by detailed nuclear magnetic resonance and mass spectrometry analysis, and those of two of the major components were confirmed by X-ray crystallography. This report constitutes the first description of secondary metabolites from a member of the genus Phialemoniopsis.

Diplodiatoxin, chaetoglobosins, and diplonine associated with a field outbreak of Stenocarpella ear rot in Illinois.

Stenocarpella maydis causes a fungal dry-rot of maize ears and is associated with diplodiosis, a neuromycotoxicosis in cattle grazing harvested maize fields in southern Africa and Argentina. There have been no reports of Stenocarpella metabolites in maize crop residues. Chemical investigations of S. maydis-infected grain from ears exhibiting different levels of ear rot severity following a 2010 field outbreak of Stenocarpella ear rot in Illinois led to the detection of diplodiatoxin and chaetoglobosins M and O as major components in the ethyl acetate extracts by LC-MS. Following post-harvest moist incubation of the S. maydis-infected grain, the amounts of each compound increased (approx. tenfold) and chaetoglobosin K was detected as a dominant toxin. In separate (1)H NMR-based analyses, the neurotoxin diplonine was detected as a minor component in methanol extracts of S. maydis-infected grain as well as cultures of S. maydis isolates from Midwest corn. Proline betaine (=stachydrine) and glycine betaine were also detected in these extracts as major components. This constitutes the first report of chaetoglobosin M, chaetoglobosin O, proline betaine, or glycine betaine from S. maydis, and the first record of diplodiatoxin, diplonine, proline betaine, glycine betaine, or chaetoglobosins M, O, or K being associated with a natural field outreak of S. maydis ear rot.

Bioactive metabolites from Stenocarpella maydis, a stalk and ear rot pathogen of maize.

Stenocarpella maydis is a fungal pathogen of major importance that causes a dry-rot of maize ears and is associated with a neuromycotoxicosis in cattle grazing harvested maize fields in southern Africa and Argentina. In an effort to investigate the potential roles of S. maydis metabolites in the fungal disease cycle, ethyl acetate extracts of solid-substrate fermentations of several S. maydis isolates from maize grown in the United States were found to exhibit significant phytotoxic, antifungal, and antiinsectan activity. Chemical investigations of extracts of S. maydis isolates from Illinois and Nebraska led to the isolation or detection of the known metabolites diplodiatoxin, chaetoglobosins K and L, and (all-E)-trideca-4,6,10,12-tetraene-2,8-diol as major components. A culture of Stenocarpella macrospora from maize grown in Zambia produced diplosporin and chaetoglobosins K and L as major components that were isolated. Diplodiatoxin produced significant lesions in a maize leaf puncture wound assay. Diplosporin and chaetoglobosin K displayed moderate antiinsectan activity in dietary assays against the fall armyworm Spodoptera frugiperda, while chaetoglobosin K exhibited significant antifungal activity against Aspergillus flavus and Fusarium verticillioides. Using LC-ESIMS and (1)H NMR data, diplodiatoxin was detected as a major component in S. maydis-rotted grain, stalks, and stalk residues. This constitutes the first report of chaetoglobosins K and L from S. maydis, of (all-E)-trideca-4,6,10,12-tetraene-2,8-diol from Stenocarpella, and the first reported detection of diplodiatoxin, or any other Stenocarpella metabolite, in diseased maize seeds and stalk tissues.

Acremonium zeae, a protective endophyte of maize, produces dihydroresorcylide and 7-hydroxydihydroresorcylides.

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.