Novel Types of Phyllobilins in a Fern - Molecular Reporters of the Evolution of Chlorophyll Breakdown in the Paleozoic Era.

Breakdown of chlorophyll (Chl), as studied in angiosperms, follows the pheophorbide a oxygenase/phyllobilin (PaO/PB) pathway, furnishing linear tetrapyrroles, named phyllobilins (PBs). In an investigation with fern leaves we have discovered iso-phyllobilanones (iPBs) with an intriguingly rearranged and oxidized carbon skeleton. We report here a key second group of iPBs from the fern and on their structure analysis.

Chlorophyll Breakdown in a Fern-Discovery of Phyllobilin Isomers with a Rearranged Carbon Skeleton.

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.

A Class 1 Histone Deacetylase with Potential as an Antifungal Target.

Unlabelled: Histone deacetylases (HDACs) remove acetyl moieties from lysine residues at histone tails and nuclear regulatory proteins and thus significantly impact chromatin remodeling and transcriptional regulation in eukaryotes. In recent years, HDACs of filamentous fungi were found to be decisive regulators of genes involved in pathogenicity and the production of important fungal metabolites such as antibiotics and toxins. Here we present proof that one of these enzymes, the class 1 type HDAC RpdA, is of vital importance for the opportunistic human pathogen Aspergillus fumigatus Recombinant expression of inactivated RpdA shows that loss of catalytic activity is responsible for the lethal phenotype of Aspergillus RpdA null mutants.

Structure elucidation of chlorophyll catabolites (phyllobilins) by ESI-mass spectrometry-Pseudo-molecular ions and fragmentation analysis of a nonfluorescent chlorophyll catabolite (NCC).

The hyphenation of high performance chromatography with modern mass spectrometric techniques providing high-resolution data as well as structural information from MS/MS experiments has become a versatile tool for rapid natural product identification and characterization. A recent application of this methodology concerned the investigation of the annually occurring degradation of green plant pigments. Since the first structural elucidation of a breakdown product in the early 1990s, a number of similarly structured, tetrapyrrolic catabolites have been discovered with the help of chromatographic, spectroscopic and spectrometric methods.

Improved MALDI-TOF microbial mass spectrometry imaging by application of a dispersed solid matrix.

The key step in high quality microbial matrix-assisted laser desorption/ionization mass spectrometry imaging (microbial MALDI MSI) is the fabrication of a homogeneous matrix coating showing a fine-grained morphology. This application note addresses a novel method to apply solid MALDI matrices onto microbial cultures grown on thin agar media. A suspension of a mixture of 2,5-DHB and α-CHCA is sprayed onto the agar sample surface to form highly homogeneous matrix coatings.