Iron chelators synthetic approaches

The peptide bond that is cleaved is the bond between Leu-189 and Asp-190. There are two peptide bonds in close proximity to the iron chelate on Cys-212. The other peptide bond is between He-144 and Gly-145. The Cys-212 sulfur is 5.1 A from the carbonyl carbon of Gly-145, and 5.3 A from the carbonyl carbon of Leu-189. However, the main difference is that the peptide bond of Leu-189-Asp-190 is oriented parallel to Cys-212, while the peptide bond of lie-144-Gly-145 is oriented away for Cys-212. As was seen with cobalt(lll) hydrolysis of peptide bonds, the proximity and orientation of the carbonyl carbon is important for hydrolysis. This approach has been extended to the cleavage of multisubunit proteins. Palladium(n) and platinum(ll) complexes as synthetic peptidases have been reviewed elsewhere. ... 

One of synthetic approaches for the iron nanoparticles is based on the widely used decomposition of iron pentacarbonyl [19, 361, 362], The novelty of the approach is the surfactant system used. Studies with a number of strongly bound surfactants have resulted in decreased magnetic response, due to surface oxidation, disturbing the electronic structure of the surface atoms, or some other mechanism. With this in mind, ones chose to work with a weak surfactant, a p-diketone. P-diketones do have a history as adhesion promoters in bonds between metals and polymers [363], The limited reactivity of p-diketones is as an advantage the P-diketone is much weaker oxidizer than carboxylic acids or alcohols and will not oxidize iron, it is not as nucleophilic as phosphines, yet it is known to be capable of chelating iron. 

A major form of antioxidant defense in human plasma is the prevention of iron and other transition metal ions from promoting the generation of reactive oxygen species. Although many therapeutic measures to inactivate metals by chelation therapy have been advocated, the avoidance of iron supplementation in the diet may provide a simpler and more economical approach to this potential health problem The current practice of iron supplementation of flour and cereal products may be impmdent, in view of the possible risk of excessive iron in generating oxidative stress in certain segments of the adult and older population. Iron deficiency was even advocated as a more effective and practical antioxidant treatment than supplementation with either synthetic or natural antioxidants. 

For the approach detailed above to be successful, the metal binding domain must form robust complexes, yet retain synthetic flexibility. Although substituted phenanthroline and bipyridine easily form self-assembled receptors (12), the substitution stability of terpyridine (Fig. 2) makes this ligand more suited for the creation of libraries. The choice of metal also permits some flexibility in library creation. Iron complexes form easily through the addition of ammonium iron(II) sulfate hexahydrate, but can be cleaved by the addition of chelating guests (11,13), Cobalt complexes are also easily formed using cobalt(II)... 

---