Enantioselective Total Synthesis of the Morphogen (-)-Thallusin and Mediated Uptake of Fe(III) into the Green Seaweed Ulva.

A fully enantioselective, catalytic synthesis of the algal morphogen (-)-thallusin using polyene cyclization chemistry is reported. The synthesis features dedicated precursor design, introduction of a TMS-substituted arene as a regioselective terminator, very high enantiomer excess (ee) on gram scale, and productive scaffold functionalization. Furthermore, an ee determination methodology of thallusin samples was developed, and the ee of biosynthesized thallusin was determined. Fe(III)-uptake studies demonstrated that the cellular uptake of iron facilitated by thallusin derivatives was independent of their morphogenic activity, suggesting their active import via siderophore transporters as a shuttle system.

Frankobactin Metallophores Produced by Nitrogen-Fixing Frankia Actinobacteria Function in Toxic Metal Sequestration.

A series of new metallophores, referred to as frankobactins, were extracted from cultures of the symbiotic and nitrogen-fixing actinobacterium Frankia sp. CH37. Structure elucidation revealed a 2-hydroxyphenyl-substituted oxazoline core and a chain composed of five proteinogenic and nonproteinogenic amino acids, suggesting nonribosomal peptide synthesis as the biosynthetic origin. By whole-genome sequencing, bioinformatic analysis, and comparison with other Frankia strains, the genetic locus responsible for the biosynthesis was detected. Spectrophotometric titration of frankobactin with Fe(III) and Cu(II) and mass spectrometry established the 1:1 (metal:frankobactin) coordination. Uptake experiments suggested that frankobactin A1 (1) did not serve to recruit iron, but to detoxify Cu(II). As frankobactin A1 prevents the cellular entry of Cu(II), it could play a crucial role in the symbiosis of Frankia sp. and its host in the reclamation of copper-contaminated soil.

Genome Sequence of Halomonas sp. Strain MS1, a Metallophore-Producing, Algal Growth-Promoting Marine Bacterium Isolated from the Green Seaweed Ulva mutabilis (Chlorophyta).

We report the draft genome sequence of the marine gammaproteobacterium Halomonas sp. strain MS1, isolated from the green seaweed Ulva mutabilis (Chlorophyta), which releases metallophores fostering macroalga-bacterium interactions. The 4.6-Mbp sequence, which was obtained using PacBio technology, harbors 4,166 predicted coding sequences, including gene clusters for siderophore production.