Effects of Atmospheric CO2 Level on the Metabolic Response of Resistant and Susceptible Wheat to Fusarium graminearum Infection.

Rising atmospheric CO2 concentrations and associated climate changes are thought to have contributed to the steady increase of Fusarium head blight (FHB) on wheat. However, our understanding of precisely how elevated CO2 influences the defense response of wheat against Fusarium graminearum remains limited. In this study, we evaluated the metabolic profiles of susceptible (Norm) and moderately resistant (Alsen) spring wheat in response to whole-head inoculation with two deoxynivalenol (DON)-producing F. graminearum isolates (DON+), isolates 9F1 and Gz3639, and a DON-deficient (DON−) isolate (Gzt40) at ambient (400 ppm) and elevated (800 ppm) CO2 concentrations. The effects of elevated CO2 were dependent on both the Fusarium strain and the wheat variety, but metabolic differences in the host can explain the observed changes in F. graminearum biomass and DON accumulation. The complexity of abiotic and biotic stress interactions makes it difficult to determine if the observed metabolic changes in wheat are a result of CO2-induced changes in the host, the pathogen, or a combination of both. However, the effects of elevated CO2 were not dependent on DON production. Finally, we identified several metabolic biomarkers for wheat that can reliably predict FHB resistance or susceptibility, even as atmospheric CO2 levels rise

Two-Carbon Homologation of Aldehydes and Ketones to α,β-Unsaturated Aldehydes

Phosphonate reagents were developed for the two-carbon homologation of aldehydes or ketones to unbranched- or methyl-branched α,β-unsaturated aldehydes. The phosphonate reagents, diethyl methylformyl-2-phosphonate dimethylhydrazone and diethyl ethylformyl-2-phosphonate dimethylhydrazone, contained a protected aldehyde group instead of the usual ester group. A homologation cycle entailed condensation of the reagent with the starting aldehyde, followed by removal of the dimethylhydrazone protective group with a biphasic mixture of 1 M HCl and petroleum ether. This robust two-step process worked with a variety of aldehydes and ketones. Overall isolated yields of unsaturated aldehyde products ranged from 71% to 86% after the condensation and deprotection steps

Two-Carbon Homologation of Aldehydes and Ketones to α,β-Unsaturated Aldehydes

Phosphonate reagents were developed for the two-carbon homologation of aldehydes or ketones to unbranched- or methyl-branched α,β-unsaturated aldehydes. The phosphonate reagents, diethyl methylformyl-2-phosphonate dimethylhydrazone and diethyl ethylformyl-2-phosphonate dimethylhydrazone, contained a protected aldehyde group instead of the usual ester group. A homologation cycle entailed condensation of the reagent with the starting aldehyde, followed by removal of the dimethylhydrazone protective group with a biphasic mixture of 1 M HCl and petroleum ether. This robust two-step process worked with a variety of aldehydes and ketones. Overall isolated yields of unsaturated aldehyde products ranged from 71% to 86% after the condensation and deprotection steps

Structural characterization of novel extracellular liamocins (mannitol oils) produced by Aureobasidium pullulans strain NRRL 50380

Aureobasidium pullulans is a common, ubiquitous fungus, which is used industrially to produce the polysaccharide pullulan. We have previously shown that A. pullulans produces various heavier-than-water oils, first named here as liamocins, that accumulate in fermentations. Here we report the structural characterization of four liamocins, A1, A2, B1, and B2, produced by A. pullulans strain NRRL 50380 using a combination of MALDI-TOF/MS, quadrupole-TOF/MS, isotopic labeling, NMR, GC/MS, and classical carbohydrate analysis. The data showed that the liamocins are composed of a single mannitol headgroup partially O-acylated with three (for liamocin A1 and A2) or four (for liamocin B1 and B2) 3,5-dihydroxydecanoic ester groups. Liamocins A1 and B1 are non-acetylated, whereas A2 and B2 each contain a single 3′-O-acetyl group. Each of these compounds is characterized by pseudomolecular [M+Na]+ ions in the MALDI-TOF/MS spectra at m/z 763.22, 949.35, 805.22, and 991.37, respectively. The 186 Da mass difference between A-type and B-type liamocins corresponds to one O-linked 3,5-dihydroxydecanoate group. HMBC NMR showed that one 3,5-dihydroxydecanoate carbonyl group is ester linked to a primary hydroxyl on the mannitol. Other long range 13C–1H couplings across 1,5-ester bridges showed that the 3,5-dihydroxydecanoate groups form 1–5-linked polyester chains, similar in structure to the antibiotic substance exophilin A. Moreover, the MS analysis identified several non-conjugated poly-3,5-dihydroxydecanoate esters as minor components that are tentatively assigned as exophilins A1, A2, B1, and B2. The liamocins, and three of the exophilins, are new, previously unreported structures

Thiazolidine Peracetates: Carbohydrate Derivatives that Readily Assign <i>cis‑</i>,<i>trans</i>-2,3-Monosaccharides by Gas Chromatography–Mass Spectrometry Analysis

A novel group of carbohydrate derivatives is described that uniquely assign <i>cis</i>/<i>trans</i>-2,3-aldose stereoisomers at low nanomolar concentrations. Aldopentoses, aldohexoses, or component aldoses from hydrolysis of polysaccharides or oligosaccharides react with cysteamine in pyridine to give quantitative formation of thiazolidines, which are subsequently peracetylated in a one-pot reaction. The nonpolar thiazolidines peracetate (TPA) derivatives are analyzed by gas chromatography and electron impact mass spectrometry (GC/EI-MS), each aldose giving rise to two TPA geometric isomers. The quantitative ratio of these diastereomers is dependent upon whether the parent monosaccharide is <i>cis</i>-2,3-(Rib, Lyx, Man, All, Gul, and Tal), or <i>trans</i>-2,3-aldose (Xyl, Ara, Glc, Gal, Ido, and Alt). TPAs generate observed EI-MS fragment ions characteristic of C1–C2 and C3–C4 bond cleavage of the parent sugars. This has been used to estimate the extent of metabolic labeling of microbial cell-wall carbohydrates, especially into the defining anomeric carbons and during aldolase / ketolase -catalyzed rearrangements