DNA origami is a novel self-assembly technique allowing one to form various 2Dshapes and position matter with nanometer accuracy. We use DNA origami templates to engineer Surface Enhanced Raman Scattering (SERS) substrates. Specifically, gold nanoparticles were selectively placed on the corners of rectangular origami and subsequently enlarged via solution-based metal deposition. The resulting assemblies exhibit "hot spots" of enhanced electromagnetic field between the nanoparticles. We observed a significant Raman signal enhancement from molecules covalently attached to the assemblies, as compared to control nanoparticle samples which lack inter-particle hot spots. Furthermore, Raman molecules are used to map out the hot spots' distribution, as they are burned when experiencing a threshold electric field. Our method opens up the prospects of using DNA origami to rationally engineer and assemble plasmonic structures for molecular spectroscopy.

Gold nanostructures focus light to a molecular length scale at their surface, creating the possibility to visualize molecular structure. The high optical intensity leads to surface enhanced Raman scattering (SERS) from nearby molecules. SERS spectra contain information on molecular position and orientation relative to the surface but are difficult to interpret quantitatively. Here we describe a ratiometric analysis method that combines SERS and unenhanced Raman spectra with theoretical calculations of the optical field and molecular polarizability. When applied to the surfactant layer on gold nanorods, the alkane chain is found to be tilted 25° to the surface normal, which matches previous reports of the layer thickness. The analysis was also applied to fluid phase phospholipid bilayers that contain tryptophan on the surface of gold nanorods. The lipid double bond was found to be oriented normal to the bilayer and 13 Å from the nitrogen atom. Tryptophan was found to sit near the glycerol headgroup region with its indole ring 43° from the bilayer normal. This new method can determine specific interfacial structure under ambient conditions, with microscopic quantities of material, and without molecular labels.

The localized surface plasmon resonances of gold nanoparticles have been widely studied at visible and near-infrared frequencies but less so in the ultraviolet. The spectral extinction measurements of gold nanospheres at UV wavelengths reported here closely match calculated spectra down to 200 nm using the measured dielectric function of gold. The nanosphere volume attenuation coefficient, αv, is size-dependent in the 200–300 nm wavelength range where the dielectric function follows the Drude free electron model (as it does for wavelengths larger than 500 nm). In the interband transition region, the extinction is more closely proportional to mass and therefore has a value of αv that is largely independent of size. Gold nanorod solutions exhibit very strong UV extinction below 220 nm due to charge transfer to solvent (c.t.t.s.) excitations of the bromide counterion to the cationic surfactant. The gold nanorod UV properties depend on the alignment between the optical polarization and nanorod structure. For polarization along each major axis, the spectral extinction is similar to that of a sphere of nanorod size in that dimension.

Surface-enhanced Raman scattering (SERS) from gold and silver nanoparticles suspended in solution enables a more quantitative level of analysis relative to SERS from aggregated nanoparticles and roughened metal substrates.