Publications

Hierarchical assembly architectures of functional polymer particles are promising because of their physicochemical and surface properties for multi-labeling and sensing to catalysis and biomedical applications. While polymer nanoparticles' interior is mainly made up of the cross-linked network, their surface can be tailored with soft, flexible, and responsive molecules and macromolecules as potential support for the controlled particulate assemblies. Molecular surfactants and polyelectrolytes as interfacial agents improve the stability of the nanoparticles whereas swellable and soft shell-like cross-linked polymeric layer at the interface can significantly enhance the uptake of guest nano-constituents during assemblies. Besides, layer-by-layer surface-functionalization holds the ability to provide a high variability in assembly architectures of different interfacial properties. Considering these aspects, various assembly architectures of polymer nanoparticles of tunable size, shapes, morphology, and tailored interfaces together with controllable interfacial interactions are constructed here. The microfluidic-mediated platform has been used for the synthesis of constituents polymer nanoparticles of various structural and interfacial properties, and their assemblies are conducted in batch or flow conditions. The assemblies presented in this progress report is divided into three main categories: cross-linked polymeric network's fusion-based self-assembly, electrostatic-driven assemblies, and assembly formed by encapsulating smaller nanoparticles into larger microparticles.

The presence of the polycationic macromolecule poly(diallyldimethylammonium chloride) (poly-DADMAC) has a strong effect on the shape and size of colloidal gold nanoparticles formed by the reduction of tetrachloroauric acid with ascorbic acid in aqueous solution. It slows down nanoparticle growth and supports the formation of nonspherical, partially highly fractal and hierarchical nanoparticle shapes. Four structural levels have been recognized from the near-spherical gold nanoparticles in the lower nanometer range over compact aggregates in the midnanometer range and flower and star-like particles in the submicron range up to larger filamentous aggregates. High-contrast scanning electron microscope (SEM) images show that single gold nanoparticles and clusters of them are connected by bundles of macromolecules in large aggregates. The investigation showed that a large spectrum of different nanoparticle shapes and sizes can be accessed by tuning the poly-DADMAC concentrations and their ratio to other reactants. The nanoassemblies with a very high specific surface area might be of interest for SERS and heterogeneous catalysis.

Polyelectrolyte layer-by-layer assemblies are known as protective coatings for corrosion inhibition. Here, we demonstrate that polyelectrolyte multilayers of poly(ethyleneimine) (PEI) and poly(styrene sulfonate) (PSS)-(PEI/PSS)x-adsorbed at the GaP(100) photocathode surface remarkably mitigate the photocorrosion of GaP without decreasing its photoconversion efficiency. The activity of the polybase-polyacid complex is based on buffering pH changes at the solid-liquid interface. We carried out ab initio molecular dynamics-based simulations of the GaP(100) surface in contact with liquid water and demonstrated that an increase in the proton concentration enhances GaP dissolution. We used the scanning vibrating electrode technique (SVET) to characterize the distribution of photocorrosion activity areas over bare and polyelectrolyte-coated GaP surfaces and we showed that a polyelectrolyte coating impedes the dissolution kinetics. Data obtained using the SVET were compared to photoetched pores on the semiconductor surface. Voltammetric and chronoamperometric measurements were also performed to evaluate photoconversion efficiencies before and after the application of the protective coatings.