Iron chelation by polyamidoamine dendrimers: A second-order kinetic model for metal - Amine complexation

Abstract

This study presents a kinetic model of the chelation of iron ions by generation 4 hydroxyl-terminated polyamidoamine (PAMAM) with ethylenediamine core (G4-OH). The coordination processes of iron ions from ferric chloride, FeCl3, and ferrous bromide, FeBr2, to G4-OH dendrimers were analyzed using ultraviolet - visible (UV - vis) spectroscopy, proton nuclear magnetic resonance (1H NMR) spectroscopy, and liquid chromatography - mass spectrometry (LC - MS). In the visible region, a charge-transfer was observed when the dendrimer was added to a ferric chloride solution. This phenomenon is a ligand-to-metal charge-transfer (LMCT) between the free electron group of the dendrimer's internal amines and the dehalogenated iron ion that takes 2 h to complete at room temperature. Analysis of potential rate laws and diffusion effects led to a second-order kinetic model for this reaction. By measuring the rate coefficients as a function of temperature (22 - 37 °C), an apparent activation energy of 41.5 kJ/mol was obtained using the Arrhenius method. The results of this study will fuel research of PAMAM dendrimers for environmental, pharmaceutical, and materials applications. © 2011 American Chemical Society.