Dordaneh Etezadi

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.

Infrared Plasmonic Biosensor for Real-Time and Label-Free Monitoring of Lipid Membranes

In this work, we present an infrared plasmonic biosensor for chemical-specific detection and monitoring of biomimetic lipid membranes in a label-free and real-time fashion. Lipid membranes constitute the primary biological interface mediating cell signaling and interaction with drugs and pathogens. By exploiting the plasmonic field enhancement in the vicinity of engineered and surface-modified nanoantennas, the proposed biosensor is able to capture the vibrational fingerprints of lipid molecules and monitor in real time the formation kinetics of planar biomimetic membranes in aqueous environments. Furthermore, we show that this plasmonic biosensor features high-field enhancement extending over tens of nanometers away from the surface, matching the size of typical bioassays while preserving high sensitivity.

Nanoplasmonic mid-infrared biosensor for in vitro protein secondary structure detection

Plasmonic nanoantennas offer new applications in mid-infrared (mid-IR) absorption spectroscopy with ultrasensitive detection of structural signatures of biomolecules, such as proteins, due to their strong resonant near-fields. The amide I fingerprint of a protein contains conformational information that is greatly important for understanding its function in health and disease. Here, we introduce a non-invasive, label-free mid-IR nanoantenna-array sensor for secondary structure identification of nanometer-thin protein layers in aqueous solution by resolving the content of plasmonically enhanced amide I signatures. We successfully detect random coil to cross β-sheet conformational changes associated with α-synuclein protein aggregation, a detrimental process in many neurodegenerative disorders. Notably, our experimental results demonstrate high conformational sensitivity by differentiating subtle secondary-structural variations in a native β-sheet protein monolayer from those of cross β-sheets, which are characteristic of pathological aggregates. Our nanoplasmonic biosensor is a highly promising and versatile tool for in vitro structural analysis of thin protein layers.

Theoretical and experimental analysis of subwavelength bowtie-shaped antennas

Recently, bowtie-shaped apertures have received significant attention due to their extraordinary ability to generate dramatic field enhancement and light confinement in nanometer scale. In this article, we investigate both experimentally and theoretically nearfield and farfield responses of bowtie-shaped apertures in detail. We study the role of bowtie gap in creating large and highly accessible local electromagnetic fields. In order to experimentally excite strong local fields, we introduce a high-resolution and lift-off free fabrication method which enables bowtie apertures with gap sizes down to sub-10 nm. We also show that for identical geometries, bowtie-shaped apertures support much stronger local electromagnetic fields compared to particle-based bowtie-shaped antennas. We investigate the role of polarization on the gap effect, which plays the dominant role for creating strong nearfield intensities. Finally, we introduce a mechanism to fine-tune the optical response of bowtie apertures through geometrical parameters.

Plasmonic nanohole arrays on Si-Ge heterostructures: an approach for integrated biosensors

Nanohole array surface plasmon resonance (SPR) sensors offer a promising platform for high-throughput label-free biosensing. Integrating nanohole arrays with group-IV semiconductor photodetectors could enable low-cost and disposable biosensors compatible to Si-based complementary metal oxide semiconductor (CMOS) technology that can be combined with integrated circuitry for continuous monitoring of biosamples and fast sensor data processing. Such an integrated biosensor could be realized by structuring a nanohole array in the contact metal layer of a photodetector. We used Fouriertransform infrared spectroscopy to investigate nanohole arrays in a 100 nm Al film deposited on top of a vertical Si-Ge photodiode structure grown by molecular beam epitaxy (MBE). We find that the presence of a protein bilayer, constitute of protein AG and Immunoglobulin G (IgG), leads to a wavelength-dependent absorptance enhancement of ~ 8 %.

Real-time in-situ secondary structure analysis of protein monolayer with mid-infrared plasmonic nanoantennas

Dynamic detection of protein conformational changes at physiological conditions on a minute amount of samples is immensely important for understanding the structural determinants of protein function in health and disease and to develop assays and diagnostics for protein misfolding and protein aggregation diseases. Herein, we experimentally demonstrate the capabilities of a mid-infrared plasmonic biosensor for real-time and in situ protein secondary structure analysis in aqueous environment at nanoscale. We present label-free ultrasensitive dynamic monitoring of β-sheet to disordered conformational transitions in a monolayer of the disease-related α-synuclein protein under varying stimulus conditions. Our experiments show that the extracted secondary structure signals from plasmonically enhanced amide I signatures in the protein monolayer can be reliably and reproducibly acquired with second derivative analysis for dynamic monitoring. Furthermore, by using a polymer layer we show that our nanoplasmonic approach of extracting the frequency components of vibrational signatures matches with the results attained from gold-standard infrared transmission measurements. By facilitating conformational analysis on small quantities of immobilized proteins in response to external stimuli such as drugs, our plasmonic biosensor could be used to introduce platforms for screening small molecule modulators of protein misfolding and aggregation.

Nanoimaging and Control of Molecular Vibrations through Electromagnetically Induced Scattering Reaching the Strong Coupling Regime

Optical resonators can enhance light–matter interaction, modify intrinsic molecular properties such as radiative emission rates, and create new molecule–photon hybrid quantum states. To date, corresponding implementations are based on electronic transitions in the visible spectral region with large transition dipoles yet hampered by fast femtosecond electronic dephasing. In contrast, coupling molecular vibrations with their weaker dipoles to infrared optical resonators has been less explored, despite long-lived coherences with 2 orders of magnitude longer dephasing times. Here, we achieve excitation of molecular vibrations through configurable optical interactions of a nanotip with an infrared resonant nanowire that supports tunable bright and nonradiative dark modes. The resulting antenna–vibrational coupling up to 47 ± 5 cm–1 exceeds the intrinsic dephasing rate of the molecular vibration, leading to hybridization and mode splitting. We observe nanotip-induced quantum interference of vibrational excitation pathways in spectroscopic nanoimaging, which we model classically as plasmonic electromagnetically induced scattering as the phase-controlled extension of the classical analogue of electromagnetically induced transparency and absorption. Our results present a new regime of IR spectroscopy for applications of vibrational coherence from quantum computing to optical control of chemical reactions.

Mid-infrared nanoplasmonics for label-free real-time biosensing of proteins and lipid membranes

We present our surface-engineered Mid-infrared plasmonic biosensor for real-time, label-free chemical-specific monitoring of biomimetic lipid membrane kinetics. Our experiments and simulations demonstrate high field enhancements with probing depth of tens of nanometers suitable for bioassays.

Graphene as enabling material for infrared plasmonic biosensors

We demonstrate a graphene infrared biosensor for chemical-specific label-free protein detection. Graphene plasmon resonances are dynamically tuned to enhance protein vibrational bands. We show that the extreme light confinement makes graphene plasmons extremely sensitive to nanometric molecules.

Accessible Field Enhancements with Plasmonic Nanoparticles on Nanopedestals for Nanospectroscopy

We show that plasmonic nanoparticle arrays on dielectric nanopedestals support easily accessible hot spots for target molecules, which is crucial for increasing signals in biosensors and vibrational nanospectroscopy.