Anomalous solubility behavior of mixed monolayer protected metal nanoparticles

Thesis (S.B.)--Massachusetts Institute of Technology, Dept. of Materials Science and Engineering, 2005.Includes bibliographical references (leaves 30-32).The solubility of mixed monolayer protected gold nanoparticles was studied. Monolayer protected metal nanoparticles are attractive materials because of the optical and electronic properties of their metal cores and because of the surface properties of their ligand coating. Recently, it was discovered that a mixture of ligands phase separate into ordered domains of single nanometer or subnanometer width on the surface of metal nanoparticles. The morphology and length of the ligand domains (which take the form of ripples on the particle surface) has given these nanoparticles novel properties. Because monolayer protected nanoparticles can be dissolved and dried many times, they can be handled and processed in ways not available to other nanomaterials. Understanding the solubility of mixed monolayer protected metal nanoparticles could help in implementing their unique new properties. This study demonstrates that the solubility of these particles in organic solvents cannot be explained only in terms of the composition of the ligand shell. Instead, solubility is also closely linked to morphology of the ligand shell via relationships between the size of the solvent molecule and the size of the features in the morphology.by Jacob W. Myerson.S.B

Spontaneous assembly of subnanometre-ordered domains in the ligand shell of monolayer-protected nanoparticles

The properties of materials can be created and improved either by confining their dimensions in the nanoscale or by controlling their nanostructure. We have combined these two concepts, and here we describe a new class of nanostructured nanosized materials that show ordered phase-separated domains at an unprecedented molecular length scale. Scanning tunnelling and transmission electron microscope images of monolayer-protected metal nanoparticles, with ligand shells composed of a mixture of molecules, show that the ligands phase-separate into ordered domains as small as 5 Angstrom. Importantly, the domain shape and dimensions can be controlled by varying the ligand composition or the metallic core size. We demonstrate that the formation of ordered domains depends on the curvature of the underlying substrate, and that novel properties result from this nanostructuring. For example, because the size of the domains is much smaller than the typical dimensions of a protein, these materials are extremely effective in avoiding non-specific adsorption of a variety of proteins

Nanoparticle Properties Modulate Their Attachment and Effect on Carrier Red Blood Cells

Attachment of nanoparticles (NPs) to the surface of carrier red blood cells (RBCs) profoundly alters their interactions with the host organism, decelerating NP clearance from the bloodstream while enabling NP transfer from the RBC surface to the vascular cells. These changes in pharmacokinetics of NPs imposed by carrier RBCs are favorable for many drug delivery purposes. On the other hand, understanding effects of NPs on the carrier RBCs is vital for successful translation of this novel drug delivery paradigm. Here, using two types of distinct nanoparticles (polystyrene (PSNP) and lysozyme-dextran nanogels (LDNG)) we assessed potential adverse and sensitizing effects of surface adsorption of NPs on mouse and human RBCs. At similar NP loadings (approx. 50 particles per RBC), adsorption of PSNPs, but not LDNGs, induces RBCs agglutination and sensitizes RBCs to damage by osmotic, mechanical and oxidative stress. PSNPs, but not LDNGs, increase RBC stiffening and surface exposure of phosphatidylserine, both known to accelerate RBC clearance in vivo. Therefore, NP properties and loading amounts have a profound impact on RBCs. Furthermore, LDNGs appear conducive to nanoparticle drug delivery using carrier RBCs