Small Angle Neutron Scattering Studies of the Counterion Effects on the Molecular Conformation and Structure of Charged G4 PAMAM Dendrimers in Aqueous Solutions

Abstract

The structural properties of generation 4 (G4) poly(amidoamine) starburst dendrimers (PAMAM) with an ethylenediamine (EDA) central core in D2O solutions have been studied by small-angle neutron scattering (SANS). Upon the addition of DCl, SANS patterns show pronounced inter-particle correlation peaks due to the strong repulsion introduced by the protonation of the amino groups of the dendrimers. By solving the Ornstein−Zernike integral equation (OZ) with hypernetted chain closure (HNC), the dendrimer−dendrimer structure factor S(Q) is determined and used to fit the experimental data, where Q is the magnitude of the scattering wave vector. Quantitative information such as the effective charge per dendrimer and the radius of gyration, RG, at different pD values is obtained. The results show that RG only changes by about 4% when the pD value varies from 10.25 to 4.97, and significant counterion association/condensation occurs, strongly mediating the inter-dendrimer interaction. The influence of interplay between counterions and molecular protonation of dendrimers imposes a strong effect on the dendrimer conformation and effective interaction. Although the change of RG is very small, careful analyses of the high Q data and fitting parameters indicate a possible internal structure change of a dendrimer when the amino groups are progressively charged.