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Deposition of silica from an organosilane tetraethoxysilane (TEOS) onto parent polyethylenimine (PEI) microgel particles produces a novel PEI–silica nanocomposite, which possesses greater adsorption capacity for copper ions than either parent material. This study explores factors governing interactions of silica with the PEI matrix, along with structural features of resulting PEI–silica composite particles, to explain their properties and determine their application potential. The influence of initial TEOS/PEI mass ratio and the duration of silica deposition on the final silica content and distribution in the composite are studied. A comparative analysis of the structural architecture of chemically etched silica remnants, original PEI–silica composite particles and the parent PEI-microgel is carried out using X-ray photoelectron spectroscopy, small-angle X-ray scattering, and electron microscopy techniques. It is found that silica sol nanoparticles are evenly distributed throughout the PEI-microgel framework and interlinked with it via electrostatic interactions, enabling a structural model of the PEI–silica nanocomposite to be proposed. The chemical stability of resulting nanocomposite particles in parallel with the parent PEI-microgel is tested and shown to be robust for more than 100 days of storage in aqueous dispersions across a range of pH conditions, highlighting the application potential for these particles in copper capture.

Increasing demand for copper resources, accompanied by increasing pollution, has resulted in an urgent need for effective materials for copper binding and extraction. Polyethylenimine (PEI) is one of the strongest copper-chelating agents but is not suitable directly (as is) for most applications due to its high solubility in water. PEI-based composite materials show potential as efficient and practical alternatives. In the present work, the interaction of copper ions with PEI–silica nanocomposite particles and precursor PEI microgels (as a reference) is investigated. It is hypothesized that the main driving force of the reaction is chelation of copper ions by amino groups in the PEI network. The presence of silica in the PEI–silica composites was shown to increase the copper-binding capacity in comparison with the parent microgel. The copper-binding behavior of etched (PEI-free “ghost”) composite particles in comparison with the original composites and microgel particles shows that silica nanoparticles in the composite structure increase the number of copper-binding sites in the PEI network rather than adsorbing copper themselves. PEI–silica composites can be easily recycled after copper adsorption by simply washing in 1 M nitric acid, which results in complete copper extraction. Employing this recovery method, PEI–silica composite particles can be used for multiple, efficient cycles of copper removal and extraction.

Azobenzene-containing surfactants (azo-surfactants) have garnered significant attention for their use in generating photoresponsive foams, interfaces, and colloidal systems. The photoresponsive behavior of azo-surfactants is driven by the conformational and electronic changes that occur when the azobenzene chromophore undergoes light-induced trans⇌ cisisomerization. Effective design of surfactants and targeting of their properties requires a robust understanding of how the azobenzene functionality interacts with surfactant structure and influences overall surfactant behavior. Herein, a library of tail substituted azo-surfactants were synthesized and studied to better understand how surfactant structure can be tailored to exploit the azobenzene photoswitch. This work shows that tail group structure (length and branching) has a profound influence on the critical micelle concentration of azo-surfactants and their properties once adsorbed to an air–water interface. Neutron scattering studies revealed the unique role that intermolecular π–π azobenzene interactions have on the self-assembly of azo-surfactants, and how the influence of these interactions can be tuned using tail group structure to target specific aqueous aggregate morphologies.

Fluorinated hydrocarbon (FHC) contamination has attracted global attention recently because of persistence within the environment and ecosystems of many types of FHC. The surfactant perfluorooctanoic acid (PFOA) is particularly commonly found in contaminated sites, and thus, urgent action is needed for its removal from the environment. In this study, water dispersible hybrid capsules were successfully prepared from an oil-in-water emulsion stabilized by graphene oxide and including a silicate precursor to grow a strong, mesoporous capsule shell surrounding the droplets. These capsules were decorated with amine groups to present a positively charged outer corona that attracts negative PFOA molecules. The aminated capsules were effectively applied as a novel technology to adsorb and sequester PFOA contamination in water. It was confirmed that PFOA removal by the capsules was pH and PFOA concentration dependent, with adsorption efficiencies of >60 mg g–1under ideal conditions. PFOA removal kinetics followed using high-performance liquid chromatography and liquid chromatography–mass spectrometry showed that capture of PFOA by the capsules reached a maximum of >99.9% in 2–3 days.