The crystal structures of some nickel hexacyanoferrates (II, III), including mixed compositions containing Na+, K+ and Cs+, were resolved and refined from XRD powder patterns. Data from infrared, Mössbauer and adsorption techniques provided complementary structural information. The crystal structures of Ni3[Fe(CN)6]2⋅16H2O and NiCs2[Fe(CN)6] were refined in space group Fm3m. NiNa2[Fe(CN)6]⋅2H2O and NiK2[Fe(CN)6]⋅2H2O were found to be orthorhombic (space group Pmn21). This structure (Pmn21) results from a distortion around the alkali ion, which appears as a monohydrated interstitial species. On ionic exchange in an aqueous solution containing Cs+, the orthorhombic distortion disappears and the cubic cell is obtained. Cs+ is a large cation and space is not available for interstitial water molecules. This orthorhombic model is also supported by the Mössbauer spectra of the ferrous analogs, FeK2[Fe(CN)6]⋅xH2O and Fe[Pt(CN)6]. © 2004 International Centre for Diffraction Data.

Mn2+ and Cd2+ form a family of isostructural hexacyanoferrates(II,III). Their crystal structures, including those of mixed compositions containing K+ and Cs+ as charge balance cations, were resolved and refined from XRD powder patterns. The crystal structures of M3[Fe(CN)6]2⋅xH2O and MCs2[Fe(CN)6] (where M=Mn, Cd) were refined in the space group Fm3m. The mixed salts, MK2[Fe(CN)6]⋅2H2O, were found to be orthorhombic (space group Pmn21). The orthorhombic structure results from a local distortion due to monohydrated potassium ions located in interstitial sites. On ionic exchange in an aqueous solution containing Cs+, the orthorhombic distortion disappears and the cubic cell is obtained. Cs+ is a large ion, which practically fills the available interstitial voids stabilizing the cubic structure. In solutions of K+ and Cs+ the single salts, M2[Fe(CN)6]⋅8H2O (monoclinic P21/n) also transform, in this case liberating M2+ ions and forming the corresponding mixed salts. An analogous but slow structural transformation was also observed in the anhydrous forms of these single salts. These structural transformations could be relevant to the use of these compounds as ion exchangers and particularly for the sorption of 137Cs+ from radioactive waste solutions. The XRD data were complemented with structural information from infrared (IR), Mössbauer and water vapor adsorption techniques. © 2004 International Centre for Diffraction Data.

The plasma membrane oxidoreductase (PMOR) activity, which mainly utilises ascorbate as intracellular electron donor, represents a major mechanism for cell-dependent reduction of extracellular oxidants and might be an important process used by the erythrocytes to keep a reduced plasma environment. We previously reported that in human erythrocytes, myricetin and quercetin act as intracellular substrates of a PMOR showing a novel mechanism whereby these flavonoids could exert beneficial effects under oxidative stress conditions. Here, we evaluated the ability of different flavonoids (quercetin, myricetin, morin, kaempferol, fisetin, catechin, luteolin, apigenin, acacetin, rutin, taxifolin, naringenin, genistein) and of two in vivoO-methylated metabolites of quercetin (isorhamnetin and tamarixetin) to be substrates of PMOR, by comparing their antioxidant capacity (i.e. direct interaction with the oxidant ferricyanide or with the free radical 1,1-diphenyl-2-picryl-hydrazil) with their ability to penetrate the erythrocytes and donate electrons to the PMOR. The results obtained indicate that, although most of the flavonoids display significant antioxidant activities, only those (quercetin, myricetin, fisetin) that combine the cathecol structure of the B ring (responsible for the reducing activity) with the 2,3 double bond and 4-oxo function of the C ring (responsible for the uptake by erythrocytes) can act as intracellular substrates for PMOR. It is of note that the metabolites of quercetin enter erythrocytes and donate electrons to the PMOR as the parent compound. The present data show a relationship between the flavonoid structures and their ability to provide electrons to the PMOR, suggesting an additional mechanism whereby dietary flavonoids may exert beneficial effects in man.