RESUMO
The controlled synthesis of stable silver nanoparticles (AgNPs), that do not undergo surface oxidation and Ag+ ion dissolution, continues to be a major challenge. Here the synthesis of robust hybrid lipid-coated AgNPs, comprised of l-α-phosphatidylcholine (PC) membranes anchored by a stoichiometric amount of long-chained hydrophobic thiols and sodium oleate (SOA) as hydrophobic binding partners, that do not undergo surface oxidation and Ag+ ion dissolution, is described. UV-Visible (UV-Vis) spectroscopy, transmission electron microscopy (TEM), and inductively coupled plasma mass spectrometry (ICP-MS) demonstrate that in the presence of strong oxidants, such as potassium cyanide (KCN), the hybrid lipid-coated AgNPs are stable and do not undergo surface oxidation even in the presence of membrane destabilizing surfactants. UV-Vis studies show that the stability of hybrid lipid-coated AgNPs of various sizes and shapes is dependent on the length of the thiol hydrocarbon chain and can be ranked in the order of increasing stability as follows: propanethiol (PT) < hexanethiol (HT) ≤ decanethiol (DT). UV-Vis and ICP-MS studies show that the hybrid lipid-coated AgNPs do not change in size or shape confirming that the AgNPs do not undergo surface oxidation and Ag+ ion dissolution when placed in the presence of strong oxidants, chlorides, thiols, and low pH. Long-term stability studies, over 21 days, show that the hybrid lipid-coated AgNPs do not release Ag+ ions and are more stable. Overall, these studies demonstrate hybrid membrane encapsulation of nanomaterials is a viable method for stabilizing AgNPs in a "shape-locked" form that is unable to undergo surface oxidation, Ag+ ion release, aging, or shape conversion. More importantly, this design strategy is a simple approach to the synthesis and stabilization of AgNPs for a variety of biomedical and commercial applications where Ag+ ion release and toxicity is a concern. With robust and shielded AgNPs, investigators can now evaluate and correlate how the physical features of AgNPs influence toxicity without the confounding factor of Ag+ ions present in samples. This design strategy also provides an opportunity where the membrane composition can be tuned to control the release rate of Ag+ ions for optimizing antimicrobial activity.
RESUMO
The preparation of gold nanoparticles (AuNPs) of high purity and stability remains a major challenge for biological applications. This paper reports a simple synthetic strategy to prepare water-soluble peptide-stabilized AuNPs. Reduced glutathione, a natural tripeptide, was used as a synthon for the growth of two peptide chains directly on the AuNP surface. Both nonpolar (tryptophan and methionine) and polar basic (histidine and dansylated arginine) amino acids were conjugated to the GSH-capped AuNPs. Ultracentrifugation concentrators with polyethersulfone (PES) membranes were used to purify precursor materials in each stage of the multi-step synthesis to minimize side reactions. Thin layer chromatography, transmission electron microscopy, UV-Visible, 1H-NMR, and fluorescence spectroscopies demonstrated that ultracentrifugation produces high purity AuNPs, with narrow polydispersity, and minimal aggregation. More importantly, it allows for more control over the composition of the final ligand structure. Studies under conditions of varying pH and ionic strength revealed that peptide length, charge, and hydrophobicity influence the stability as well as solubility of the peptide-capped AuNPs. The synthetic and purification strategies used provide a facile route for developing a library of tailored biocompatible peptide-stabilized AuNPs for biomedical applications.
