Non-targeted chemical analysis is a powerful tool for exploration of the unknown chemistry of complex matrices such as food, biological, geochemical, environmental and even extra-terrestrial samples. It allows researchers to ask open, unbiased questions about their system chemistry. Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR-MS) offers these options and has been widely used to study complex mixtures, with its unmatched mass resolution enabling direct infusion methods and eliminating the challenges of chromatographic alignment in large-scale longitudinal projects.
View Article and Find Full Text PDFSolid-state magic angle spinning P NMR spectroscopy is used to identify and quantify phosphorus-containing species in pet foods. The measurement is challenging due to the long spin-lattice relaxation times (s). Data acquisition times are shortened by acquiring data with a tip angle smaller than 90° and shortening the repetition time.
View Article and Find Full Text PDFIdentification of chemically modified peptides in mass spectrometry (MS)-based glycation studies is a crucial yet challenging task. There is a need to establish a mode for matching tandem mass spectrometry (MS/MS) data, allowing for both known and unknown peptide glycation modifications. We present an open search approach that uses classic and modified peptide fragment ions.
View Article and Find Full Text PDFPhosphorus (P) is an essential nutrient; however, potential health impacts of high dietary levels of added soluble, highly bioavailable P salts especially are a concern. P sources with lower bioavailability are considered safer. Yet, speciation of different P sources to assess diets' risk to health is challenging.
View Article and Find Full Text PDFPeptide glycation is an important, yet poorly understood reaction not only found in food but also in biological systems. The enormous heterogeneity of peptides and the complexity of glycation reactions impeded large-scale analysis of peptide derived glycation products and to understand both the contributing factors and how this affects the biological activity of peptides. Analyzing time-resolved Amadori product formation, we here explored site-specific glycation for 264 peptides.
View Article and Find Full Text PDFFusarochromene isolated from the plant pathogenic fungus, Fusarium sacchari is closely related to a group of mycotoxins including fusarochromanone previously isolated from various Fusaria spp. Despite their assumed polyketide biogenesis, incorporation studies with 13C-labelled acetate, glycerol and tryptophans show that fusarochromene is unexpectedly derived via oxidative cleavage of the aromatic amino acid tryptophan. A putative biosynthetic gene cluster has been identified.
View Article and Find Full Text PDFReactions between sugars and amino acids in the Maillard reaction produce a multitude of compounds through interconnected chemical pathways. The course of the pathways changes depending on the nature of the amino acids and sugars as well as the processing conditions (e.g.
View Article and Find Full Text PDFSterilised food products undergo chemical changes during processing that ultimately determine the product quality. To provide detailed information on the chemistry of each stage of a pet-food sterilisation process, a laboratory-scale system was developed, which allowed sampling under the high temperatures and pressures associated with sterilisation. Products from the laboratory-scale system were representative of the factory process.
View Article and Find Full Text PDFIn this study, we monitored the thermal formation of early ribose-glycine Maillard reaction products over time by ion cyclotron resonance mass spectrometry. Here, we considered sugar decomposition (caramelization) apart from compounds that could only be produced in the presence of the amino acid. More than 300 intermediates as a result of the two initial reactants were found after ten hours (100 °C) to participate in the interplay of the Maillard reaction cascade.
View Article and Find Full Text PDFPeroxiredoxin 1 is a member of the ubiquitous peroxiredoxin family of thiol peroxidases that catalyse the reduction of peroxides. In recent years eukaryotic peroxiredoxins have emerged as a critical component of cellular redox signalling, particularly in response to alterations in production of hydrogen peroxide. Peroxiredoxins are exquisitely sensitive to oxidation by hydrogen peroxide making them key peroxide sensing enzymes within cells.
View Article and Find Full Text PDFThe and genes from the avirulence signalling gene cluster of the rice blast fungus were expressed in and itself. Expression of alone produced a polyenyl pyrone (magnaporthepyrone), which is regioselectively epoxidised and hydrolysed to give different diols, and , in the two host organisms. Analysis of the three introns present in determined that does not process intron 2 correctly, while processes all introns correctly in both appressoria and mycelia.
View Article and Find Full Text PDFA retrospective medical record review was conducted to identify factors from veterinary clinic medical records that may have contributed to suspected ineffectiveness of a heartworm preventive product. Patient records of 271 dogs, comprising 301 instances of positive heartworm antigen test results while the dogs were receiving heartworm preventive were evaluated. Nineteen veterinary practices in 17 counties and parishes in Arkansas, Louisiana, Mississippi, and Tennessee participated in the study.
View Article and Find Full Text PDFFSN1, a gene isolated from the sugar-cane pathogen Fusarium sacchari, encodes a 4707-residue nonribosomal peptide synthetase consisting of three complete adenylation, thiolation and condensation modules followed by two additional thiolation and condensation domain repeats. This structure is similar to that of ferricrocin synthetase, which makes a siderophore that is involved in intracellular iron storage in other filamentous fungi. Heterologous expression of FSN1 in Aspergillus oryzae resulted in the accumulation of a secreted metabolite that was identified as ferrirhodin.
View Article and Find Full Text PDFThe tenS gene encoding tenellin synthetase (TENS), a 4239-residue polyketide synthase nonribosomal-peptide synthetase (PKS-NRPS) from Beauveria bassiana, was expressed in Aspergillus oryzae M-2-3. This led to the production of three new compounds, identified as acyl tetramic acids, and numerous minor metabolites. Consideration of the structures of these compounds indicates that the putative C-terminal thiolester reductase (R) domain does not act as a reductase, but appears to act as a Dieckmann cyclase (DKC).
View Article and Find Full Text PDFPhotorhabdus is a virulent pathogen that kills its insect host by overcoming immune responses. The bacterium also secretes a range of antibiotics to suppress the growth of other invading microorganisms. Here we show that Photorhabdus produces a small-molecule antibiotic (E)-1,3-dihydroxy-2-(isopropyl)-5-(2-phenylethenyl)benzene (ST) that also acts as an inhibitor of phenoloxidase (PO) in the insect host Manduca sexta.
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