RESUMEN
Measuring the orientation dynamics of nanoparticles and nonfluorescent molecules in real time with optical methods is still a challenge in nanoscience and biochemistry. Here, we examine optoplasmonic sensing taking the rotational diffusion of plasmonic nanorods as an experimental model. Our detection method is based on monitoring the dark-field scattering of a relatively large sensor gold nanorod (GNR) (40 nm in diameter and 112 nm in length) as smaller plasmonic nanorods cross its near field. We observe the rotational motion of single small gold nanorods (three samples with about 5 nm in diameter and 15.5, 19.1, and 24.6 nm in length) in real time with a time resolution around 50 ns. Plasmonic coupling enhances the signal of the diffusing gold nanorods, which are 1 order of magnitude smaller in volume (about 300 nm3) than those used in our previous rotational diffusion experiments. We find a better angular sensitivity with plasmonic coupling in comparison to the free diffusion in the confocal volume. Yet, the angle sensitivity we find with plasmonic coupling is reduced compared to the sensitivity expected from simulations at fixed positions due to the simultaneous translational and rotational diffusion of the small nanorods. To get a reliable plasmonic sensor with the full angular sensitivity, it will be necessary to construct a plasmonic assembly with positions and orientations nearly fixed around the optimum geometry.
RESUMEN
Circular dichroism (CD) is the property of chiral nanoobjects to absorb circularly polarized light of either handedness to different extents. Photothermal microscopy enables the detection of CD signals with high sensitivity and provides a direct absorptive response of the samples under study. To achieve CD measurements at the single-particle level, one must reduce such artifacts as leakage of linear dichroism (LD) and residual intensity modulation. We have simulated our setup with a simple model, which allows us to tune modulation parameters to obtain a CD signal virtually free from artifacts. We demonstrate the sensitivity of our setup by measuring the very weak inherent CD signals of single gold nanospheres. We furthermore demonstrate that our method can be extended to obtain spectra of the full absorptive properties of single nanoparticles, including isotropic absorption, linear dichroism, and circular dichroism. We then investigate nominally achiral gold nanoparticles immersed in a chiral liquid. Carefully taking into account the intrinsic chirality of the particles and its change due to heat-induced reshaping, we find that the chiral liquid carvone surrounding the particle has no measurable effect on the particles' chirality, down to g-factors of 3 × 10-4.
