Jeong Ae Yoon

One-Pot Synthesis of Robust Core/Shell Gold Nanoparticles

A one-pot synthesis of thermally stable core/shell gold nanoparticles (Au-NPs) was developed via surface-initiated atom transfer radical polymerization (ATRP) of n-butyl acrylate (BA) and a dimethacrylate-based cross-linker. The higher reactivity of the cross-linker enabled the formation of a thin cross-linked polymer shell around the surface of the Au-NP before the growth of linear polymer chains from the shell. The cross-linked polymer shell served as a robust protective layer, prevented the dissociation of linear polymer brushes from the surfaces of Au-NPs, and provided the Au-NPs excellent thermal stability at elevated temperature (e.g., 110 degrees C for 24 h). This synthetic method could be easily expanded for preparation of other types of inorganic/polymer nanocomposites with significantly improved stability.

Dual-Reactive Surfactant Used for Synthesis of Functional Nanocapsules in Miniemulsion

Dual-functional amphiphilic block copolymers, alpha-azido-omega-2-chloroisobutyrate-poly(oligo(ethylene oxide) monomethyl ether methacrylate)-b-poly(n-butyl methacrylate), prepared by atom-transfer radical polymerization were used as dual-reactive surfactants (i.e., macroinitiators for a miniemulsion copolymerization of a monovinyl monomer and divinyl cross-linker as well as surfactants with latent functionality). Because of the amphiphilic nature of the block copolymers used as surfactant/initiators, the polymerization was initiated at the oil-water interface, with polymer chains slowly growing inward in a controlled manner after activation by the catalyst. Polymeric nanocapsules with cross-linked shells and the latent azido functionality were obtained. Introduction of various degradable cross-linking agents into the system resulted in the formation of nanocapsules that were cleaved under specific conditions. The preserved latent alpha-terminal azido groups in the dual-reactive surfactant were utilized to attach a fluorescent dansyl probe and/or atom-transfer radical polymerization initiators to grow linear polymer chains forming an additional shell covalently connected to the nanocapsules.

Photo-Cross-Linkable Thermoresponsive Star Polymers Designed for Control of Cell-Surface Interactions

Star polymers with thermoresponsive arms, consisting of 2-(2-methoxyethoxy)ethyl methacrylate (MEO₂MA) and oligo(ethylene glycol) methacrylate with ~4 ethylene oxide units (OEOMA₃₀₀, M(n) = 300), were synthesized via atom transfer radical polymerization (ATRP). 25% of the arms contained benzophenone chain-end functionality at the star periphery. A mixture of linear poly(MEO₂MA-co-OEOMA₃₀₀)-Br macroinitiators without and with benzophenone end-group macroinitiators were (MI and Bzp-MI, respectively) cross-linked with ethylene glycol dimethacrylate to form star polymers. Formation of star polymers was monitored by GPC, and the presence of benzophenone functionality in the stars was confirmed by ¹H NMR. The UV-vis spectroscopy revealed that the star polymers exhibit the low critical solution temperature (LCST) at 27 °C, slightly lower than LCST of either MI or Bzp-MI. Commercially available tissue culture grade polystyrene surface was modified by depositing a thin film of functionalized stars and UV cross-linking (λ = 365 nm). The star polymers covalently attached onto surfaces allowed a control of cell shrinkage and attachment in response to temperature changes.

Thermoresponsive hydrogel scaffolds with tailored hydrophilic pores.

Thermoresponsive hydrogels with efficient water-release channels were prepared by incorporating star-shaped macromolecular pore precursors, with degradable disulfide crosslinked cores and hydrophilic poly(ethylene oxide) (PEO) arms, into the gel network. The gel framework exhibiting lower critical solution temperature (LCST) behavior was synthesized by atom transfer radical polymerization (ATRP) of 2-(2-methoxyethoxy)ethyl methacrylate and ethylene glycol dimethacrylate. The incorporation of degradable star macromolecules (dSM) was facilitated by growing the gel from ATRP initiator sites contained within their cores. Following the formation of the gel, the dSM cores were degraded, yielding uniform pores lined with hydrophilic PEO chains. The effect of hydrophilic pores on thermoresponsive hydrogel performances was studied by comparing hydrogels containing hydrophilic pores with analogous hydrogels with neutral pores or with pore-free controls. Dye absorption/release experiments pointed to the suitability of newly synthesized hydrogels as controlled-release media, for example, for drug delivery. Cell culture experiments confirmed their nontoxicity and biocompatibility (cell viability >98%).