Chelate complexes of FeII were investigated with respect to their reactivity against nitric oxide and dioxygen. Through a systematic variation of the structure of the polyaminocarboxylate EDTA, a series of 38 potential chelate ligands were selected for FeII. The nitrosyl complexes were prepared from the FeII chelates with NO gas and examined spectroscopically by UV/Vis and ATR‐IR techniques, and themodynamically by determining the overall binding constants for NO. In addition, the reversibility of NO binding to these FeII chelates and the rate of the competing oxidation by dioxygen were studied qualitatively. Whereas the studied complexes all form more or less stable nitrosyl complexes with a characteristic band pattern in the UV/Vis spectra and only slightly diverging frequencies for the NO stretching vibration in the IR spectra, they differ considerably in the reversibility of NO binding, the overall NO binding constants and the sensitivity towards dioxygen. It was found that an increasing number of donor groups on the chelate ligand causes a stronger coordination to FeII, and increases the tendency of the FeII chelates to transfer electron density from iron to substrates like dioxygen or nitric oxide. This results in an accelerated oxidation of FeII to FeIII by dioxygen and a more pronounced tendency of the corresponding nitrosyl complexes to slowly decompose to FeIII and N2O. In addition, the overall binding constant for NO (KNO), which spans a range from 1·103 to 2·107 M−1, increases in the same direction as a result of the inductive effect of the chelate ligand.
Chelate complexes of Fe II were investigated with respect to their reactivity against nitric oxide and dioxygen. Through a systematic variation of the structure of the polyaminocarboxylate EDTA, a series of 38 potential chelate ligands were selected for Fe II . The nitrosyl complexes were prepared from the Fe II chelates with NO gas and examined spectroscopically by UV/Vis and ATR-IR techniques, and themodynamically by determining the overall binding constants for NO. In addition, the reversibility of NO binding to these Fe II chelates and the rate of the competing oxidation by dioxygen were studied qualitatively. Whereas the studied complexes all form more or less stable nitrosyl complexes with a characteristic band pattern in the UV/Vis spectra and only slightly diverging frequencies for the NO stretching vibration in the [a]
The current maximum acceptable daily intake (ADI) of ethylenediaminetetraacetic acid (EDTA) of 1.9 mg day−1 per kilogram bodyweight (mg day−1 kgbw−1) limits the daily intake of iron as iron EDTA [ferric sodium EDTA; sodium iron(III) EDTA] to approximately 2–2.5 mg day−1 for children 6–24 months of age. This limit was defined by the Joint FAO/WHO Expert Committee on Food Additives (JECFA) in 1973 based on data from an animal-feed study published in 1963. Other animal studies indicate that this limit can be raised to 4.4 or possibly up to 21.7 mg day−1 kgbw−1, which is 2.3–11.4 times higher than the current value. For nearly 50 years, iron EDTA has been used in France in medicinal syrup for infants 1–6 months of age. The maximum recommended dosage of this drug is 37 times higher than the maximum ADI of EDTA. No adverse health effects have been reported as a result of this medicinal consumption of iron EDTA. Raising the maximum ADI of EDTA to only 4.4 mg day−1 kgbw−1 would enable iron EDTA, an iron fortificant with proven bioavailability in phytate-rich meals, to be added in adequate amounts to cereal-based meals for children 6–24 months of age, who are at risk of iron deficiency.
The bifunctional phosphorylating reagent O,O-bis[1-benzotriazolyl]phosphoromorpholidate was used to introduce a 5'-O-triphosphate and a 3'-O-diphosphate function in a partially protected riboguanosine. Pilot studies indicated that protection of the 2'-OH of ribonucleosides with the acid-labile tetrahydropyranyl group, instead of the more labile 4-methoxytetrahydropyran-4-yl group, was most satisfactory for the preparation of the Magic Spot II.
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