This work examines the effect of nanocrystal diameter and surface coating on the reactivity of cerium oxide nanocrystals with H2O2 both in chemical solutions and in cells. Monodisperse nanocrystals were formed in organic solvents from the decomposition of cerium precursors, and subsequently phase transferred into water using amphiphiles as nanoparticle coatings. Quantitative analysis of the antioxidant capacity of CeO2-x using gas chromatography and a luminol test revealed that 2 mol of H2O2 reacted with every mole of cerium(III), suggesting that the reaction proceeds via a Fenton-type mechanism. Smaller diameter nanocrystals containing more cerium(III) were found to be more reactive toward H2O2. Additionally, the presence of a surface coating did not preclude the reaction between the nanocrystal surface cerium(III) and hydrogen peroxide. Taken together, the most reactive nanoparticles were the smallest (e.g., 3.8 nm diameter) with the thinnest surface coating (e.g., oleic acid). Moreover, a benchmark test of their antioxidant capacity revealed these materials were 9 times more reactive than commercial antioxidants such as Trolox. A unique feature of these antioxidant nanocrystals is that they can be applied multiple times: over weeks, cerium(IV) rich particles slowly return to their starting cerium(III) content. In nearly all cases, the particles remain colloidally stable (e.g., nonaggregated) and could be applied multiple times as antioxidants. These chemical properties were also observed in cell culture, where the materials were able to reduce oxidative stress in human dermal fibroblasts exposed to H2O2 with efficiency comparable to their solution phase reactivity. These data suggest that organic coatings on cerium oxide nanocrystals do not limit the antioxidant behavior of the nanocrystals, and that their redox cycling behavior can be preserved even when stabilized.
Quantum dots (QDs) are increasingly being used for electronics, solar energy generation, and medical imaging applications. Most QDs consist of a heavy metal core/shell coated with amphiphilic organics that stabilize the nanoparticles and allow conjugation with biological molecules. In this study, QDs were evaluated for their effects on bacterial pure cultures, which serve as models of cell toxicity and indicators of potential impact to ecosystem health. QDs with intact surface coatings decreased growth rates of Gram positive Bacillus subtilis and Gram negative Escherichia coli but were not bactericidal. In contrast, weathering of various types of QDs under acidic (pH < or = 4) or alkaline (pH > or = 10) conditions significantly increased bactericidal activity due to the rapid (< 1 min) release of cadmium and selenite ions following QD destabilization upon loss of the organic coating. Toxicity was mitigated by humic acids, proteins, and other organic ligands that reduced metal bioavailability. The best available science, which is limited, suggests that QDs are potentially safe materials when used in their intended applications at near-neutral pH. These results forewarn us that even moderately acidic or alkaline conditions could lead to significant and localized organism effects due to toxic exposure to dissolved heavy metals. Thus, biocompatibility and ecotoxicity tests for QDs should consider in vivo and/or in situ transformations to fully characterize the potential risks to environmental health.
The effective water dispersion of highly uniform nanoparticles synthesized in organic solvents is a major issue for their broad applications. In an effort to overcome this problem, iron oxide and cadmium selenide nanocrystals were surrounded by lipid bilayers to create stable, aqueous dispersions. The core inorganic particles were originally generated in oleic acid and 1-octadecene. When these organic solutions were mixed with water and a sparing amount of excess fatty acid, up to 70% of the nanoparticles transferred into the aqueous phase. This simple approach was applied to two different nanocrystal types, and nanocrystal diameters ranging from 5 to 15 nm. In all cases, the resulting materials were stable, nonaggregated suspensions that retained their original magnetic and optical properties. The phase transfer efficiency is maximum when very little oleic acid is added (e.g. 0.2 w/w %). At higher concentrations, above the critical micelle concentration, the formation of micelles begins to compete with bilayer generation leading to less effective phase transfer. Unlike other approaches for water dispersion that rely on amphiphiles with significant water solubility, the fatty acids used in this work are only sparingly soluble in water. As a result, there is minimal dynamic exchange between free and bound surface agents and the resulting aqueous solutions contain little residual free organic carbon. Thermogravimetric analysis (TGA) confirmed the presence of bilayers around the nanocrystal cores. The particle size, size distribution, process yield, and colloidal stability were found using a suite of methods including transmission electron microscopy, small angle X-ray scattering, dynamic light scattering, inductively coupled plasma-optical emission spectroscopy, and ultraviolet-visible spectroscopy. Bilayer-nanocrystal complexes possess many of the same size-dependent features as the original materials, and as such offer new avenues for exploring and exploiting the interface between nanocrystals and biology.
Many of the solution phase properties of nanoparticles, such as their colloidal stability and hydrodynamic diameter, are governed by the number of stabilizing groups bound to the particle surface (i.e., grafting density). Here we show how two techniques, analytical ultracentrifugation (AUC) and total organic carbon analysis (TOC), can be applied separately to the measurement of this parameter. AUC directly measures the density of nanoparticle–polymer conjugates while TOC provides the total carbon content of its aqueous dispersions. When these techniques are applied to model gold nanoparticles capped with thiolated poly(ethylene glycol), the measured grafting densities across a range of polymer chain lengths, polymer concentrations, and nanoparticle diameters agree to within 20%. Moreover, the measured grafting densities correlate well with the polymer content determined by thermogravimetric analysis of solid conjugate samples. Using these tools, we examine the particle core diameter, polymer chain length, and polymer solution concentration dependence of nanoparticle grafting densities in a gold nanoparticle–poly(ethylene glycol) conjugate system.
Nanocrystalline ceria is an interesting inorganic material for biological application that can exhibit antioxidant properties due to facile electron transfer between cerium(III) and cerium(IV). In this work, ceria nanocrystals with uniform and tunable size, surface chemistry, and variable cerium(III) content were formed via the high temperature thermal decomposition of ceria precursors including cerium acetylacetonate hydrate, cerium oleylamine, and cerium nitrate hexahydrate. When combined with organic acid and amine surfactants at temperatures between 260 and 320 °C, these cerium precursors decomposed to yield near-spherical cerium oxide nanocrystals with diameters ranging from 3 to 10 nm. For all shapes of nanocrystals, the smallest primary particle sizes had the most cerium(III) content. Both poly(acrylic acid)–octyl amine as well as oleic acid could be used to transfer the hydrophobic nanocrystals into water; acute in vitro toxicology studies revealed that even at high concentrations (e.g., 10 ppm) 3 nm nanocrystalline ceria suspensions had had no measurable effect on human dermal fibroblasts (HDF). Additionally, hydrogen peroxide effectively converted cerium(III) to cerium(IV) without any change in the colloidal stability of the nanocrystals. These data illustrate that highly uniform nanocrystalline cerium oxide formed in organic solutions can be a potential antioxidant in the aqueous environments relevant for biological applications.
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