ABSTRACT
We report the results of cross-linking of two-dimensional gold nanoparticle (Au-NP) assemblies at the air-water interface in situ. We introduce an aqueous soluble ruthenium benzylidene catalyst into the water subphase to generate a robust, elastic two-dimensional network of nanoparticles containing cyclic olefins in their ligand framework. The most striking feature of the cross-linked Au-NP assemblies is that the extended connectivity of the nanoparticles enables the film to preserve much of its integrity under compression and expansion, features that are absent in its non-cross-linked counterparts. The cross-linking process appears to "stitch" the nanoparticle crystalline domains together, allowing the cross-linked monolayers to behave like a piece of fabric under lateral compression.
ABSTRACT
Novel pentafluorophenyl (PFP)-ester-functionalized phosphorylcholine (PC) polymers of different architectures were prepared and conjugated to lysozyme as a model protein. Linear and two-arm poly(2-methacryloyloxyethyl phosphorylcholine) (polyMPC) structures containing PFP functionality at the chain-end were prepared by atom transfer radical polymerization (ATRP) from novel initiators. Additional conjugates were prepared from phosphorylcholine-substituted cyclooctene (PC-COE) polymers containing PFP-ester bearing comonomers. The polymer-protein conjugates were characterized by HPLC, FPLC, and DLS and were seen to retain most (~80% or greater) of their native enzymatic activity. Pharmacokinetic profiles of the polymer-protein conjugates were studied in mice and found to increase the circulation half-life compared with lysozyme alone.
Subject(s)
Fluorobenzenes/chemistry , Fluorocarbon Polymers/chemical synthesis , Muramidase/chemistry , Phosphorylcholine/analogs & derivatives , Phosphorylcholine/chemical synthesis , Animals , Area Under Curve , Enzyme Stability , Esters , Fluorocarbon Polymers/chemistry , Half-Life , Mice , Mice, Inbred C57BL , Micrococcus/chemistry , Molecular Weight , Muramidase/pharmacokinetics , Particle Size , Phosphorylcholine/chemistry , PolymerizationABSTRACT
Nanoparticles have useful properties, but it is often important that they only start working after they are placed in a desired location. The encapsulation of nanoparticles allows their function to be preserved until they are released at a specific time or location, and this has been exploited in the development of self-healing materials and in applications such as drug delivery. Encapsulation has also been used to stabilize and control the release of substances, including flavours, fragrances and pesticides. We recently proposed a new technique for the repair of surfaces called 'repair-and-go'. In this approach, a flexible microcapsule filled with a solution of nanoparticles rolls across a surface that has been damaged, stopping to repair any defects it encounters by releasing nanoparticles into them, then moving on to the next defect. Here, we experimentally demonstrate the repair-and-go approach using droplets of oil that are stabilized with a polymer surfactant and contain CdSe nanoparticles. We show that these microcapsules can find the cracks on a surface and selectively deliver the nanoparticle contents into the crack, before moving on to find the next crack. Although the microcapsules are too large to enter the cracks, their flexible walls allow them to probe and adhere temporarily to the interior of the cracks. The release of nanoparticles is made possible by the thin microcapsule wall (comparable to the diameter of the nanoparticles) and by the favourable (hydrophobic-hydrophobic) interactions between the nanoparticle and the cracked surface.
