(472f) Iron Chelation by Polyamidoamine Dendrimers: A Second Order Kinetic Model for Metal-Amine Complexation

Michael R. Mankbadi and John N. Kuhn


Department of Chemical & Biomedical Engineering, University of South Florida, 4202 East Fowler Avenue, ENB 118, Tampa, FL 33620

To whom correspondence should be addressed. jnkuhn@usf.edu & (813) 974-6498

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 hours 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 ºC to 37 ºC), 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.