Abstract

All structure‐based information on chlorophyll (Chl) breakdown in the higher plants relies on studies with angiosperms. Herein, the first investigation of a fern is reported, revealing a novel type of Chl catabolites (phyllobilins) in leaves of this large division of the vascular plants, and providing structural insights into an astounding metabolic process of the higher plants that appears to have played a role even in early phases of plant evolution. The tetrapyrrolic Chl catabolites in the cosmopolitan bracken fern were discovered to be phyllobilin isomers with an unprecedented skeleton, proposed to be the striking result of a rearrangement of a hypothetical phyllobilin precursor.

Highlights

  • All structure-based information on chlorophyll (Chl) breakdown in the higher plants relies on studies with angiosperms

  • A variety of colorless Chl catabolites have been characterized as structurally related phyllobilins (PBs),[4] and essential pieces of the puzzle of Chl breakdown have been revealed.[2a,5] so far, all structure-based information on Chl breakdown in the higher plants relies on work with PBs from angiosperms,[2,5,6] the contemporarily most diverse division of the plant kingdom.[7]

  • The “primary” FCC is converted further into colorless nonfluorescent Chl-catabolites (NCCs) or to dioxobilin-type NCCs (DNCCs), with various natural substituents R1, R2, and R3.[5c]. The ringopening Pheo a oxygenase (PaO) and RCC reductase (RCCR) are highlighted as two key enzymes of the PaO/phyllobilin path.[2a]

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Summary

Introduction

All structure-based information on chlorophyll (Chl) breakdown in the higher plants relies on studies with angiosperms.

Results
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