Pattern formation in the ferrocyanide-iodate-sulfite reaction: the control of space scale separation

We revisit the conditions for the development of reaction-diffusion patterns in the ferrocyanide-iodate-sulfite bistable and oscillatory reaction. This hydrogen ion autoactivated reaction is the only example known to produce sustained stationary lamellar patterns and a wealth of other spatio-temporal phenomena including self-replication and localized oscillatory domain of spots, due to repulsive front interactions and to a parity-breaking front bifurcation (nonequilibrium Ising-Bloch bifurcation). We show experimentally that the space scale separation necessary for the observation of stationary patterns is mediated by the presence of low mobility weak acid functional groups. The presence of such groups was overlooked in the original observations made with hydrolyzable polyacrylamide gels. This missing information made the original observations difficult to reproduce and frustrated further experimental exploitation of the fantastic potentialities of this system. Using one-side-fed spatial reactors filled with agarose gel, we can reproduce all the previous pattern observations, in particular the stationary labyrinthine patterns, by introducing, above a critical concentration, well controlled amounts of polyacrylate chains in the gel network. We use two different geometries of spatial reactors (annular and disk shapes) to provide complementary information on the actual three-dimensional character of spatial patterns. We also reinvestigate the role of other feed parameters and show that the system exhibits both a domain of spatial bistability and of large-amplitude pH oscillations associated in a typical cross-shape diagram. The experimental method presented here can be adapted to produce patterns in the large number of oscillatory and bistable reactions, since the iodate-sulfite-ferrocynide reaction is a prototype of these systems.     

Electrochemical and photochemical approaches for the synthesis of the C28–C38 fragment of okadaic acid

Okadaic acid, a potent and selective inhibitor of Protein Phosphatases 1 and 2A (PP1 and PP2A), is widely used as a probe for various biochemical processes. We describe herein two innovative methods for the synthesis of the terminal C28–C38 fragment of the natural polyether. Suárez photochemical oxidative cyclization and electrochemical oxidation of malonates to their ketals equivalents have been successfully applied for the assembly of the key spiroketal core.     

Complexation of hydroxamate-based siderophores with cobalt(II/III): growth inhibitory effect of cobalt(III)-desferricoprogen complex on fungi

Solution equilibrium results for Co(II) and Co(III) complexes of two natural hydroxamate-based siderophores, the exocyclic desferricrocin (DFR) and the endocyclic triacetylfusarinine (TAF) are presented. The three hydroxamate chelating functions of TAF were found to complete the octahedral coordination sphere of a Co(II) ion in stepwise processes, but following the coordination of two hydroxamates of DFR practically in one step, the third function, most probably because of sterical reasons, remained uncoordinated. A comparison with corresponding results for the previously studied acyclic desferrioxamine B (DFB) and desferricoprogen (DFC) provided some information about the effects of the molecular framework of siderophores on their cobalt-binding ability. The oxidation of the central metal ion under basic conditions and investigation of the cobalt(III) complexes by cyclic voltammetry were also made. Compared to Fe(III), by several orders of magnitude, higher stability complexes were formed with Co(III). The possibility of any effect of the Co(III)-siderophore complex on microbial Fe(III) uptake was tested by investigation of the antifungal effect of Co(III)-DFC in comparison with that of CoCl₂ on two fungi cultures, Penicillium brevicompactum and Aspergillus fumigatus.