Ultrasensitive Raman Detection of Biomolecular Conformation at the Attomole Scale using Chiral Nanophotonics.

Understanding the function of a biomolecule hinges on its 3D conformation or secondary structure. Chirally sensitive, optically active techniques based on the differential absorption of UV-vis circularly polarized light excel at rapid characterisation of secondary structures. However, Raman spectroscopy, a powerful method for determining the structure of simple molecules, has limited capacity for structural analysis of biomolecules because of intrinsically weak optical activity, necessitating millimolar (mM) sample quantities. A breakthrough is presented for utilising Raman spectroscopy in ultrasensitive biomolecular conformation detection, surpassing conventional Raman optical activity by 15 orders of magnitude. This strategy combines chiral plasmonic metasurfaces with achiral molecular Raman reporters and enables the detection of different conformations (α-helix and random coil) of a model peptide (poly-L/D-lysine) at the ≤attomole level (monolayer). This exceptional sensitivity stems from the ability to detect local, molecular-scale changes in the electromagnetic (EM) environment of a chiral nanocavity induced by the presence of biomolecules using molecular Raman reporters. Further signal enhancement is achieved by incorporating achiral Au nanoparticles. The introduction of the nanoparticles creates highly localized regions of extreme optical chirality. This approach, which exploits Raman, a generic phenomenon, paves the way for next-generation technologies for the ultrasensitive detection of diverse biomolecular structures.

Beaming Elastic and SERS Emission from Bent-Plasmonic Nanowire on a Mirror Cavity.

We report on the experimental observation of beaming elastic and surface enhanced Raman scattering (SERS) emission from a bent-nanowire on a mirror (B-NWoM) cavity. The system was probed with polarization resolved Fourier plane and energy-momentum imaging to study the spectral and angular signature of the emission wavevectors. The out-coupled elastically scattered light from the kink occupies a narrow angular spread. We used a self-assembled monolayer of molecules with a well-defined molecular orientation to utilize the out-of-plane electric field in the cavity for enhancing Raman emission from the molecules and in achieving beaming SERS emission. Calculated directionality for elastic scattering and SERS emission was found to be 16.2 and 12.5 dB, respectively. The experimental data were corroborated with three-dimensional numerical finite element and finite difference time domain based numerical simulations. The results presented here may find relevance in understanding coupling of emitters with elongated plasmonic cavities and in designing on-chip optical antennas.

Large-scale optothermal assembly of colloids mediated by a gold microplate.

Light-activated colloidal assembly and swarming can act as model systems to explore non-equilibrium state of matter. In this context, creating new experimental platforms to facilitate and control two-dimensional assembly of colloidal crystals are of contemporary interest. In this paper, we present an experimental study of assembly of colloidal silica microparticles in the vicinity of a single-crystalline gold microplate evanescently excited by a 532 nm laser beam. The gold microplate acts as a source of heat and establishes a thermal gradient in the system. The created optothermal potential assembles colloids to form a two-dimensional poly-crystal, and we quantify the coordination number and hexagonal packing order of the assembly in such a driven system. Our experimental investigation shows that for a given particle size, the variation in assembly can be tuned as a function of excitation-polarization and surface to volume ratio of the gold microplates. Furthermore, we observe that the assembly is dependent on size of the particle and its material composition. Specifically, silica colloids assemble but polystyrene colloids do not, indicating an intricate behaviour of the forces under play. Our work highlights a promising direction in utilizing metallic microstructures that can be harnessed for optothermal colloidal crystal assembly and swarming studies. Our experimental system can be utilized to explore optically driven matter and photophoretic interactions in soft-matter including biological systems such as cells and micro organisms.

Directional second-harmonic generation controlled by sub-wavelength facets of an organic mesowire.

Directional harmonic generation is an important property characterizing the ability of nonlinear optical antennas to diffuse the signal in a well-defined region of space. Herein, we show how sub-wavelength facets of an organic molecular mesowire crystal can be utilized to systematically vary the directionality of second-harmonic generation (SHG) in the forward-scattering geometry. We demonstrate this capability on crystalline diamonoanthraquinone (DAAQ) mesowires with sub-wavelength facets. We observed that the radial angles of the SHG emission can be tuned over a range of 130 deg. This angular variation arises due to spatially distributed nonlinear dipoles in the focal volume of the excitation as well as the geometrical cross section and facet orientation of the mesowire. Numerical simulations of the near-field excitation profile corroborate the role of the mesowire geometry in localizing the electric field. In addition to directional SHG from the mesowire, we experimentally observe optical waveguiding of the nonlinear two-photon excited fluorescence (TPEF). Interestingly, we observed that for a given pump excitation, the TPEF signal is isotropic and delocalized, whereas the SHG emission is directional and localized at the location of excitation. All the observed effects have direct implications not only in active nonlinear optical antennas but also in nonlinear signal processing.

Spin-Hall effect in the scattering of structured light from plasmonic nanowire.

Spin-orbit interactions are subwavelength phenomena that can potentially lead to numerous device-related applications in nanophotonics. Here, we report the spin-Hall effect in the forward scattering of Hermite-Gaussian (HG) and Gaussian beams from a plasmonic nanowire. Asymmetric scattered radiation distribution was observed for circularly polarized beams. Asymmetry in the scattered radiation distribution changes the sign when the polarization handedness inverts. We found a significant enhancement in the spin-Hall effect for a HG beam compared to a Gaussian beam for constant input power. The difference between scattered powers perpendicular to the long axis of the plasmonic nanowire was used to quantify the enhancement. In addition, the nodal line of the HG beam acts as the marker for the spin-Hall shift. Numerical calculations corroborate experimental observations and suggest that the spin flow component of the Poynting vector associated with the circular polarization is responsible for the spin-Hall effect and its enhancement.

Doughnut-shaped emission from vertical organic nanowire coupled to thin plasmonic film.

Vertical nanowires facilitate an innovative mechanism to channel the optical field in the orthogonal direction and act as a nanoscale light source. Subwavelength, vertically oriented nanowire platforms, both of plasmonic and semiconducting variety, can facilitate interesting far-field emission profiles and potentially carry orbital angular momentum states. Motivated by these prospects, in this Letter, we show how a hybrid plasmonic-organic platform can be harnessed to engineer far-field radiation. The system that we have employed is an organic nanowire made of diaminoanthroquinone grown on a plasmonic gold film. We experimentally and numerically studied angular distribution of surface plasmon polariton mediated emission from a single, vertical organic nanowire by utilizing evanescent excitation and Fourier plane microscopy. Photoluminescence and elastic scattering from a single nanowire was analyzed individually in terms of inplane momentum states of the outcoupled photons. We found that the emission is doughnut-shaped in both photoluminescence and elastic scattering regimes. We anticipate that the discussed results can be relevant in designing efficient, polariton-mediated nanoscale photon sources that can carry orbital angular momentum states.

Differential Wavevector Distribution of Surface-Enhanced Raman Scattering and Fluorescence in a Film-Coupled Plasmonic Nanowire Cavity.

We report on the experimental observation of differential wavevector distribution of surface-enhanced Raman scattering (SERS) and fluorescence from dye molecules confined to a gap between plasmonic silver nanowire and a thin, gold mirror. The fluorescence was mainly confined to higher values of in-plane wavevectors, whereas SERS signal was uniformly distributed along all the wavevectors. The optical energy-momentum spectra from the distal end of the nanowire revealed strong polarization dependence of this differentiation. All these observations were corroborated by full-wave three-dimensional numerical simulations, which further revealed an interesting connection between out-coupled wavevectors and parameters such as hybridized modes in the gap-plasmon cavity, and orientation and location of molecular dipoles in the geometry. Our results reveal a new prospect of discriminating electronic and vibrational transitions in resonant dye molecules using a subwavelength gap plasmonic cavity in the continuous-wave excitation limit, and can be further harnessed to engineer molecular radiative relaxation processes in momentum space.