Nanoparticle-Mediated, Light-Induced Phase Separations

Nanoparticles that both absorb and scatter light, when dispersed in a liquid, absorb optical energy and heat a reduced fluid volume due to the combination of multiple scattering and optical absorption. This can induce a localized liquid–vapor phase change within the reduced volume without the requirement of heating the entire fluid. For binary liquid mixtures, this process results in vaporization of the more volatile component of the mixture. When subsequently condensed, these two steps of vaporization and condensation constitute a distillation process mediated by nanoparticles and driven by optical illumination. Because it does not require the heating of a large volume of fluid, this process requires substantially less energy than traditional distillation using thermal sources. We investigated nanoparticle-mediated, light-induced distillation of ethanol-H₂O and 1-propanol-H₂O mixtures, using Au–SiO₂ nanoshells as the absorber-scatterer nanoparticle and nanoparticle-resonant laser irradiation to drive the process. For ethanol-H₂O mixtures, the mole fraction of ethanol obtained in the light-induced process is substantially higher than that obtained by conventional thermal distillation, essentially removing the ethanol-H₂O azeotrope that limits conventional distillation. In contrast, for 1-propanol-H₂O mixtures the distillate properties resulting from light-induced distillation were very similar to those obtained by thermal distillation. In the 1-propanol-H₂O system, a nanoparticle-mediated, light-induced liquid–liquid phase separation was also observed

Fluorescence Enhancement of Molecules Inside a Gold Nanomatryoshka

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

Hot-Electron-Induced Dissociation of H₂ on Gold Nanoparticles Supported on SiO₂

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

The Surprising <i>in Vivo</i> Instability of Near-IR-Absorbing Hollow Au–Ag Nanoshells

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 <i>in vivo</i> 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 <i>in vivo</i>. 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 <i>in vivo</i>. 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 <i>in vivo</i> trial application

Toward Surface Plasmon-Enhanced Optical Parametric Amplification (SPOPA) with Engineered Nanoparticles: A Nanoscale Tunable Infrared Source

Active optical processes such as amplification and stimulated emission promise to play just as important a role in nanoscale optics as they have in mainstream modern optics. The ability of metallic nanostructures to enhance optical nonlinearities at the nanoscale has been shown for a number of nonlinear and active processes; however, one important process yet to be seen is optical parametric amplification. Here, we report the demonstration of surface plasmon-enhanced difference frequency generation by integration of a nonlinear optical medium, BaTiO₃, in nanocrystalline form within a plasmonic nanocavity. These nanoengineered composite structures support resonances at pump, signal, and idler frequencies, providing large enhancements of the confined fields and efficient coupling of the wavelength-converted idler radiation to the far-field. This nanocomplex works as a nanoscale tunable infrared light source and paves the way for the design and fabrication of a surface plasmon-enhanced optical parametric amplifier

Impurity-Induced Plasmon Damping in Individual Cobalt-Doped Hollow Au Nanoshells

The optical properties of plasmonic nanoparticles in the size range corresponding to the electrostatic, or dipole, limit have the potential to reveal effects otherwise masked by phase retardation. Here we examine the optical properties of individual, sub-50 nm hollow Au nanoshells (Co-HGNS), where Co is the initial sacrificial core nanoparticle, using single particle total internal reflection scattering (TIRS) spectroscopy. The residual Co present in the metallic shell induces a substantial broadening of the homogeneous plasmon resonance line width of the Co-HGNS, where the full width at half-maximum (fwhm) broadens proportionately with increasing Co content. This doping-induced line broadening provides a strategy for controlling plasmon line width independent of nanoparticle size, and has the potential to substantially modify the relative decay channels for localized nanoparticle surface plasmons