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π-Extension of the BODIPY core is an effective strategy to modulate the physical properties of BODIPYs. However, π-extension on the zig-zag edge of BODIPYs remains unexplored. Here, we disclose the synthesis of zig-zag-fused BODIPYs through gold-catalysed cycloisomerisation. The obtained BODIPYs show fascinating photophysical properties including near-infrared absorption and emission. [ABSTRACT FROM AUTHOR]

Systematic reaction path exploration revealed the entire mechanism of Knowles's light‐promoted catalytic intramolecular hydroamination. Bond formation/cleavage competes with single electron transfer (SET) between the catalyst and substrate. These processes are described by adiabatic processes through transition states in an electronic state and non‐radiative transitions through the seam of crossings (SX) between different electronic states. This study determined the energetically favorable SET path by introducing a practical computational model representing SET as non‐adiabatic transitions via SXs between substrate's potential energy surfaces for different charge states adjusted based on the catalyst's redox potential. Calculations showed that the reduction and proton shuttle process proceeded concertedly. Also, the relative importance of SET paths (giving the product and leading back to the reactant) varies depending on the catalyst's redox potential, affecting the yield. [ABSTRACT FROM AUTHOR]

We cloned a DNA fragment that suppressed the aerial-mycelium-deficient phenotype in an amfS mutant of Streptomyces griseus when it was introduced into the cells via a high-copy-number plasmid. The sasABCDR gene cluster was identified as being responsible for this suppressive activity. The proteins encoded by sasABCD were of unknown function, but the operon structure was found to be conserved in all the strains of Streptomyces spp. and related organisms whose genomes have been sequenced, sasR, the flanking opposite coding sequence, encoded a putative DNA-binding protein. Subcloning revealed that the presence of all five coding sequences was essential for complete suppression. Scanning electron microscopy of Streptomyces griseus strains carrying the sas gene cluster at a high copy-number revealed that bundle-like structures consisting of several aerial hyphae were often formed. S1 nuclease protection analyses were performed to identify the transcriptional start site in the promoters preceding sasA and sasR. The promoter preceding sasA was highly active during vegetative growth. Null mutants for sasABCD among the S. griseus and S. coelicolor A3(2) cells exhibited bald phenotypes; this suggested a positive regulatory role of this gene cluster in the onset of morphogenesis in these two phylogenetically distinct Streptomyces species.

The authors previously reported that interspecific stimulatory events between Streptomyces species for antibiotic production and/or morphological differentiation mediated by putative diffusible metabolites take place at a high frequency. This paper reports the isolation and characterization of a substance produced by Streptomyces griseus that stimulates the growth and development of Streptomyces tanashiensis. The substance was purified from the culture supernatant of S. griseus by using anion-exchange chromatography, gel filtration chromatography and reverse-phase HPLC. FAB-MS and NMR analyses of the purified preparation indicated the substance to be desferrioxamine E (synonym: nocardamine), a siderophore that is widely produced by Streptomyces species and related organisms. Similar stimulatory effects on the growth and development of S. tanashiensis were exerted by desferrioxamine E produced by another actinomycete strain, but not by other siderophores tested, including ferrichrome and nocobactin and free ferric ion. An exogenous supply of desferrioxamine E stimulated secondary metabolite formation and/or morphological differentiation in various actinomycete strains. Disruption of the desferrioxamine biosynthesis gene cluster in Streptomyces coelicolor A3(2) abolished the production of desferrioxamine E and the activity to stimulate the growth and differentiation of S. tanashiensis. The S. coelicolor mutant showed impaired growth and development on Bennett's/glucose agar medium, but it was rescued by the exogenous supply of desferrioxamine E. These results indicate that desferrioxamines play an important role in streptomycete physiology. Similar to several pathogenic bacteria and fungi, S. tanashiensis may be defective in the production of siderophores; however, it can utilize the siderophores excreted by other organisms.