Composites made of polymer brushes with inclusions of gold nanoparticles (AuNPs) combine the responsive nature of polymer brushes with the optical properties of the AuNPs, which offers the possibility to be used as colorimetric sensors. To this end, it is crucial to know how AuNPs are distributed inside the brush. Here, this distribution was elucidated by neutron reflectometry with contrast variation and a self-consistent reflectivity analysis based on the analytical parameterization of the volume fraction profiles of all chemical components. In contrast to former studies, this analysis allows the determination of the spatial distribution of components separately from each other: polyelectrolyte, AuNP, and water. Cationic poly-[2-(Methacryloyloxy) ethyl] trimethylammonium chloride (PMETAC) brushes were loaded with 5 nm AuNPs, which were coated with a pH-sensitive capping. The pH was varied during the incubation of the brush in the AuNP suspension. At a lower pH, AuNPs form aggregates in suspension and are attached to the brush periphery. They adsorb into the brush but do not fully penetrate it due to their bulkiness. At a higher pH, AuNP suspensions are electrostatically stabilized and the AuNPs penetrate the brush entirely. However, the AuNP distribution over the brush is not homogeneous but decreases gradually toward the substrate. Penetration of the AuNPs leads to a more extended conformation of the brush. According to the results of the detailed analysis of all components, an increase in water content could be excluded as a reason for brush swelling but replacement of water by the AuNP was observed.

Doping polymer brushes with gold nanoparticles (AuNPs) results in composite materials with colorimetric sensor properties. The present paper addresses the effect of electrostatic particle-particle interaction and the effect of the polymer brush type on particle assembly formation within the polymer matrix. The prospect for long-term use as colorimetric sensors is tested. Therefore, two different types of brushes of pH-insensitive polymers, non-ionic poly(N-isopropylacrylamide) (PNIPAM) and cationic poly-[2-(methacryloyloxy)ethyl] trimethylammonium chloride (PMETAC), are studied. After incubation of the non-ionic PNIPAM brush in an aqueous suspension of AuNPs with a pH-sensitive carboxylic acid capping, hydrogen binding led to attachment of the AuNPs, but they were easily detached at high pH due to loss of the hydrogen binding. In contrast, the anionic AuNPs adhere well to cationic PMETAC brushes even after post-treatment at low pH where the charge density of the AuNPs is strongly reduced. Therefore, the PMETAC/AuNP composites were further tested with respect to their stability against pH variations and their impact for colorimetric sensors. Although the neat PMETAC brush is not pH-sensitive, after embedding pH-sensitive AuNPs, the PMETAC/AuNP composite becomes pH-sensitive in a reversible manner. This is detectable by the reversible shift of the plasmon band and the reversible thickness change of the composites by exposing them to different pH.

No abstract

No abstract