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  1. The fungi that cause brown rot of wood are essential contributors to biomass recycling in forest ecosystems. Their highly efficient cellulolytic systems, which may have practical applications, apparently depend on a combination of two mechanisms: nonselective oxidation of the lignocellulose by reactive oxygen species (ROS) coupled with hydrolysis of the polysaccharide components by a limited set of glycoside hydrolases (GHs). Since the production of strongly oxidizing ROS appears incompatible with the operation of GHs, it has been proposed that the fungi regulate ROS production by maintaining concentration gradients of the chelated metal ions they use to generate extracellular oxidants. However,more » calculations have indicated that this protective mechanism is physically infeasible. We examined a different hypothesis, that expression of ROS and GH components is temporally staggered by brown rot fungi in wood. We sectioned thin wafers of spruce and aspen that had been colonized directionally by Postia placenta and measured expression of relevant genes and some of the encoded enzymes, thus using the spatial distribution of fungal hyphae to resolve a fine-scale temporal sequence. Hierarchical clustering of gene expression for eight oxidoreductases thought to have a role in ROS production and of eight GHs revealed a zone of oxidoreductase upregulation at the hyphal front that persisted about 48 h before upregulation of the GHs. Additional evidence for differential expression was provided by localization of endoglucanase, xylanase, mannanase, and laccase activities in the colonized wood. Our results support a two-step mechanism for brown rot, in which substrate oxidation precedes enzymatic hydrolysis.« less
    Cited by 11Full Text Available
  2. Redox flow batteries have shown outstanding promise for grid-scale energy storage to promote utilization of renewable energy and improve grid stability. Nonaqueous battery systems can potentially achieve high energy density because of their broad voltage window. In this paper, we report a new organic redox-active material for use in a nonaqueous redox flow battery, 2-phenyl-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide (PTIO) that has high solubility (>2.6 M) in organic solvents. PTIO exhibits electrochemically reversible disproportionation reactions and thus can serve as both anolyte and catholyte redox materials in a symmetric flow cell. The PTIO flow battery has a moderate cell voltage of ~1.7 V andmore » shows good cyclability under both cyclic voltammetry and flow cell conditions. Moreover, we demonstrate that FTIR can offer accurate estimation of the PTIO concentration in electrolytes and determine the state of charge of the PTIO flow cell, which suggests FTIR potentially as a powerful online battery status sensor. In conclusion, this study is expected to inspire more insights in this under-addressed area of state of charge analysis aiming at operational safety and reliability of flow batteries.« less
    Cited by 30Full Text Available

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