Tuesday, June 17, 2008 - 10:20 AM
Room 7b (McKimmon Conference Center)
316

Reconfigurable Core-Satellite Nanoassemblies as Molecularly-Driven Plasmonic Switches

David S. Sebba, Jack. J. Mock, David R. Smith, Thom LaBean, and Anne A. Lazarides. Duke University, Durham, NC

Colloidal metal nanoparticles (MNPs) support localized surface plasmon resonances that are sensitive to the presence of molecules, materials, and other polarizable particles that assemble in their near fields. Biomolecule nanoparticle conjugates have been implemented in various molecular detection applications in formats that allow monitoring of plasmonic response. Each specific format has vulnerabilities as well as advantages. For instance, monolayers of immobilized particles functionalized with receptors respond sensitively to target molecules and can be used to track kinetics, but are equally sensitive to non-specific adsorbates, a disadvantage shared with traditional, thin film surface plasmon resonance (SPR). Other formats, such as target induced particle aggregation offer strong plasmon modulation, but involve a complex bulk phase process that presents a significant barrier to quantitative interpretation of the optical data. Here, we report plasmon modulation in pre-formed, few particle assemblies linked by reconfigurable DNA nanostructures. The investigation is motivated by the potential of reconfigurable few particle assemblies to provide control of plasmon coupling in a format that displays high specificity and responsiveness per molecule. In the coupled system upon which we report, DNA nanostructures tether gold satellite particles to a gold core particle. The DNA nanostructures use duplex DNA to control interparticle separation and are responsive to target strands that modulate interparticle helix length resulting in an observable change in assembly plasmon resonance. These reconfigurable assemblies are characterized structurally using dynamic light scattering and transmission electron microscopy and optically using elastic scattering spectroscopy. We demonstrate that DNA nanostructures provide molecular control of interparticle separation by correlating measured plasmonic signals with simulated signals derived from models based upon measured structural parameters. In order to study the sensitivity of core-satellite spectral response to colloid material properties, single assembly scattering spectroscopy and multi-color CCD image analysis are used to monitor perturbation of the gold core plasmon resonance induced by assembly of gold or silver satellites. In the absence of structural data, scattering spectra are simulated for assemblies with various numbers of satellite particles and various satellite configurations. While assembly of either satellite type results in enhanced scattering of red light,the properties of the modulated plasmon are found to display less assembly-to-assembly variation when the satellite plasmon is offset from the core particle plasmon frequency.