Hot carrier multiplication in plasmonic photocatalysis.

Light-induced hot carriers derived from the surface plasmons of metal nanostructures have been shown to be highly promising agents for photocatalysis. While both nonthermal and thermalized hot carriers can potentially contribute to this process, their specific role in any given chemical reaction has generally not been identified. Here, we report the observation that the H2-D2 exchange reaction photocatalyzed by Cu nanoparticles is driven primarily by thermalized hot carriers. The external quantum yield shows an intriguing S-shaped intensity dependence and exceeds 100% for high light intensities, suggesting that hot carrier multiplication plays a role. A simplified model for the quantum yield of thermalized hot carriers reproduces the observed kinetic features of the reaction, validating our hypothesis of a thermalized hot carrier mechanism. A quantum mechanical study reveals that vibrational excitations of the surface Cu-H bond is the likely activation mechanism, further supporting the effectiveness of low-energy thermalized hot carriers in photocatalyzing this reaction.

Anti-Stokes Emission from Hot Carriers in Gold Nanorods.

The origin of light emission from plasmonic nanoparticles has been strongly debated lately. It is present as the background of surface-enhanced Raman scattering and, despite the low yield, has been used for novel sensing and imaging applications because of its photostability. Although the role of surface plasmons as an enhancing antenna is widely accepted, the main controversy regarding the mechanism of the emission is its assignment to either radiative recombination of hot carriers (photoluminescence) or electronic Raman scattering (inelastic light scattering). We have previously interpreted the Stokes-shifted emission from gold nanorods as the Purcell effect enhanced radiative recombination of hot carriers. Here we specifically focused on the anti-Stokes emission from single gold nanorods of varying aspect ratios with excitation wavelengths below and above the interband transition threshold while still employing continuous wave lasers. Analysis of the intensity ratios between Stokes and anti-Stokes emission yields temperatures that can only be interpreted as originating from the excited electron distribution and not a thermally equilibrated phonon population despite not using pulsed laser excitation. Consistent with this result as well as previous emission studies using ultrafast lasers, the power-dependence of the upconverted emission is nonlinear and gives the average number of participating photons as a function of emission wavelength. Our findings thus show that hot carriers and photoluminescence play a major role in the upconverted emission.

Photoluminescence of Gold Nanorods: Purcell Effect Enhanced Emission from Hot Carriers.

We demonstrate, experimentally and theoretically, that the photon emission from gold nanorods can be viewed as a Purcell effect enhanced radiative recombination of hot carriers. By correlating the single-particle photoluminescence spectra and quantum yields of gold nanorods measured for five different excitation wavelengths and varied excitation powers, we illustrate the effects of hot carrier distributions evolving through interband and intraband transitions and the photonic density of states on the nanorod photoluminescence. Our model, using only one fixed input parameter, describes quantitatively both emission from interband recombination and the main photoluminescence peak coinciding with the longitudinal surface plasmon resonance.

Plasmon-induced hot carriers in metallic nanoparticles.

Plasmon-induced hot carrier formation is attracting an increasing research interest due to its potential for applications in photocatalysis, photodetection and solar energy harvesting. However, despite very significant experimental effort, a comprehensive theoretical description of the hot carrier generation process is still missing. In this work we develop a theoretical model for the plasmon-induced hot carrier process and apply it to spherical silver nanoparticles and nanoshells. In this model, the conduction electrons of the metal are described as free particles in a finite spherical potential well, and the plasmon-induced hot carrier production is calculated using Fermi's golden rule. We show that the inclusion of many-body interactions has only a minor influence on the results. Using the model we calculate the rate of hot carrier generation, finding that it closely follows the spectral profile of the plasmon. Our analysis reveals that particle size and hot carrier lifetime play a central role in determining both the production rate and the energy distribution of the hot carriers. Specifically, larger nanoparticle sizes and shorter lifetimes result in higher carrier production rates but smaller energies, and vice versa. We characterize the efficiency of the hot carrier generation process by introducing a figure of merit that measures the number of high energy carriers generated per plasmon. Furthermore, we analyze the spatial distribution and directionality of these excitations. The results presented here contribute to the basic understanding of plasmon-induced hot carrier generation and provide insight for optimization of the process.

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.

Safety and low molecular weight heparin in older people in a hospital with ambulatory care.

UNLABELLED: To examine major bleeding and mortality rates of low molecular weight heparin (LMWH) and unfractionated heparin (UFH) for patients with pulmonary embolism (PE) and/or deep vein thrombosis (DVT), a retrospective review of the medical records for 286 patients who presented at a local hospital with PE and/or DVT during the period November 2002-August 2003 was performed. DATA COLLECTED: presence of co-morbidities, concurrent medications, presence, site and severity of bleeding, outcome. Of all the patients, 50.7% received LMWH plus warfarin, 21.0% received UFH plus LMWH plus warfarin, 14.0% received UFH and warfarin, and 9.8% received LMWH only. There were nine minor bleeds and six major bleeds, which resulted in four deaths. Being a hospitalized patient and being age > or =70 years were associated with a major bleed (p<0.05). For hospital inpatients age > or =70 years on UFH and LMWH the number of major bleeds/1000 patient days was 18.9 and 9.2, respectively. The major bleeding rate is comparable if not better than that reported in the literature in our hospital setting where nearly half of the anticoagulation services were provided as ambulatory care. The increased rate of bleeding in the elderly we found is consistent with the findings of previous studies.