0000000000012794
AUTHOR
Andreas Lutz
Fractionation of unsubstituted cellulose from solutions in either Ni-tren or (N,N-dimethylacetamide + LiCl)
Starting from solutions of unsubstituted cellulose (Avicel PH101, M w = 30.1 kg/mol and M w /M n = 3 or Solucell 500, M w = 230 kg/mol, M w /M n = 2.8) in either Nitren (0.8 M aqueous solution of the dihydroxotris(2-aminoethly)amine nickel(II) complex) or in a mixed solvent DMAc+LiCl (consisting of N,N-dimethylacetamide plus lithium chloride) it was investigated whether the segregation of a second phase caused by the addition of suitable precipitants leads to polymer fractionation. With Ni-tren the long chains accumulate in the precipitate formed upon the addition of sulfuric acid; as the pH falls below 9, the solution is free of cellulose. Nevertheless this route option for fractionation m…
An Iron-Based Molecular Redox Switch as a Model for Iron Release from Enterobactin via the Salicylate Binding Mode
The iron release mechanism from protonated ferric enterobactin [Fe(III)(enterobactinH(3))] via the salicylate binding mode was probed. For this purpose, a tripodal dodecadentate ligand incorporating three salicylamide (OO) and three bipyridine (NN) binding sites was synthesized as well as iron complexes thereof. It was shown that a ferric ion coordinates selectively to the hard salicylamides and a ferrous ion binds to the softer bipyridines. Upon reduction or oxidation, the iron translocates reversibly and intramolecularly from one site to the other, thus displaying switchlike properties. Both states were characterized by cyclic voltammetry and visible and Mössbauer spectroscopy. The Mössba…