Synthesis and Characterization of Polyethylenimine-Silica Nanocomposite Microparticles.

A novel procedure for the synthesis of polyethylenimine (PEI)-silica nanocomposite particles with high adsorption capacities has been developed based on an emulsion templating concept. The exceptional chelating properties of PEI as the parent polymer for the particle core promote the binding abilities of the resulting composite for charged species. Further, the subsequent introduction of silica via the self-catalyzed hydrolysis of tetraethoxysilane facilitates production of robust composite particles with smooth surfaces, enabling potential use in multiphase environments. To enable tailored application in solid/liquid porous environments, the production of particles with reduced sizes was attempted by modulating the shear rates and surfactant concentrations during emulsification. The use of high-speed homogenization resulted in a substantial decrease in average particle size, while increasing surfactant loading only had a limited effect. All types of nanocomposites produced demonstrated excellent binding capacities for copper ions as a test solute. The maximum binding capacities of the PEI-silica nanocomposites of 210-250 mg/g are comparable to or exceed those of other copper binding materials, opening up great application potential in resources, chemical processing, and remediation industries.

Copper-Binding Properties of Polyethylenimine-Silica Nanocomposite Particles.

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.

Polynorepinephrine as an Efficient Antifouling-Coating Material and Its Application as a Bacterial Killing Photothermal Agent.

Biomedical device-related infection (BDI) is of great concern in modern clinical and medical applications. Various approaches to combat BDI are based on two major principles: the prevention of biofoulants adhering on medical devices and the ability to eradicate biofouling once formed. To minimize the risk of BDI, an antifouling coating with bactericidal ability is highly desirable. In this work, we report on the use of polynorepinephrine (PNE) as a promising strategy to prevent BDI due to its excellent antifouling and photothermal bacterial killing capabilities. PNE coatings show superior protein resistance against a model biofoulant (bovine serum albumin (BSA)) when compared with poly(ethylene glycol) (PEG) and polydopamine (PDA) coatings. The antifouling mechanism between BSA protein molecules and coating films is investigated using atomic force microscopy (AFM). We also demonstrate that PNE-modified surfaces show remarkable bacterial killing ability against both Gram-positive Staphylococcus aureus and Gram-negative Escherichia coli bacteria after being irradiated with an 850 nm near-infrared (NIR) laser. These results indicate that PNE coatings present a highly promising candidate for biomedical antifouling applications.

Bioinspired polynorepinephrine nanoparticles as an efficient vehicle for enhanced drug delivery.

An innovative drug delivery vehicle based on polynorepinephrine (PNE) with controllable size modification, high delivery efficacy and low cytotoxicity is presented. Highly monodisperse PNE nanoparticles are fabricated by the autoxidation of norepinephrine monomers in an alkaline water/ethanol mixture via stirring at room temperature. We demonstrated the facile optimization of particle size to enhance particle stability and biocompatibility by varying solvent and monomer dosage. To demonstrate the suitability and potential application of PNE particles in cancer therapy, we show that these particles are biocompatible in vitro with HeLa cells and in vivo in zebrafish embryos. After loading the anti-cancer chemotherapy drug doxorubicin (DOX) into the PNE nanoparticles, a consistent and pH responsive drug release profile of DOX was achieved in different environmental conditions. It was found that DOX loaded PNE nanoparticles (PNE/DOX) exhibit much higher pharmaceutical cytotoxicity than free DOX on HeLa cells. Furthermore, the amount of drug released was significantly enhanced in acidic environments that mimic the pH of extracellular tumour microenvironments. Taken together, the PNE nanoparticles represent a new class of melanin particles with promising potential in drug delivery and as a therapeutic platform for cancer treatment.

Synthesis, Characterization, and Applications of Polymer-Silica Core-Shell Microparticle Capsules.

Encapsulation is a powerful method for the targeted delivery of concentrated reagents and capture of valuable materials in dilute systems. To this end, many encapsulation schemes for specific scenarios have been devised that incorporate chemospecificity or stimulus response in terms of uptake or release. However, an encapsulation platform that enables highly tailorable surface chemistry for targeting, stimulus response, and core chemistry for capture and release of reagents remains elusive. Here, we present such a system comprising composite core-shell capsule particles of hydrophilic polymers coated with thin silica layers synthesized via straightforward one-pot syntheses. Silica is found to encapsulate a range of polymer hydrogels through a mechanism independent of the specific core chemistry. The hybrid materials possess significantly enhanced rigidity while allowing surface modification through simple yet versatile silane coupling reactions without a reduction in the functionality of the core. They are shown to have applications as diverse as recyclable catalysis and controlled delivery vehicles for agrochemicals. The successful synthesis and utilization of this catalog of materials indicate the broader capability of simple composite structures in an array of high-value applications.

Synthesis and characterisation of robust emulsion-templated silica microcapsules.

Robust silica microcapsules were synthesised using an emulsion template via a seeded growth strategy. Multiple additions of the silica precursor tetraethyl orthosilicate (TEOS) were observed to result in a number of physical and property changes of the capsule shells as compared to a single coating. Scanning electron microscopy indicated a morphological transition from a smooth to a roughened surface. Improved cargo retention and consolidation of the pore structure of the silica shells were observed using dye release experiments and nitrogen porosimetry respectively. In comparison to a typical hollow silica shell synthesis procedure, this one-pot loading and synthesis allows the simple production of robust capsules that are capable of sustained release, using mild conditions and reagents.