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  • 1
    In: Proceedings of the National Academy of Sciences, Proceedings of the National Academy of Sciences, Vol. 106, No. 6 ( 2009-02-10), p. 1954-1959
    Abstract: Brown-rot fungi such as Postia placenta are common inhabitants of forest ecosystems and are also largely responsible for the destructive decay of wooden structures. Rapid depolymerization of cellulose is a distinguishing feature of brown-rot, but the biochemical mechanisms and underlying genetics are poorly understood. Systematic examination of the P. placenta genome, transcriptome, and secretome revealed unique extracellular enzyme systems, including an unusual repertoire of extracellular glycoside hydrolases. Genes encoding exocellobiohydrolases and cellulose-binding domains, typical of cellulolytic microbes, are absent in this efficient cellulose-degrading fungus. When P. placenta was grown in medium containing cellulose as sole carbon source, transcripts corresponding to many hemicellulases and to a single putative β-1–4 endoglucanase were expressed at high levels relative to glucose-grown cultures. These transcript profiles were confirmed by direct identification of peptides by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Also up-regulated during growth on cellulose medium were putative iron reductases, quinone reductase, and structurally divergent oxidases potentially involved in extracellular generation of Fe(II) and H 2 O 2 . These observations are consistent with a biodegradative role for Fenton chemistry in which Fe(II) and H 2 O 2 react to form hydroxyl radicals, highly reactive oxidants capable of depolymerizing cellulose. The P. placenta genome resources provide unparalleled opportunities for investigating such unusual mechanisms of cellulose conversion. More broadly, the genome offers insight into the diversification of lignocellulose degrading mechanisms in fungi. Comparisons with the closely related white-rot fungus Phanerochaete chrysosporium support an evolutionary shift from white-rot to brown-rot during which the capacity for efficient depolymerization of lignin was lost.
    Type of Medium: Online Resource
    ISSN: 0027-8424 , 1091-6490
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    RVK:
    Language: English
    Publisher: Proceedings of the National Academy of Sciences
    Publication Date: 2009
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    detail.hit.zdb_id: 1461794-8
    SSG: 11
    SSG: 12
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  • 2
    Online Resource
    Online Resource
    Wiley ; 1999
    In:  FEBS Letters Vol. 461, No. 1-2 ( 1999-11-12), p. 115-119
    In: FEBS Letters, Wiley, Vol. 461, No. 1-2 ( 1999-11-12), p. 115-119
    Abstract: Past work has shown that the extracellular manganese‐dependent peroxidases (MnPs) of ligninolytic fungi degrade the principal non‐phenolic structures of lignin when they peroxidize unsaturated fatty acids. This reaction is likely to be relevant to ligninolysis in sound wood, where enzymes cannot penetrate, only if it employs a small, diffusible lipid radical as the proximal oxidant of lignin. Here we show that a non‐phenolic β‐ O ‐4‐linked lignin model dimer was oxidized to products indicative of hydrogen abstraction and electron transfer by three different peroxyl radical‐generating systems: (a) MnP/Mn(II)/linoleic acid, (b) arachidonic acid in which peroxidation was initiated by a small amount of H 2 O 2 /Fe(II), and (c) the thermolysis in air of either 4,4′‐azobis(4‐cyanovaleric acid) or 2,2′‐azobis(2‐methylpropionamidine) dihydrochloride. Some quantitative differences in the product distributions were found, but these were attributable to the presence of electron‐withdrawing substituents on the peroxyl radicals derived from azo precursors. Our results introduce a new hypothesis: that biogenic peroxyl radicals may be agents of lignin biodegradation.
    Type of Medium: Online Resource
    ISSN: 0014-5793 , 1873-3468
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    Language: English
    Publisher: Wiley
    Publication Date: 1999
    detail.hit.zdb_id: 1460391-3
    SSG: 12
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  • 3
    Online Resource
    Online Resource
    American Society for Microbiology ; 2001
    In:  Applied and Environmental Microbiology Vol. 67, No. 6 ( 2001-06), p. 2705-2711
    In: Applied and Environmental Microbiology, American Society for Microbiology, Vol. 67, No. 6 ( 2001-06), p. 2705-2711
    Abstract: The brown rot fungus Gloeophyllum trabeum uses an extracellular hydroquinone-quinone redox cycle to reduce Fe 3+ and produce H 2 O 2 . These reactions generate extracellular Fenton reagent, which enables G. trabeum to degrade a wide variety of organic compounds. We found that G. trabeum secreted two quinones, 2,5-dimethoxy-1,4-benzoquinone (2,5-DMBQ) and 4,5-dimethoxy-1,2-benzoquinone (4,5-DMBQ), that underwent iron-dependent redox cycling. Experiments that monitored the iron- and quinone-dependent cleavage of polyethylene glycol by G. trabeum showed that 2,5-DMBQ was more effective than 4,5-DMBQ in supporting extracellular Fenton chemistry. Two factors contributed to this result. First, G. trabeum reduced 2,5-DMBQ to 2,5-dimethoxyhydroquinone (2,5-DMHQ) much more rapidly than it reduced 4,5-DMBQ to 4,5-dimethoxycatechol (4,5-DMC). Second, although both hydroquinones reduced ferric oxalate complexes, the predominant form of Fe 3+ in G. trabeum cultures, the 2,5-DMHQ-dependent reaction reduced O 2 more rapidly than the 4,5-DMC-dependent reaction. Nevertheless, both hydroquinones probably contribute to the extracellular Fenton chemistry of G. trabeum , because 2,5-DMHQ by itself is an efficient reductant of 4,5-DMBQ.
    Type of Medium: Online Resource
    ISSN: 0099-2240 , 1098-5336
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    Language: English
    Publisher: American Society for Microbiology
    Publication Date: 2001
    detail.hit.zdb_id: 223011-2
    detail.hit.zdb_id: 1478346-0
    SSG: 12
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  • 4
    In: FEBS Letters, Wiley, Vol. 354, No. 3 ( 1994-11-14), p. 297-300
    Abstract: A non‐phenolic lignin model dimer, 1‐(4‐ethoxy‐3‐methoxyphenyl)‐2‐phenoxypropane‐1,3‐diol, was oxidized by a lipid peroxidation system that consisted of a fungal manganese peroxidase, Mn(II), and unsaturated fatty acid esters. The reaction products included 1‐(4‐ethoxy‐3‐methoxyphenyl)‐1‐oxo‐2‐phenoxy‐3‐hydroxypropane and 1‐(4‐ethoxy‐3‐methoxyphenyl)‐1‐oxo‐3‐hydroxypropane, indicating that substrate oxidation occurred via benzylic hydrogen abstraction. The peroxidation system depolymerized both exhaustively methylated (non‐phenolic) and unmethylated (phenolic) synthetic lignins efficiently. It may therefore enable white‐rot fungi to accomplish the initial delignification of wood.
    Type of Medium: Online Resource
    ISSN: 0014-5793 , 1873-3468
    RVK:
    Language: English
    Publisher: Wiley
    Publication Date: 1994
    detail.hit.zdb_id: 1460391-3
    SSG: 12
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  • 5
    Online Resource
    Online Resource
    American Society for Microbiology ; 2002
    In:  Applied and Environmental Microbiology Vol. 68, No. 6 ( 2002-06), p. 2699-2703
    In: Applied and Environmental Microbiology, American Society for Microbiology, Vol. 68, No. 6 ( 2002-06), p. 2699-2703
    Abstract: The brown-rot basidiomycete Gloeophyllum trabeum uses a quinone redox cycle to generate extracellular Fenton reagent, a key component of the biodegradative system expressed by this highly destructive wood decay fungus. The hitherto uncharacterized quinone reductase that drives this cycle is a potential target for inhibitors of wood decay. We have identified the major quinone reductase expressed by G. trabeum under conditions that elicit high levels of quinone redox cycling. The enzyme comprises two identical 22-kDa subunits, each with one molecule of flavin mononucleotide. It is specific for NADH as the reductant and uses the quinones produced by G. trabeum (2,5-dimethoxy-1,4-benzoquinone and 4,5-dimethoxy-1,2-benzoquinone) as electron acceptors. The affinity of the reductase for these quinones is so high that precise kinetic parameters were not obtainable, but it is clear that k cat / K m for the quinones is greater than 10 8 M −1 s −1 . The reductase is encoded by a gene with substantial similarity to NAD(P)H:quinone reductase genes from other fungi. The G. trabeum quinone reductase may function in quinone detoxification, a role often proposed for these enzymes, but we hypothesize that the fungus has recruited it to drive extracellular oxyradical production.
    Type of Medium: Online Resource
    ISSN: 0099-2240 , 1098-5336
    RVK:
    Language: English
    Publisher: American Society for Microbiology
    Publication Date: 2002
    detail.hit.zdb_id: 223011-2
    detail.hit.zdb_id: 1478346-0
    SSG: 12
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  • 6
    Online Resource
    Online Resource
    American Society for Microbiology ; 1994
    In:  Applied and Environmental Microbiology Vol. 60, No. 2 ( 1994-02), p. 709-714
    In: Applied and Environmental Microbiology, American Society for Microbiology, Vol. 60, No. 2 ( 1994-02), p. 709-714
    Abstract: Veratryl alcohol (VA) is a secondary metabolite of white-rot fungi that produce the ligninolytic enzyme lignin peroxidase. VA stabilizes lignin peroxidase, promotes the ability of this enzyme to oxidize a variety of physiological substrates, and is accordingly thought to play a significant role in fungal ligninolysis. Pulse-labeling and isotope-trapping experiments have now clarified the pathway for VA biosynthesis in the white-rot basidiomycete Phanerochaete chrysosporium . The pulse-labeling data, obtained with 14 C-labeled phenylalanine, cinnamic acid, benzoic acid, and benzaldehyde, showed that radiocarbon labeling followed a reproducible sequence: it peaked first in cinnamate, then in benzoate and benzaldehyde, and finally in VA. Phenylalanine, cinnamate, benzoate, and benzaldehyde were all efficient precursors of VA in vivo. The isotope-trapping experiments showed that exogenous, unlabeled benzoate and benzaldehyde were effective traps of phenylalanine-derived 14 C. These results support a pathway in which VA biosynthesis proceeds as follows: phenylalanine → cinnamate → benzoate and/or benzaldehyde → VA.
    Type of Medium: Online Resource
    ISSN: 0099-2240 , 1098-5336
    RVK:
    Language: English
    Publisher: American Society for Microbiology
    Publication Date: 1994
    detail.hit.zdb_id: 223011-2
    detail.hit.zdb_id: 1478346-0
    SSG: 12
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  • 7
    In: FEBS Letters, Wiley, Vol. 446, No. 1 ( 1999-03-05), p. 49-54
    Abstract: We have identified key components of the extracellular oxidative system that the brown rot fungus Gloeophyllum trabeum uses to degrade a recalcitrant polymer, polyethylene glycol, via hydrogen abstraction reactions. G. trabeum produced an extracellular metabolite, 2,5‐dimethoxy‐1,4‐benzoquinone, and reduced it to 2,5‐dimethoxyhydroquinone. In the presence of 2,5‐dimethoxy‐1,4‐benzoquinone, the fungus also reduced extracellular Fe 3+ to Fe 2+ and produced extracellular H 2 O 2 . Fe 3+ reduction and H 2 O 2 formation both resulted from a direct, non‐enzymatic reaction between 2,5‐dimethoxyhydroquinone and Fe 3+ . polyethylene glycol depolymerization by G. trabeum required both 2,5‐dimethoxy‐1,4‐benzoquinone and Fe 3+ and was completely inhibited by catalase. These results provide evidence that G. trabeum uses a hydroquinone‐driven Fenton reaction to cleave polyethylene glycol. We propose that similar reactions account for the ability of G. trabeum to attack lignocellulose.
    Type of Medium: Online Resource
    ISSN: 0014-5793 , 1873-3468
    RVK:
    Language: English
    Publisher: Wiley
    Publication Date: 1999
    detail.hit.zdb_id: 1460391-3
    SSG: 12
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  • 8
    Online Resource
    Online Resource
    Elsevier BV ; 2002
    In:  Enzyme and Microbial Technology Vol. 30, No. 4 ( 2002-04), p. 445-453
    In: Enzyme and Microbial Technology, Elsevier BV, Vol. 30, No. 4 ( 2002-04), p. 445-453
    Type of Medium: Online Resource
    ISSN: 0141-0229
    Language: English
    Publisher: Elsevier BV
    Publication Date: 2002
    detail.hit.zdb_id: 1497704-7
    SSG: 12
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  • 9
    Online Resource
    Online Resource
    Wiley ; 2002
    In:  FEBS Letters Vol. 531, No. 3 ( 2002-11-20), p. 483-488
    In: FEBS Letters, Wiley, Vol. 531, No. 3 ( 2002-11-20), p. 483-488
    Abstract: It is often proposed that brown rot basidiomycetes use extracellular reactive oxygen species (ROS) to accomplish the initial depolymerization of cellulose in wood, but little evidence has been presented to show that the fungi produce these oxidants in physiologically relevant quantities. We used [ 14 C]phenethyl polyacrylate as a radical trap to estimate extracellular ROS production by two brown rot fungi, Gloeophyllum trabeum and Postia placenta , that were degrading cellulose. Both fungi oxidized aromatic rings on the trap to give monohydroxylated and more polar products in significant yields. All of the cultures contained 2,5‐dimethoxyhydroquinone, a fungal metabolite that has been shown to drive Fenton chemistry in vitro. These results show that extracellular ROS occur at significant levels in cellulose colonized by brown rot fungi, and suggest that hydroquinone‐driven ROS production may contribute to decay by diverse brown rot species.
    Type of Medium: Online Resource
    ISSN: 0014-5793 , 1873-3468
    RVK:
    Language: English
    Publisher: Wiley
    Publication Date: 2002
    detail.hit.zdb_id: 1460391-3
    SSG: 12
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  • 10
    In: Holzforschung, Walter de Gruyter GmbH, Vol. 52, No. 3 ( 1998-01), p. 311-318
    Type of Medium: Online Resource
    ISSN: 0018-3830 , 1437-434X
    Language: English
    Publisher: Walter de Gruyter GmbH
    Publication Date: 1998
    detail.hit.zdb_id: 1466072-6
    SSG: 23
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