Hot-electron-induced photodissociation of H2 was demonstrated on small Au nanoparticles (AuNPs) supported on SiO2. The rate of dissociation of H2 was found to be almost 2 orders of magnitude higher than that observed on equivalently prepared AuNPs on TiO2. The rate of H2 dissociation was found to be linearly dependent on illumination intensity with a wavelength dependence resembling the absorption spectrum of the plasmon of the AuNPs. This result provides strong additional support for the hot-electron-induced mechanism for H2 dissociation in this photocatalytic system.

Aqueous solutions containing light-absorbing nanoparticles have recently been shown to produce steam at high efficiencies upon solar illumination, even when the temperature of the bulk fluid volume remains far below its boiling point. Here we show that this phenomenon is due to a collective effect mediated by multiple light scattering from the dispersed nanoparticles. Randomly positioned nanoparticles that both scatter and absorb light are able to concentrate light energy into mesoscale volumes near the illuminated surface of the liquid. The resulting light absorption creates intense localized heating and efficient vaporization of the surrounding liquid. Light trapping-induced localized heating provides the mechanism for low-temperature light-induced steam generation and is consistent with classical heat transfer.

Au nanoparticles with plasmon resonances in the near-infrared (NIR) region of the spectrum efficiently convert light into heat, a property useful for the photothermal ablation of cancerous tumors subsequent to nanoparticle uptake at the tumor site. A critical aspect of this process is nanoparticle size, which influences both tumor uptake and photothermal efficiency. Here, we report a direct comparative study of ∼90 nm diameter Au nanomatryoshkas (Au/SiO2/Au) and ∼150 nm diameter Au nanoshells for photothermal therapeutic efficacy in highly aggressive triple negative breast cancer (TNBC) tumors in mice. Au nanomatryoshkas are strong light absorbers with 77% absorption efficiency, while the nanoshells are weaker absorbers with only 15% absorption efficiency. After an intravenous injection of Au nanomatryoshkas followed by a single NIR laser dose of 2 W/cm2 for 5 min, 83% of the TNBC tumor-bearing mice appeared healthy and tumor free >60 days later, while only 33% of mice treated with nanoshells survived the same period. The smaller size and larger absorption cross section of Au nanomatryoshkas combine to make this nanoparticle more effective than Au nanoshells for photothermal cancer therapy.

Plasmonic nanostructures enable the generation of large electromagnetic fields confined to small volumes, potentially providing a route for the development of nanoengineered nonlinear optical media. A metal-capped hemispherical nanoparticle, also known as a nanocup, generates second harmonic light with increasing intensity as the angle between the incident fundamental beam and the nanocup symmetry axis is increased. Nanoparticle orientation also modifies the emission direction of the second harmonic light. With conversion efficiencies similar to those of inorganic SHG crystals, these structures provide a promising approach for the design and fabrication of stable, synthetic second-order nonlinear optical materials tailored for specific wavelengths.

Monolayer molybdenum disulfide (MoS 2) produced by controlled vapor-phase synthesis is a commercially promising new two-dimensional material for optoelectronics because of its direct bandgap and broad absorption in the visible and ultraviolet regimes. By tuning plasmonic core-shell nanoparticles to the direct bandgap of monolayer MoS 2 and depositing them sparsely (<1% coverage) onto the material's surface, we observe a threefold increase in photocurrent and a doubling of photoluminescence signal for both excitonic transitions, amplifying but not altering the intrinsic spectral response. V

Metallic nanoparticles exhibiting plasmonic Fano resonances can provide large enhancements of their internal electric near field. Here we show that nanomatryoshkas, nanoparticles consisting of an Au core, an interstitial nanoscale SiO2 layer, and an Au shell layer, can selectively provide either a strong enhancement or a quenching of the spontaneous emission of fluorophores dispersed within their internal dielectric layer. This behavior can be understood by taking into account the near-field enhancement induced by the Fano resonance of the nanomatryoshka, which is responsible for enhanced absorption of the fluorophores incorporated into the nanocomplex. The combination of compact size and enhanced light emission with internal encapsulation of the fluorophores for increased biocompatibility suggests outstanding potential for this type of nanoparticle complex in biomedical applications.

Photothermal ablation based on resonant illumination of near-infrared-absorbing noble metal nanoparticles that have accumulated in tumors is a highly promising cancer therapy, currently in multiple clinical trials. A crucial aspect of this therapy is the nanoparticle size for optimal tumor uptake. A class of nanoparticles known as hollow Au (or Au–Ag) nanoshells (HGNS) is appealing because near-IR resonances are achievable in this system with diameters less than 100 nm. However, in this study, we report a surprising finding that in vivo HGNS are unstable, fragmenting with the Au and the remnants of the sacrificial Ag core accumulating differently in various organs. We synthesized 43, 62, and 82 nm diameter HGNS through a galvanic replacement reaction, with nanoparticles of all sizes showing virtually identical NIR resonances at ∼800 nm. A theoretical model indicated that alloying, residual Ag in the nanoparticle core, nanoparticle porosity, and surface defects all contribute to the presence of the plasmon resonance at the observed wavelength, with the major contributing factor being the residual Ag. While PEG functionalization resulted in stable nanoparticles under laser irradiation in solution, an anomalous, strongly element-specific biodistribution observed in tumor-bearing mice suggests that an avid fragmentation of all three sizes of nanoparticles occurred in vivo. Stability studies across a wide range of pH environments and in serum confirmed HGNS fragmentation. These results show that NIR resonant HGNS contain residual Ag, which does not stay contained within the HGNS in vivo. This demonstrates the importance of tracking both materials of a galvanic replacement nanoparticle in biodistribution studies and of performing thorough nanoparticle stability studies prior to any intended in vivo trial application.

As optical frequency nanoantennas, reduced-symmetry plasmonic nanoparticles have light-scattering properties that depend strongly on geometry, orientation, and variations in dielectric environment. Here we investigate how these factors influence the spectral and angular dependence of light scattered by Au nanocups. A simple dielectric substrate causes the axial, electric dipole mode of the nanocup to deviate substantially from its characteristic cos(2) θ free space scattering profile, while the transverse, magnetic dipole mode remains remarkably insensitive to the presence of the substrate. Nanoscale irregularities of the nanocup rim and the local substrate permittivity have a surprisingly large effect on the spectral- and angle-dependent light-scattering properties of these structures.