An overview of the different inhibitors formed by pre-treatment of lignocellulosic materials and their inhibition of ethanol production in yeast and bacteria is given. Different high temperature physical pre-treatment methods are available to render the carbohydrates in lignocellulose accessible for ethanol fermentation. The resulting hydrolyzsates contain substances inhibitory to fermentation—depending on both the raw material (biomass) and the pre-treatment applied. An overview of the inhibitory effect on ethanol production by yeast and bacteria is presented. Apart from furans formed by sugar degradation, phenol monomers from lignin degradation are important co-factors in hydrolysate inhibition, and inhibitory effects of these aromatic compounds on different ethanol producing microorganisms is reviewed. The furans and phenols generally inhibited growth and ethanol production rate (QEtOH) but not the ethanol yields (YEtOH) in Saccharomyces cerevisiae. Within the same phenol functional group (aldehyde, ketone, and acid) the inhibition of volumetric ethanol productivity was found to depend on the amount of methoxyl substituents and hence hydrophobicity (log P). Many pentose-utilizing strains Escherichia coli, Pichia stipititis, and Zymomonas mobilis produce ethanol in concentrated hemicellulose liquors but detoxification by overliming is needed. Thermoanaerobacter mathranii A3M3 can grow on pentoses and produce ethanol in hydrolysate without any need for detoxification.

Inhibition of ethanol-producing yeast and bacteria by degradation products produced during pre-treatment of biomass.

In this review, primary attention is given to the antioxidant (and prooxidant) activity of polyphenols arising from their interactions with iron both in vitro and in vivo. In addition, an overview of oxidative stress and the Fenton reaction is provided, as well as a discussion of the chemistry of iron binding by catecholate, gallate, and semiquinone ligands along with their stability constants, UV–vis spectra, stoichiometries in solution as a function of pH, rates of iron oxidation by O2 upon polyphenol binding, and the published crystal structures for iron–polyphenol complexes. Radical scavenging mechanisms of polyphenols unrelated to iron binding, their interactions with copper, and the prooxidant activity of iron–polyphenol complexes are briefly discussed.

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A Review of the Antioxidant Mechanisms of Polyphenol Compounds Related to Iron Binding

Minerals and organic matter (OM) may form intricate associations via myriad interactions. In soils, the associations of OM with mineral surfaces are mainly investigated because of their role in determining the long-term retention of OM. OM “must decay in order to release the energy and nutrients that drive live processes all over the planet” ( Janzen, 2006 ). Thus, the processes and mechanisms that retain OM in soil are a central concern to very different branches of environmental research. An agronomist may want to synchronize periods of high nutrient and energy release with the growth stages of a crop. An environmental chemist may wish to either immobilize an organic soil contaminant or enhance its decomposition into less harmful metabolites, while climate scientists need to understand the processes that mediate the production of potent greenhouse gases from decomposing OM. Associations of OM with pedogenic minerals (henceforth termed mineral–organic associations (MOAs)) are known to be key controls in these and many other processes. Here we strive to present an overview of the current knowledge on MOAs and identify key questions and future research needs.

Chapter One – Mineral–Organic Associations: Formation, Properties, and Relevance in Soil Environments

Ten phenols were selected as natural laccase mediators after screening 44 different compounds with a recalcitrant dye (Reactive Black 5) as a substrate. Their performances were evaluated at different mediator/dye ratios and incubation times (up to 6 h) by the use of Pycnoporus cinnabarinus and Trametes villosa laccases and were compared with those of eight known synthetic mediators (including -NOH- compounds). Among the six types of dyes assayed, only Reactive Blue 38 (phthalocyanine) was resistant to laccase-mediator treatment under the conditions used. Acid Blue 74 (indigoid dye), Reactive Blue 19 (anthraquinoid dye), and Aniline Blue (triarylmethane-type dye) were partially decolorized by the laccases alone, although decolorization was much more efficient and rapid with mediators, whereas Reactive Black 5 (diazo dye) and Azure B (heterocyclic dye) could be decolorized only in the presence of mediators. The efficiency of each natural mediator depended on the type of dye to be treated but, with the only exception being Azure B (<50% decolorization), nearly complete decolorization (80 to 100%) was attained in all cases. Similar rates were attained with the best synthetic mediators, but the reactions were significantly slower. Phenolic aldehydes, ketones, acids, and esters related to the three lignin units were among the best mediators, including p-coumaric acid, vanillin, acetovanillone, methyl vanillate, and above all, syringaldehyde and acetosyringone. The last two compounds are especially promising as ecofriendly (and potentially cheap) mediators for industrial applications since they provided the highest decolorization rates in only 5 to 30 min, depending on the type of dye to be treated.

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Lignin-derived compounds as efficient laccase mediators for decolorization of different types of recalcitrant dyes.

In mammals, cadmium is widely considered as a non-genotoxic carcinogen acting through a methylation-dependent epigenetic mechanism. Here, the effects of Cd treatment on the DNA methylation patten are examined together with its effect on chromatin reconfiguration in Posidonia oceanica. DNA methylation level and pattern were analysed in actively growing organs, under short- (6 h) and long- (2 d or 4 d) term and low (10 mM) and high (50 mM) doses of Cd, through a Methylation-Sensitive Amplification Polymorphism technique and an immunocytological approach, respectively. The expression of one member of the CHROMOMETHYLASE (CMT) family, a DNA methyltransferase, was also assessed by qRT-PCR. Nuclear chromatin ultrastructure was investigated by transmission electron microscopy. Cd treatment induced a DNA hypermethylation, as well as an up-regulation of CMT, indicating that de novo methylation did indeed occur. Moreover, a high dose of Cd led to a progressive heterochromatinization of interphase nuclei and apoptotic figures were also observed after long-term treatment. The data demonstrate that Cd perturbs the DNA methylation status through the involvement of a specific methyltransferase. Such changes are linked to nuclear chromatin reconfiguration likely to establish a new balance of expressed/repressed chromatin. Overall, the data show an epigenetic basis to the mechanism underlying Cd toxicity in plants.

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In Posidonia oceanica cadmium induces changes in DNA methylation and chromatin patterning

The literature relating to the pKa -values of guaiacyl- and syringyl-derived phenols has been thoroughly surveyed and summarized. In addition, the pKa -values of a number of guaiacyl, syringyl and other phenols related to lignin have been determined using a spectrophotometric method combined with multivariate evaluation. Differences and similarities between the acidities of a number of substances are extensively discussed. The pKa -value strongly affects the delignification during pulping, bleaching and leaching of lignin during pulp washing.

pKa-Values of Guaiacyl and Syringyl Phenols Related to Lignin

Hexenuronic acid reactions in chlorine dioxide bleaching - aspects on in situ formation of molecular chlorine

Ways to reduce the amount of organically bound chlorine in bleached pulp and the AOX discharges from ECF bleaching

A novel spectrophotometric tool for bleaching studies and determination of hexenuronic acid removal

Fifteen different hardwood species have been investigated with regard to their kraft cooking characteristics. Firstly, all the species were cooked to a reference kappa number of 16.4+/-1.0. The evaluation of the results includes cooking yield, viscosity, xylan content and hexenuronic acid concentration. The difference between the different species is very large in many respects. In a second part of the study, ten Eucalypt species were cooked under identical conditions. Interestingly, the species yielding pulps with the highest kappa numbers also showed the lowest cooking yield, which emphasizes the importance of the choice of Eucalypt species when a forest is planted for pulping purposes. In a third part of the investigation, the mechanisms determining the concentration of hexenuronic acid in a pulp are discussed and exemplified with trials on Oak and Birch.

Martin Ragnar

Papers

pKa-Values of Guaiacyl and Syringyl Phenols Related to Lignin

Hexenuronic acid reactions in chlorine dioxide bleaching - aspects on in situ formation of molecular chlorine

Ways to reduce the amount of organically bound chlorine in bleached pulp and the AOX discharges from ECF bleaching

A novel spectrophotometric tool for bleaching studies and determination of hexenuronic acid removal

Kraft cooking characteristics and hexenuronic acid concentration of pulps from Eucalypt and other hardwood species