Glycan Node Analysis of Plasma-Derived Extracellular Vesicles.

Blood plasma is a readily accessible source of extracellular vesicles (EVs), i.e., cell-secreted nanosized carriers that contain various biomolecules, including glycans. Previous studies have demonstrated that glycans play a major role in physiological and pathological processes, and certain plasma glycans have been associated with disease conditions. However, glycome studies have been limited by a lack of analytical techniques with the throughput capacity necessary to study hundreds of clinical samples. This study is the first to characterize the EV plasma glycome based on all major glycan classes. The results based on glycan node analysis revealed, as expected, that plasma-derived EVs have distinct glycan features from donor-matched whole plasma. Specifically, glycan nodes corresponding to those observed in chondroitin sulfate, dermatan sulfate, type I keratan sulfate, and type II keratan sulfate were enriched on EVs. The identification of specific differences in glycan features in plasma vs. plasma-derived EVs is relevant for understanding the physiological role of EVs and as a reference for future diagnostic studies. Additionally, the results indicate that EV glycan nodes do not substantially differ among a small set of healthy donors. These results lay the framework for the further evaluation of all EV glycan classes as diagnostic markers, therapeutic targets, and biologically active components in health and disease.

Designer photonic dynamics by using non-uniform electron temperature distribution for on-demand all-optical switching times.

While free electrons in metals respond to ultrafast excitation with refractive index changes on femtosecond time scales, typical relaxation mechanisms occur over several picoseconds, governed by electron-phonon energy exchange rates. Here, we propose tailoring these intrinsic rates by engineering a non-uniform electron temperature distribution through nanostructuring, thus, introducing an additional electron temperature relaxation channel. We experimentally demonstrate a sub-300 fs switching time due to the wavelength dependence of the induced hot electron distribution in the nanostructure. The speed of switching is determined by the rate of redistribution of the inhomogeneous electron temperature and not just the rate of heat exchange between electrons and phonons. This effect depends on both the spatial overlap between control and signal fields in the metamaterial and hot-electron diffusion effects. Thus, switching rates can be controlled in nanostructured systems by designing geometrical parameters and selecting wavelengths, which determine the control and signal mode distributions.

Generalization of the optical theorem: experimental proof for radially polarized beams.

The optical theorem, which is a consequence of the energy conservation in scattering processes, directly relates the forward scattering amplitude to the extinction cross-section of the object. Originally derived for planar scalar waves, it neglects the complex structure of the focused beams and the vectorial nature of the electromagnetic field. On the other hand, radially or azimuthally polarized fields and various vortex beams, essential in modern photonic technologies, possess a prominent vectorial field structure. Here, we experimentally demonstrate a complete violation of the commonly used form of the optical theorem for radially polarized beams at both visible and microwave frequencies. We show that a plasmonic particle illuminated by such a beam exhibits strong extinction, while the scattering in the forward direction is zero. The generalized formulation of the optical theorem provides agreement with the observed results. The reported effect is vital for the understanding and design of the interaction of complex vector beams carrying longitudinal field components with subwavelength objects important in imaging, communications, nanoparticle manipulation, and detection, as well as metrology.

Universal switching of plasmonic signals using optical resonator modes.

We propose and investigate, both experimentally and theoretically, a novel mechanism for switching and modulating plasmonic signals based on a Fano interference process, which arises from the coupling between a narrow-band optical Fabry-Pérot cavity and a surface plasmon polariton (SPP) source. The SPP wave emitted from the cavity is actively modulated in the vicinity of the cavity resonances by altering the cavity Q-factor and/or resonant frequencies. We experimentally demonstrate dynamic SPP modulation both by mechanical control of the cavity length and all-optically by harnessing the ultrafast nonlinearity of the Au mirrors that form the cavity. An electro-optical modulation scheme is also proposed and numerically illustrated. Dynamic operation of the switch via mechanical means yields a modulation in the SPP coupling efficiency of ~80%, while the all-optical control provides an ultrafast modulation with an efficiency of 30% at a rate of ~0.6 THz. The experimental observations are supported by both analytical and numerical calculations of the mechanical, all-optical and electro-optical modulation methods.

Integrated plasmonic circuitry on a vertical-cavity surface-emitting semiconductor laser platform.

Integrated plasmonic sources and detectors are imperative in the practical development of plasmonic circuitry for bio- and chemical sensing, nanoscale optical information processing, as well as transducers for high-density optical data storage. Here we show that vertical-cavity surface-emitting lasers (VCSELs) can be employed as an on-chip, electrically pumped source or detector of plasmonic signals, when operated in forward or reverse bias, respectively. To this end, we experimentally demonstrate surface plasmon polariton excitation, waveguiding, frequency conversion and detection on a VCSEL-based plasmonic platform. The coupling efficiency of the VCSEL emission to waveguided surface plasmon polariton modes has been optimized using asymmetric plasmonic nanostructures. The plasmonic VCSEL platform validated here is a viable solution for practical realizations of plasmonic functionalities for various applications, such as those requiring sub-wavelength field confinement, refractive index sensitivity or optical near-field transduction with electrically driven sources, thus enabling the realization of on-chip optical communication and lab-on-a-chip devices.

Hyperbolic metamaterial antenna for second-harmonic generation tomography.

The detection and processing of information carried by evanescent field components are key elements for subwavelength optical microscopy as well as single molecule sensing applications. Here, we numerically demonstrate the potential of a hyperbolic medium in the design of an efficient metamaterial antenna enabling detection and tracking of a nonlinear object, with an otherwise hidden second-harmonic signature. The presence of the antenna provides 103-fold intensity enhancement of the second harmonic generation (SHG) from a nanoparticle through a metamaterial-assisted access to evanescent second-harmonic fields. Alternatively, the observation of SHG from the metamaterial itself can be used to detect and track a nanoparticle without a nonlinear response. The antenna allows an optical resolution of several nanometers in tracking the nanoparticle's location via observations of the far-field second-harmonic radiation pattern.

Bulk plasmon-polaritons in hyperbolic nanorod metamaterial waveguides.

Hyperbolic metamaterials comprised of an array of plasmonic nanorods provide a unique platform for designing optical sensors and integrating nonlinear and active nanophotonic functionalities. In this work, the waveguiding properties and mode structure of planar anisotropic metamaterial waveguides are characterized experimentally and theoretically. While ordinary modes are the typical guided modes of the highly anisotropic waveguides, extraordinary modes, below the effective plasma frequency, exist in a hyperbolic metamaterial slab in the form of bulk plasmon-polaritons, in analogy to planar-cavity exciton-polaritons in semiconductors. They may have very low or negative group velocity with high effective refractive indices (up to 10) and have an unusual cut-off from the high-frequency side, providing deep-subwavelength (λ0/6-λ0/8 waveguide thickness) single-mode guiding. These properties, dictated by the hyperbolic anisotropy of the metamaterial, may be tuned by altering the geometrical parameters of the nanorod composite.

Superluminal and stopped light due to mode coupling in confined hyperbolic metamaterial waveguides.

Anisotropic metamaterials with hyperbolic dispersion can be used to design waveguides with unusual properties. We show that, in contrast to planar waveguides, geometric confinement leads to coupling of ordinary (forward) and extraordinary (backward) modes and formation of hybrid waveguided modes, which near the crossing point may exhibit slow, stopped or superluminal behavior accompanied by very strong group velocity dispersion. These modes can be used for designing stopped-light nanolasers for nanophotonic applications and dispersion-facilitated signal reshaping in telecom applications.

Hyperbolic polaritonic crystals based on nanostructured nanorod metamaterials.

Surface plasmon polaritons usually exist on a few suitable plasmonic materials; however, nanostructured plasmonic metamaterials allow a much broader range of optical properties to be designed. Here, bottom-up and top-down nanostructuring are combined, creating hyperbolic metamaterial-based photonic crystals termed hyperbolic polaritonic crystals, allowing free-space access to the high spatial frequency modes supported by these metamaterials.

Eliminating material constraints for nonlinearity with plasmonic metamaterials.

Nonlinear optical materials comprise the foundation of modern photonics, offering functionalities ranging from ultrafast lasers to optical switching, harmonic and soliton generation. Optical nonlinearities are typically strong near the electronic resonances of a material and thus provide limited tuneability for practical use. Here we show that in plasmonic nanorod metamaterials, the Kerr-type nonlinearity is not limited by the nonlinear properties of the constituents. Compared with gold's nonlinearity, the measured nonlinear absorption and refraction demonstrate more than two orders of magnitude enhancement over a broad spectral range that can be engineered via geometrical parameters. Depending on the metamaterial's effective plasma frequency, either a focusing or defocusing nonlinearity is observed. The ability to obtain strong and fast optical nonlinearities in a given spectral range makes these metamaterials a flexible platform for the development of low-intensity nonlinear applications.

Looking into meta-atoms of plasmonic nanowire metamaterial.

Nanowire-based plasmonic metamaterials exhibit many intriguing properties related to the hyperbolic dispersion, negative refraction, epsilon-near-zero behavior, strong Purcell effect, and nonlinearities. We have experimentally and numerically studied the electromagnetic modes of individual nanowires (meta-atoms) forming the metamaterial. High-resolution, scattering-type near-field optical microscopy has been used to visualize the intensity and phase of the modes. Numerical and analytical modeling of the mode structure is in agreement with the experimental observations and indicates the presence of the nonlocal response associated with cylindrical surface plasmons of nanowires.

Ultrafast all-optical modulation with hyperbolic metamaterial integrated in Si photonic circuitry.

The integration of optical metamaterials within silicon integrated photonic circuitry bears significantly potential in the design of low-power, nanoscale footprint, all-optical functionalities. We propose a novel concept and provide detailed analysis of an on-chip ultrafast all-optical modulator based on an hyperbolic metamaterial integrated in a silicon waveguide. The anisotropic metamaterial based on gold nanorods is placed on top of the silicon waveguide to form a modulator with a 300x440x600 nm(3) footprint. For the operating wavelength of 1.5 µm, the optimized geometry of the device has insertion loss of about 5 dB and a modulation depth of 35% with a sub-ps switching rate. The switching energy estimated from nonlinear transient dynamic numerical simulations is 3.7 pJ/bit when the transmission is controlled optically at a wavelength of 532 nm, resonant with the transverse plasmonic mode of the metamaterial. The switching mechanism is based on the control of the hybridization of eigenmodes in the metamaterial slab and the Si waveguide.

Hydrogen detected by the naked eye: optical hydrogen gas sensors based on core/shell plasmonic nanorod metamaterials.

Gold-core/palladium-shell metamaterials for hydrogen detection are presented. The more than 30% change in both the reflection and transmission from the metamaterial layer that is observed when the layer is exposed to 2% hydrogen mixture is clearly noticeable to the naked eye as a change in the brightness of light transmitted by the metamaterial. This sensor should make a contribution to the safety of processes involving hydrogen.

Near-field hyperspectral optical imaging.

This Minireview presents an overview of near-field hyperspectral imaging and discusses its applications. Based on a fibre-tip probe, the hyperspectral near-field optical microscope allows the simultaneous acquisition of near-field images over a broad spectral range (400 to 1000 nm), enabling the recovery of local spectroscopic information, which is essential for understanding the resonant interaction of light with nanostructured objects because the far-field and near-field spectral responses can differ significantly, as is the case for plasmonic nanostructures. The optical information is collected through local interactions with the evanescent fields at the surface of the sample; therefore, the approach provides spectroscopic information with nanoscale spatial resolution. Several applications of spectroscopic near-field microscopy are described for the visualisation of plasmonic modes in metallic nanostructures and near-field fluorescence spectroscopy.

Photonic spin Hall effect in hyperbolic metamaterials for polarization-controlled routing of subwavelength modes.

The routing of light in a deep subwavelength regime enables a variety of important applications in photonics, quantum information technologies, imaging and biosensing. Here we describe and experimentally demonstrate the selective excitation of spatially confined, subwavelength electromagnetic modes in anisotropic metamaterials with hyperbolic dispersion. A localized, circularly polarized emitter placed at the boundary of a hyperbolic metamaterial is shown to excite extraordinary waves propagating in a prescribed direction controlled by the polarization handedness. Thus, a metamaterial slab acts as an extremely broadband, nearly ideal polarization beam splitter for circularly polarized light. We perform a proof of concept experiment with a uniaxial hyperbolic metamaterial at radio-frequencies revealing the directional routing effect and strong subwavelength λ/300 confinement. The proposed concept of metamaterial-based subwavelength interconnection and polarization-controlled signal routing is based on the photonic spin Hall effect and may serve as an ultimate platform for either conventional or quantum electromagnetic signal processing.

Near-field interference for the unidirectional excitation of electromagnetic guided modes.

Wave interference is a fundamental manifestation of the superposition principle with numerous applications. Although in conventional optics, interference occurs between waves undergoing different phase advances during propagation, we show that the vectorial structure of the near field of an emitter is essential for controlling its radiation as it interferes with itself on interaction with a mediating object. We demonstrate that the near-field interference of a circularly polarized dipole results in the unidirectional excitation of guided electromagnetic modes in the near field, with no preferred far-field radiation direction. By mimicking the dipole with a single illuminated slit in a gold film, we measured unidirectional surface-plasmon excitation in a spatially symmetric structure. The surface wave direction is switchable with the polarization.

Low-temperature plasmonics of metallic nanostructures.

The requirements for spatial and temporal manipulation of electromagnetic fields on the nanoscale have recently resulted in an ever-increasing use of plasmonics for achieving various functionalities with superior performance to those available from conventional photonics. For these applications, ohmic losses resulting from free-electron scattering in the metal is one major limitation for the performance of plasmonic structures. In the low-frequency regime, ohmic losses can be reduced at low temperatures. In this work, we study the effect of temperature on the optical response of different plasmonic nanostructures and show that the extinction of a plasmonic nanorod metamaterial can be efficiently controlled with temperature with transmission changes by nearly a factor of 10 between room and liquid nitrogen temperatures, while temperature effects in plasmonic crystals are relatively weak (transmission changes only up to 20%). Because of the different nature of the plasmonic interactions in these types of plasmonic nanostructures, drastically differing responses (increased or decreased extinction) to temperature change were observed despite identical variations of the metal's permittivity.

Electronically controlled surface plasmon dispersion and optical transmission through metallic hole arrays using liquid crystal.

The enhanced optical properties of metal films periodically perforated with an array of sub-wavelength size holes have recently been widely studied in the field of surface plasmon optics. The ability to design the optical transmission of such nanostructures, which act as plasmonic crystals, by varying their geometrical parameters gives them great flexibility for numerous applications in photonics, opto-electronics, and sensing. Transforming these passive optical elements into devices that may be actively controlled has presented a new challenge. Here, we report on the realization of an electrically controlled nanostructured optical system based on the unique properties of surface plasmon polaritonic crystals in contact with a liquid crystal (LC) layer. We discuss the effect of LC layer modulation on the surface plasmon dispersion, the related optical transmission and the underlying mechanism. The reported effect may be used to achieve active spectral tuneability and switching in a wide range of applications.

Molecular plasmonics with tunable exciton-plasmon coupling strength in J-aggregate hybridized Au nanorod assemblies.

Controlling coherent electromagnetic interactions in molecular systems is a problem of both fundamental interest and important applicative potential in the development of photonic and opto-electronic devices. The strength of these interactions determines both the absorption and emission properties of molecules coupled to nanostructures, effectively governing the optical properties of such a composite metamaterial. Here we report on the observation of strong coupling between a plasmon supported by an assembly of oriented gold nanorods (ANR) and a molecular exciton. We show that the coupling is easily engineered and is deterministic as both spatial and spectral overlap between the plasmonic structure and molecular aggregates are controlled. We think that these results in conjunction with the flexible geometry of the ANR are of potential significance to the development of plasmonic molecular devices.

J-aggregates on metal nanoparticles characterized through ultrafast spectroscopy and near-field optics.

Illumination of metal nanoparticles at the plasmon resonance produces enhanced evanescent fields on the nanoparticles' surfaces. The unusual strength of the field makes it a target for exploring photoinduced phenomena at the nanoscale, if efficient functionalization or coating of the nanoparticle surface with appropriate chromophores is possible. One direction is to use cyanine dyes that form monolayers of J-aggregates on the surface of noble metal nanoparticle colloids. The unique, collective electronic properties of J-aggregates produce excitons with enormous extinction coefficients that are of interest for their efficient energy transfer, electron transfer, and nonlinear optical properties. In that vein, we report our results on time-resolved spectroscopy and near-field scanning optical microscopy (NSOM) of J-aggregate exciton dynamics on Ag and Au nanoparticle colloids. Ultrafast transient absorption studies show that J-aggregate exciton lifetimes on Ag nanoparticles are much longer than on Au nanoparticles, with a 300 ps lifetime that is two orders of magnitude longer than the electronic processes in the nanoparticles themselves. Complementary NSOM studies of the colloids show that fluorescence from the J-aggregates on the Ag nanoparticles is induced by the scanning probe. These results may be significant for improving the nanophotonic performance of hybrid materials for nanoscale applications.