Resonant coupling between plasmonic nanoantennas and molecular vibrational excitations is employed to amplify the weak overtone transitions that reside in the near-infrared. We explore for the first time the differential extinction of forbidden molecular overtone transitions coupled to the localized surface plasmons. We show a non-trivial interplay between the molecular absorption enhancement and suppression of plasmonic absorption in a coupled system. When the resonance conditions are met at 1.5 $\mu$m, two orders of magnitude enhancement of differential extinction as compared to the extinction of the same amount of free probe molecules is achieved. Our results pave a road toward a new class of surface enhanced near-infrared absorption-based sensors.
Chiral plasmonic nanostructures have emerged as promising objects for numerous applications in nanophotonics, optoelectronics, biosensing, chemistry, and pharmacy. Here, we propose a novel method to induce strong chirality in achiral ensembles of gold nanoparticles via irradiation with circularly-polarized light of a picosecond Nd:YAG laser. Embedding of gold nanoparticles into a nanoporous silicate matrix leads to the formation of a racemic mixture of metal nanoparticles of different chirality that is enhanced by highly asymmetric dielectric environment of the nanoporous matrix. Then, illumination with intense circularly-polarized light selectively modifies the particles with the chirality defined by the handedness of the laser light, while their “enantiomers” survive the laser action almost unaffected. This novel modification of the spectral hole burning technique leads to the formation of an ensemble of plasmonic metal nanoparticles that demonstrates circular dichroism up to 100 mdeg. An unforeseen peculiarity of the chiral nanostructures obtained in this way is that 2D and 3D nanostructures contribute almost equally to the observed circular dichroism signals. Thus, the circular dichroism is neither even nor odd under reversal of direction of light propagation. These findings will help guide the development of a passive optical modulator and nanoplatform for enhanced chiral sensing and catalysis.
Whispering gallery mode (WGM) resonators doped with fluorescent materials find impressive applications in biological sensing. They do not require special conditions for the excitation of WGM inside that provide the basis for in vivo sensing. Currently, the problem of materials for in vivo WGM sensors are substantial since their fluorescence should have stable optical properties as well as they should be biocompatible. To address this we present WGM microresonators of 5–7 m, where the dopant is made of carbon quantum dots (CDs). CDs are biocompatible since they are produced from carbon and demonstrate bright optical emission, which shows different bands depending on the excitation wavelength. The WGM sensors developed here were tested as label-free biosensors by detecting bovine serum albumin molecules. The results showed WGM frequency shifting, with the limit of detection down to M level.
Molecular overtones stretching modes that occupy the near-infrared (NIR) are weak compared to the fundamental vibrations. Here we report on the enhancement of absorption by molecular vibrations overtones via electromagnetic field enhancement of plasmonic nanoparallelepipeds comprising a square lattice. We explore numerically, using finite element method (FEM), gold metasurfaces on a transparent dielectric substrate covered by weakly absorbing analyte supporting N-H and C-H overtone absorption bands around 1.5 m and around 1.67 m, respectively. We found that the absorption enhancement in N-H overtone transition can be increased up to the factor of 22.5 due to the combination of localized surface plasmon resonance in prolonged nanoparticles and lattice Rayleigh anomaly. Our approach may be extended for sensitive identification of other functional group overtone transitions in the near-infrared spectral range.