Zusammenfassung:
Sekundärmetabolite sind chemische Stoffe, die von Pilzen, Bakterien und Pflanzen syntheti- viert werden. Sie sind im Gegensatz zu den Primärmetaboliten nicht für das Überleben eines Organismus notwendig, bringen aber Vorteile gegenüber anderen Organismen mit sich. Zu den Sekundärmetaboliten zählen Biotenside, bei denen es sich um mikrobiell hergestellte, chemisch strukturell gleiche Tenside handelt. Sie bestehen aus einem hydrophoben und einem hydrophilen Teil. Dieser amphiphile Aufbau führt zu typischen oberflächenaktiven Eigenschaften. Im Ge- gensatz zu industriell chemisch hergestellten Tenside sind Biotenside unter anderem biologisch abbaubar, ungiftig und hitzestabil. Glycolipide sind eine Gruppe von Biotensiden. Sie bestehen immer aus einem oder mehreren Zuckern, die mit Hydroxyfettsäuren verbunden sind. Im Reich der Pilze gibt es viele verschiedene Glycolipide, zu denen auch die von dem phytopathogenen Basidiomycet phytopathogenen Basidiomycet Ustilago maydis synthetisierte Ustilaginsäure und Mannosylerythritollipide zählen. Diese beiden Glycolipide werden unter Stickstoffmangelbedin- gungen synthetisiert. Die Ustilaginsäure besitzt eine starke Oberflächenaktivität und wirkt anti- biotisch gegen Hefen und Gram-positive Bakterien, wohingegen Mannosylerythritollipide zudem hämolytische Aktivität zeigen. Die Biosynthesewege dieser beiden Glycolipide wurden bereits gut charakterisiert.
Bei dem Screening vieler verschiedenster Pilzisolate wurden zwei weitere Basidiomyceten, Ma- calpinomyces eriachnes und Sporisorium scitamineum, gefunden, die ebenfalls in der Lage sind verschiedene Varianten dieser Glycolipide zu synthetisieren. Bei diesen handelt es sich einen um Macalpinomyces eriachnes und Sporisorium scitamineum. Die Glycolipide von M. eriachnes sind oberflächenaktiv und wirken hämolytisch. Die Glycolipide von S. scitamineum hingegen sind auch oberflächenaktiv und wirken antibiotisch gegenüber Hefen. Neben diesen beiden phy- topathogenen Pilzen wurde ein weiterer Pilz gefunden, der in der Lage war einen zuckerhaltigen Sekundärmetabolit zu synthetisieren. Durch Sequenzierung konnte diese schwarze Hefe als Do- thiora cannabinae identifiziert werden. Unter Stickstoffmangelbedingungen ist D. cannabinae in der Lage eine glycolipidartige Substanz zu synthetisieren. Mit Hilfe von Massenspektrometrie und Kernspinresonanzspektroskopie konnte die Substanz als oberflächaktives und hämolytisches Glyco-Oligo-Hydroxy-Alkanoat identifiziert werden.
Die Hexadecansäure der Ustilaginsäure liegt in U. maydis in di- und trihydroxylierter Form vor. Die Hydroxylierung wird von den beiden P450 Monooxigenasen Cyp1 und Cyp2 kataly- siert. Die Überexpression von Cyp1 in einem Ustilaginsäure defiziten U. maydis Stamm führt zu einer Monohydroxylierung der Hexadecansäure der MELs. Die Überexpression beider P450 Mo- nooxigenasen führt zur Dihydroxylierung. Diese Modifikation der MELs hatte allerdings keinen Einfluss auf die Eigenschaften der Glycolipide.
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