Evidence for a reversible drought induced shift in the species composition of mycotoxin producing Fusarium head blight pathogens isolated from symptomatic wheat heads.

Fusarium species are fungal plant pathogens producing toxic secondary metabolites such as deoxynivalenol (DON), 15-acetyl-deoxynivalenol (15AcDON) and nivalenol (NIV). In Luxembourg, the Fusarium species composition isolated from symptomatic winter wheat heads was dominated by Fusarium graminearum sensu stricto strains (genetic 15AcDON chemotype) between the years 2009 and 2012, except for 2011, when Fusarium culmorum strains (genetic NIV chemotype) dominated the pathogen complex. Previous reports indicated that F. graminearum sensu stricto (genetic 15AcDON chemotype) was also most frequently isolated from randomly sampled winter wheat kernels including symptomatic as well as asymptomatic kernels in 2007 and 2008. The annual precipitation (average of 10 weather stations scattered across the country) decreased continuously from 924.31mm in 2007 over 917.15mm in 2008, to 843.38mm in 2009, 736.24mm in 2010, and 575.09mm in 2011. In 2012, the annual precipitation increased again to 854.70mm. Hardly any precipitation was recorded around the time of wheat anthesis in the years 2010 and 2011, whereas precipitation levels >50mm within the week preceding anthesis plus the week post anthesis were observed in the other years. The shift to genetic NIV chemotype F. culmorum strains in 2011 was accompanied by a very minor elevation of average NIV contents (2.9ngg(-1)) in the grain. Our data suggest that high NIV levels in Luxembourgish winter wheat are at present rather unlikely, because the indigenous F. culmorum strains with the genetic NIV chemotype seem to be outcompeted under humid in vivo conditions by F. graminearum DON producing strains on the one hand and seem to be inhibited - even though to a lower extent than DON producing strains - under dry in vivo conditions on the other hand.

Bioinspired insights into silicic acid stabilization mechanisms: the dominant role of polyethylene glycol-induced hydrogen bonding.

Mono- and disilicic acids were stabilized by uncharged polyethylene glycols (PEGs) in silica-supersaturated solutions (the starting solution contained 500 ppm/8.3 mM sodium orthosilicate, Na2SiO3·5H2O, expressed as SiO2) at pH = 7, most likely by hydrogen bonding between the silanol groups and -CH2-CH2-O-ether moieties. The stabilization was monitored by measuring molybdate-reactive silica and also by a combination of liquid- and solid-state (29)Si NMR spectroscopy. It depends on PEG concentration (20-100 ppm) and molecular weight (1550-20,000 Da). Two narrow (29)Si NMR signals characteristic for monosilicic acid (Q(0)) and disilicic acid (Q(1)) can be observed in (29)Si NMR spectra of solutions containing PEG 10000 with intensities distinctly higher than the control, that is, in the absence of PEG. Silica-containing precipitates are observed in the presence of PEG, in contrast to the gel formed in the absence of PEG. These precipitates exhibit similar degrees of silica polycondensation as found in the gel as can be seen from the (29)Si MAS NMR spectra. However, the (2)D HETCOR spectra show different (1)H NMR signal shifts: The signal due to H-bonded SiOH/H2O, which is found at 6 ppm in the control, is shifted to ~7 ppm in the PEG-containing precipitate. This indicates the formation of slightly stronger H-bonds than in the control sample, most likely between PEG and the silica species. The presence of PEG in these precipitates is unequivocally proven by (13)C CP MAS NMR spectroscopy. The (13)C signal of PEG significantly shifts and is much narrower in the precipitates as compared to the pristine PEG, indicating that PEG is embedded into the silica or at least bound to its surface (or both), and not phase separated. FT-IR spectra corroborate the above arguments. The H-bonding between silanol and ethereal O perturbs the band positions attributed to vibrations involving the O atom. This work may invoke an alternative way to envision silica species stabilization (prior to biosilica formation) in diatoms by investigating possible scenarios of uncharged biomacromolecules playing a role in biosilica synthesis.