title: Dendritic chelating agents. 1. Cu(II) binding to ethylene diamine core poly(amidoamine) dendrimers in aqueous solutions.
abstract: This paper describes an investigation of the uptake of Cu(II) by poly(amidoamine) (PAMAM) dendrimers with an ethylenediamine (EDA) core in aqueous solutions. We use bench scale measurements of proton and metal ion binding to assess the effects of (i) metal ion-dendrimer loading, (ii) dendrimer generation/terminal group chemistry, and (iii) solution pH on the extent of binding of Cu(II) in aqueous solutions of EDA core PAMAM dendrimers with primary amine, succinamic acid, glycidol, and acetamide terminal groups. We employ extended X-ray absorption fine structure (EXAFS) spectroscopy to probe the structures of Cu(II) complexes with Gx-NH2 EDA core PAMAM dendrimers in aqueous solutions at pH 7.0. The overall results of the proton and metal ion binding measurements suggest that the uptake of Cu(II) by EDA core PAMAM dendrimers involves both the dendrimer tertiary amine and terminal groups. However, the extents of protonation of these groups control the ability of the dendrimers to bind Cu(II). Analysis of the EXAFS spectra suggests that Cu(II) forms octahedral complexes involving the tertiary amine groups of Gx-NH2 EDA core PAMAM dendrimers at pH 7.0. The central Cu(II) metal ion of each of these complexes appears to be coordinated to 2-4 dendrimer tertiary amine groups located in the equatorial plane and 2 axial water molecules. Finally, we combine the results of our experiments with literature data to formulate and evaluate a phenomenological model of Cu(II) uptake by Gx-NH2 PAMAM dendrimers in aqueous solutions. At low metal ion-dendrimer loadings, the model provides a good fit of the measured extent of binding of Cu(II) in aqueous solutions of G4-NH2 and G5-NH2 PAMAM dendrimers at pH 7.0.
authors.affiliation: Materials and Process Simulation Center, Beckman Institute, California Institute of Technology, Pasadena, California 91125, USA. diallo@wag.caltech.edu
authors.forename: Mamadou S
authors.initials: MS
authors.lastname: Diallo
authors.forename: Simone
authors.initials: S
authors.lastname: Christie
authors.forename: Pirabalini
authors.initials: P
authors.lastname: Swaminathan
authors.forename: Lajos
authors.initials: L
authors.lastname: Balogh
authors.forename: Xiangyang
authors.initials: X
authors.lastname: Shi
authors.forename: Wooyong
authors.initials: W
authors.lastname: Um
authors.forename: Charalambos
authors.initials: C
authors.lastname: Papelis
authors.forename: William A
authors.initials: WA
authors.lastname: Goddard
authors.forename: James H
authors.initials: JH
authors.lastname: Johnson
mesh_terms: D002614:Chelating Agents / Q000138:chemical synthesis* / Q000737:chemistry; D003300:Copper / Q000737:chemistry*; D005029:Ethylenediamines / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D011073:Polyamines / Q000737:chemistry*; D013499:Surface Properties; D014867:Water / Q000737:chemistry
chemical_list: D002614:Chelating Agents; D005029:Ethylenediamines; D009942:Organometallic Compounds; D011073:Polyamines; D014867:Water; D003300:Copper