Nanosphere Arrays with Controlled Sub-10-nm Gaps as Surface-Enhanced Raman Spectroscopy Substrates

We demonstrate a convenient and cost-effective chemical approach for fabricating highly ordered Au nanoparticle arrays with sub-10-nm interparticle gaps. Near-field enhancements inside the interparticle gaps create uniform periodic arrays of well-defined “hot spots” exploitable for large surface-enhanced Raman spectroscopy (SERS) enhancements. A cetyltrimethylammonium bromide (CTAB) bilayer surrounding each individual nanoparticle upon array crystallization is responsible for this periodic gap structure; displacement of the CTAB by smaller thiolated molecules does not affect the structural integrity of the arrays. As SERS substrates, the as-fabricated Au nanoparticle arrays exhibit high SERS sensitivity, long-term stability, and consistent reproducibility

Interactions of Ibuprofen with Hybrid Lipid Bilayers Probed by Complementary Surface-Enhanced Vibrational Spectroscopies

The incorporation of small molecules into lipid bilayers is a process of biological importance and clinical relevance that can change the material properties of cell membranes and cause deleterious side effects for certain drugs. Here we report the direct observation, using surface-enhanced Raman and IR spectroscopies (SERS, SEIRA), of the insertion of ibuprofen molecules into hybrid lipid bilayers. The alkanethiol-phospholipid hybrid bilayers were formed onto gold nanoshells by self-assembly, where the underlying nanoshell substrates provided the necessary enhancements for SERS and SEIRA. The spectroscopic data reveal specific interactions between ibuprofen and phospholipid moieties and indicate that the overall hydrophobicity of ibuprofen plays an important role in its intercalation in these membrane mimics

Chain-Length-Dependent Vibrational Resonances in Alkanethiol Self-Assembled Monolayers Observed on Plasmonic Nanoparticle Substrates

Alkanethiol self-assembled monolayers (SAMs) on gold exhibit a series of sharp resonances in their surface-enhanced Raman spectrum that depend dramatically on carbon chain length. This unusual behavior suggests a coupling of the gold−sulfur bond stretch with the longitudinal acoustic, “accordion”, vibrations of the molecular alkane chain. A simple model of a one-dimensional chain attached to a surface quantitatively reproduces these previously unreported experimental observations in this important nanomaterial system

Nanoshells Made Easy: Improving Au Layer Growth on Nanoparticle Surfaces

The growth of a continuous, uniform Au layer on a dielectric nanoparticle is the critical step in the synthesis of nanoparticles such as nanoshells or nanorice, giving rise to their unique geometry-dependent plasmon resonant properties. Here, we report a novel, streamlined method for Au layer metallization on prepared nanoparticle surfaces using carbon monoxide as the reducing agent. This approach consistently yields plasmonic nanoparticles with highly regular shell layers and is immune to variations in precursor or reagent preparation. Single particle spectroscopy combined with scanning electron microscopy reveal that thinner, more uniform shell layers with correspondingly red-shifted optical resonances are achievable with this approach

Electromigrated Nanoscale Gaps for Surface-Enhanced Raman Spectroscopy

Single-molecule detection with chemical specificity is a powerful and much desired tool for biology, chemistry, physics, and sensing technologies. Surface-enhanced spectroscopies enable single-molecule studies, yet reliable substrates of adequate sensitivity are in short supply. We present a simple, scaleable substrate for surface-enhanced Raman spectroscopy (SERS) incorporating nanometer-scale electromigrated gaps between extended electrodes. Molecules in the nanogap active regions exhibit hallmarks of very high Raman sensitivity, including blinking and spectral diffusion. Electrodynamic simulations show plasmonic focusing, giving electromagnetic enhancements approaching those needed for single-molecule SERS

Magnetic−Plasmonic Core−Shell Nanoparticles

Nanoparticles composed of magnetic cores with continuous Au shell layers simultaneously possess both magnetic and plasmonic properties. Faceted and tetracubic nanocrystals consisting of wüstite with magnetite-rich corners and edges retain magnetic properties when coated with a Au shell layer, with the composite nanostructures showing ferrimagnetic behavior. The plasmonic properties are profoundly influenced by the high dielectric constant of the mixed iron oxide nanocrystalline core. A comprehensive theoretical analysis that examines the geometric plasmon tunability over a range of core permittivities enables us to identify the dielectric properties of the mixed oxide magnetic core directly from the plasmonic behavior of the core−shell nanoparticle

Nanoparticle Shape Conservation in the Conversion of MnO Nanocrosses into Mn₃O₄

The conversion of hexagonal-, square-, and cross-shaped MnO nanoparticles into mixed MnO−Mn3O4 nanoparticles occurs with retention of the nanoparticle shape. Upon aging, extra diffraction spots appear in the TEM analyses of both hexagonal- and cross-shaped nanoparticles (NPs). These extra diffraction spots can be assigned to the spinel form of Mn3O4 (s-Mn3O4) and exhibit moiré interference patterns arising from the presence of two closely aligned, crystallographically similar phases. Examination of a variety of reaction conditions showed that the transformation of MnO into MnO/Mn3O4 occurred while the particles are suspended in hexane at ambient temperature, by refluxing in hexadecane for 36 h, by heating to 200 °C in air, and by irradiating the NPs with a Raman laser beam. The crystal phase development and shape retention can be observed by using transmission electron microscopy (TEM). Single-crystal and polycrystalline selected area electron diffraction (SAED) patterns and dark-field TEM images confirm the coexistence of both MnO and s-Mn3O4 phases. Evaluation of the polycrystalline SAED patterns after irradiation in the Raman spectrometer indicated the presence of rings assignable to the tetragonal phase of Mn3O4 (t-Mn3O4) as well as MnO and s-Mn3O4. The growth of the tetragonal phase by laser heating in the Raman experiment was confirmed by powder X-ray diffraction

A Cellular Trojan Horse for Delivery of Therapeutic Nanoparticles into Tumors

Destruction of hypoxic regions within tumors, virtually inaccessible to cancer therapies, may well prevent malignant progression. The tumor's recruitment of monocytes into these regions may be exploited for nanoparticle-based delivery. Monocytes containing therapeutic nanoparticles could serve as “Trojan Horses” for nanoparticle transport into these tumor regions. Here we report the demonstration of several key steps toward this therapeutic strategy:  phagocytosis of Au nanoshells, and photoinduced cell death of monocytes/macrophages as isolates and within tumor spheroids