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The properties of nanoparticle superstructuresdepend on many factors,including the structural metrics of the nanoparticle superstructure(particle diameter, interparticle distances, etc.). Here, we introducea family of gold-binding peptide conjugate molecules that can directnanoparticle assembly, and we describe how these molecules can besystematically modified to adjust the structural metrics of lineardouble-helical nanoparticle superstructures. Twelve new peptide conjugatesare prepared via linking a gold-binding peptide, AYSSGAPPMPPF(PEPAu), to a hydrophobic aliphatic tail. The peptide conjugateshave 1, 2, or 3 PEPAuheadgroups and a C12,C14, C16, or C18aliphatic tail.The soft assembly of these peptide conjugates was studied using transmissionelectron microscopy (TEM), atomic force microscopy (AFM), and infrared(IR) spectroscopy. Several peptide conjugates assemble into 1-D twistedfibers having measurable structural parameters such as fiber width,thickness, and pitch that can be systematically varied by adjustingthe aliphatic tail length and number of peptide headgroups. The linearsoft assemblies serve as structural scaffolds for arranging gold nanoparticlesinto double-helical superstructures, which are examined via TEM. Thepitch and interparticle distances of the gold nanoparticle doublehelices correspond to the underlying metrics of the peptide conjugatesoft assemblies, illustrating that designed peptide conjugate moleculescan be used to not only direct the assembly of gold nanoparticlesbut also control the metrics of the assembled structure. [ABSTRACT FROM AUTHOR]

Determining the existence of any direct spectral relationship between the far-field scattering properties and the near-field Raman-enhancing properties of surface-enhanced Raman spectroscopy (SERS) substrates has been a challenging task with only a few significant results to date. Here, we prove that hot spot dominated systems show little dependence on the far-field scattering properties because of differences between near- and far-field localized surface plasmon resonance (LSPR) effects as well as excitation of new plasmon modes via a localized emitter. We directly probe the relationship between the near- and far-field light interactions using a correlated LSPR-transmission electron microscopy (TEM) surface-enhanced Raman excitation spectroscopy (SERES) technique. Fourteen individual SERS nanoantennas, Au nanoparticle aggregates ranging from dimers to undecamers, coated in a reporter molecule and encased in a protective silica shell, were excited using eight laser wavelengths. We observed no correlation between the spectral position of the LSPR maxima and the maximum enhancement factor (EF). The single nanoantenna data reveal EFs ranging from (2.5 ± 0.6) × 104 to (4.5 ± 0.6) × 108 with maximum enhancement for excitation wavelengths of 785 nm and lower energy. The magnitude of maximum EF was not correlated to the number of cores in the nanoantenna or the spectral position of the LSPR, suggesting a separation between near-field SERS enhancement and far-field Rayleigh scattering. Computational electrodynamics confirms the decoupling of maximum SERS enhancement from the peak of the scattering spectrum. It also points to the importance of a localized emitter for radiating Raman photons to the far-field which, in nonsymmetric systems, allows for the excitation of radiative plasmon modes that are difficult to excite with plane waves. Once these effects are considered, we are able to fully explain the hot spot dominated SERS response of the nanoantennas. [ABSTRACT FROM AUTHOR]