Hatice Altug

Fano-resonant asymmetric metamaterials for ultrasensitive spectroscopy and identification of molecular monolayers

Engineered optical metamaterials present a unique platform for biosensing applications owing to their ability to confine light to nanoscale regions and to their spectral selectivity. Infrared plasmonic metamaterials are especially attractive because their resonant response can be accurately tuned to that of the vibrational modes of the target biomolecules. Here we introduce an infrared plasmonic surface based on a Fano-resonant asymmetric metamaterial exhibiting sharp resonances caused by the interference between subradiant and superradiant plasmonic resonances. Owing to the metamaterials asymmetry, the frequency of the subradiant resonance can be precisely determined and matched to the molecules vibrational fingerprints. A multipixel array of Fano-resonant asymmetric metamaterials is used as a platform for multispectral biosensing of nanometre-scale monolayers of recognition proteins and their surface orientation, as well as for detecting chemical binding of target antibodies to recognition proteins.

Ultra-sensitive vibrational spectroscopy of protein monolayers with plasmonic nanoantenna arrays

Infrared absorption spectroscopy enabling direct access to vibrational fingerprints of the molecular structure is a powerful method for functional studies of bio-molecules. Although the intrinsic absorption cross-sections of IR active modes of proteins are nearly 10 orders of magnitude larger than the corresponding Raman cross-sections, they are still small compared to that of fluorescence-label based methods. Here, we developed a new tool based on collective excitation of plasmonic nanoantenna arrays and demonstrated direct detection of vibrational signatures of single protein monolayers. We first tailored the geometry of individual nanoantennas to form resonant structures that match the molecular vibrational modes. The tailored nanoantennas are then arranged in such a way that their in-phase dipolar coupling leads to a collective excitation of the ensemble with strongly enhanced near fields. The combined collective and individual plasmonic responses of the antenna array play a critical role in attaining signal enhancement factors of 104–105. We achieved measurement of the vibrational spectra of proteins at zeptomole levels for the entire array, corresponding to only 145 molecules per antenna. The near-field nature of the plasmonic enhancement of the absorption signals is demonstrated with progressive loading of the nanoantennas with varying protein film thicknesses. Finally, an advanced model based on nonequilibrium Greens function formalism is introduced, which explains the observed Fano-type absorption line-shapes and tuning of the absorption strengths with the antenna resonance.

Mid-infrared plasmonic biosensing with graphene

Graphene-based biosensors The mid-infrared (mid-IR) range is particularly well suited for biosensing because it encompasses the molecular vibrations that identify the biochemical building blocks of life, such as proteins, lipids, and DNA. However, the resulting optical signal is extremely weak and often requires complex techniques to enhance the biological detection. Rodrigo et al. present a graphene-based biosensor that they dynamically tuned over a broad spectral range through electrical gating. The authors selectively probed protein molecules at different mid-IR frequencies using a single device. Science, this issue p. 165 Graphene provides a platform for a tunable plasmon-based biosensor. Infrared spectroscopy is the technique of choice for chemical identification of biomolecules through their vibrational fingerprints. However, infrared light interacts poorly with nanometric-size molecules. We exploit the unique electro-optical properties of graphene to demonstrate a high-sensitivity tunable plasmonic biosensor for chemically specific label-free detection of protein monolayers. The plasmon resonance of nanostructured graphene is dynamically tuned to selectively probe the protein at different frequencies and extract its complex refractive index. Additionally, the extreme spatial light confinement in graphene—up to two orders of magnitude higher than in metals—produces an unprecedentedly high overlap with nanometric biomolecules, enabling superior sensitivity in the detection of their refractive index and vibrational fingerprints. The combination of tunable spectral selectivity and enhanced sensitivity of graphene opens exciting prospects for biosensing.

Seeing protein monolayers with naked eye through plasmonic Fano resonances

We introduce an ultrasensitive label-free detection technique based on asymmetric Fano resonances in plasmonic nanoholes with far reaching implications for point-of-care diagnostics. By exploiting extraordinary light transmission phenomena through high-quality factor (Qsolution ∼ 200) subradiant dark modes, we experimentally demonstrate record high figures of merits (FOMs as high as 162) for intrinsic detection limits surpassing that of the gold standard prism coupled surface-plasmon sensors (Kretschmann configuration). Our experimental record high sensitivities are attributed to the nearly complete suppression of the radiative losses that are made possible by the high structural quality of the fabricated devices as well as the subradiant nature of the resonances. Steep dispersion of the plasmonic Fano resonance profiles in high-quality plasmonic sensors exhibit dramatic light intensity changes to the slightest perturbations within their local environment. As a spectacular demonstration of the extraordinary sensitivity and the quality of the fabricated biosensors, we show direct detection of a single monolayer of biomolecules with naked eye using these Fano resonances and the associated Wood’s anomalies. To fabricate high optical-quality sensors, we introduce a high-throughput lift-off free evaporation fabrication technique with extremely uniform and precisely controlled nanofeatures over large areas, leading to resonance line-widths comparable to that of the ideally uniform structures as confirmed by our time-domain simulations. The demonstrated label-free sensing platform offers unique opportunities for point-of-care diagnostics in resource poor settings by eliminating the need for fluorescent labeling and optical detection instrumentation (camera, spectrometer, etc.) as well as mechanical and light isolation.

An Optofluidic Nanoplasmonic Biosensor for Direct Detection of Live Viruses from Biological Media

Fast and sensitive virus detection techniques, which can be rapidly deployed at multiple sites, are essential to prevent and control future epidemics and bioterrorism threats. In this Letter, we demonstrate a label-free optofluidic nanoplasmonic sensor that can directly detect intact viruses from biological media at clinically relevant concentrations with little to no sample preparation. Our sensing platform is based on an extraordinary light transmission effect in plasmonic nanoholes and utilizes group-specific antibodies for highly divergent strains of rapidly evolving viruses. So far, the questions remain for the possible limitations of this technique for virus detection, as the penetration depths of the surface plasmon polaritons are comparable to the dimensions of the pathogens. Here, we demonstrate detection and recognition of small enveloped RNA viruses (vesicular stomatitis virus and pseudotyped Ebola) as well as large enveloped DNA viruses (vaccinia virus) within a dynamic range spanning 3 orders of magnitude. Our platform, by enabling high signal to noise measurements without any mechanical or optical isolation, opens up opportunities for detection of a broad range of pathogens in typical biology laboratory settings.

In-situ ultra-sensitive infrared absorption spectroscopy of biomolecule interactions in real time with plasmonic nanoantennas

Infrared absorption spectroscopy is a powerful biochemical analysis tool as it extracts detailed molecular structural information in a label-free fashion. Its molecular specificity renders the technique sensitive to the subtle conformational changes exhibited by proteins in response to a variety of stimuli. Yet, sensitivity limitations and the extremely strong absorption bands of liquid water severely limit infrared spectroscopy in performing kinetic measurements in biomolecules’ native, aqueous environments. Here we demonstrate a plasmonic chip-based technology that overcomes these challenges, enabling the in-situ monitoring of protein and nanoparticle interactions at high sensitivity in real time, even allowing the observation of minute volumes of water displacement during binding events. Our approach leverages the plasmonic enhancement of absorption bands in conjunction with a non-classical form of internal reflection. These features not only expand the reach of infrared spectroscopy to a new class of biological interactions but also additionally enable a unique chip-based technology.

Multispectral plasmon induced transparency in coupled meta-atoms.

We introduce an approach enabling construction of a scalable metamaterial media supporting multispectral plasmon induced transparency. The composite multilayered media consist of coupled meta-atoms with radiant and subradiant hybridized plasmonic modes interacting through the structural asymmetry. A perturbative model incorporating hybridization and mode coupling is introduced to explain the observed novel spectral features. The proposed scheme is demonstrated experimentally by developing a lift-off-free fabrication scheme that can automatically register multiple metamaterial layers in the transverse plane. This metamaterial which can simultaneously enhance nonlinear processes at multiple frequency domains could open up new possibilities in optical information processing.

Fano Resonant Ring/Disk Plasmonic Nanocavities on Conducting Substrates for Advanced Biosensing

By introducing a conducting metal layer underneath a Fano resonant asymmetric ring/disk plasmonic nanocavity system, we demonstrate that electromagnetic fields can be strongly enhanced. These large electromagnetic fields extending deep into the medium are highly accessible and increase the interaction volume of analytes and optical fields. As a result, we demonstrate high refractive index sensitivities as large as 648 nm/RIU. By exciting Fano resonances with much sharper spectral features, as narrow as 9 nm, we experimentally show high figure of merits as large as 72 and reliable detection of protein mono- and bilayers. Furthermore, the conducting substrate enables strong interaction between fundamental and higher order modes of the system by minor structural asymmetries. This is very advantageous for experimental realization of systems supporting resonances with well-defined Fano-like line shape without requiring challenging fabrication resolution. Exploiting conducting metallic substrates and the associated propagating surface plasmons at their interface could be extended to other Fano resonant cavity geometries for improved biosensing performance.

High-Throughput Nanofabrication of Infrared Plasmonic Nanoantenna Arrays for Vibrational Nanospectroscopy

The introduction of high-throughput and high-resolution nanofabrication techniques operating at low cost and low complexity is essential for the advancement of nanoplasmonic and nanophotonic fields. In this paper, we demonstrate a novel fabrication approach based on nanostencil lithography for high-throughput fabrication of engineered infrared plasmonic nanorod antenna arrays. The technique relying on deposition of materials through a shadow mask enables plasmonic substrates supporting spectrally sharp collective resonances. We show that reflectance spectra of these antenna arrays are comparable to that of arrays fabricated by electron beam lithography. We also show that nanostencils can be reused multiple times to fabricate a series of infrared nanoantenna arrays with identical optical responses. Finally, we demonstrate fabrication of plasmonic nanostructures in a variety of shapes with a single metal deposition step on different substrates, including nonconducting ones. Our approach, by enabling the reusability of the stencil and offering flexibility on the substrate choice and nanopattern design, could facilitate the transition of plasmonic technologies to the real-world applications.

Integrated nanoplasmonic-nanofluidic biosensors with targeted delivery of analytes

Performances of the biosensors are often limited by the depletion zones created around the sensing area which impede the effective analyte transport. To overcome this limitation, we propose and demonstrate a nanoplasmonic-nanofluidic sensor enabling targeted delivery of analytes to the sensor surface with dramatic improvements in mass transport efficiency. Our sensing platform is based on extraordinary light transmission effect in suspended plasmonic nanoholes. This scheme allows three-dimensional control of the fluidic flow by connecting separate layers of microfluidic channels through plasmonic/nanofluidic holes. To implement the proposed sensor platform, we also introduce a lift-off free nanofabrication method.