Stoichiometry of Electrostatic Complexes Determined by Light Scattering

TL;DR

This study investigates the formation and properties of electrostatic complexes between charged polymers and inorganic nanoparticles using light scattering, revealing stable nanoparticle clusters with a fixed stoichiometry governed by electrostatic interactions.

Contribution

The paper introduces a model linking light scattering data to the stoichiometry and molecular weight of electrostatic complexes, validated across multiple nanoparticle-polymer systems.

Findings

Stable nanoparticle clusters form at ~100 nm size.

A sharp scattering peak indicates a fixed polymer-to-nanoparticle ratio.

Electrostatic interactions determine the stoichiometry of complexes.

Abstract

We report on the electrostatic complexation between oppositely charged polymers and inorganic nanoparticles investigated by static and dynamical light scattering. The nanoparticles put under scrutiny were citrate-coated nanocrystals of cerium oxide (CeO2, nanoceria), of iron oxide (Fe2O3, maghemite) and of europium-doped yttrium vanadate (Eu:YVO4) with sizes in the 10 nm range. For the polymers, we have used cationic-neutral diblock copolymers (poly(trimethylammonium ethylacrylate)-b-poly(acrylamide), hereafter referred to as PTEA-b-PAM) with different molecular weights. For the three colloidal dispersions, we show that the electrostatic complexation gives rise to the formation of stable nanoparticle clusters in the 100 nm range. The complexation was monitored by systematic measurements of the scattering intensity versus X, the mixing ratio between nanoparticles and polymers. For 5 nanoparticle/polymer pairs, namely CeO2/PTEA5K-b-PAM30K, Fe2O3/PTEA5K-b-PAM30K, Fe2O3/PTEA11K-b-PAM30K, Eu:YVO4/PTEA2K-b-PAM60K and Eu:YVO4/PTEA5K-b-PAM30K, we found a unique behavior : the scattering intensity exhibits a sharp and prominent peak in the intermediate X-range. To account for this behavior, we have developed a model which assumes that regardless of X, the mixed aggregates are formed at a fixed polymer-to-nanoparticle ratio. The agreement between the results and the model is excellent on the 5 systems. Results at different molecular weights suggest that the stoichiometry of the mixed aggregates is controlled by the electrostatic interactions between the opposite charges. The model allows to derive the molecular weight and the stoichiometry of the mixed aggregates.