Rapid Detection of Infectious Envelope Proteins by Magnetoplasmonic Toroidal Metasensors.

Unconventional characteristics of magnetic toroidal multipoles have triggered researchers to study these unique resonant phenomena by using both 3D and planar resonators under intense radiation. Here, going beyond conventional planar unit cells, we report on the observation of magnetic toroidal modes using artificially engineered multimetallic planar plasmonic resonators. The proposed microstructures consist of iron (Fe) and titanium (Ti) components acting as magnetic resonators and torus, respectively. Our numerical studies and following experimental verifications show that the proposed structures allow for excitation of toroidal dipoles in the terahertz (THz) domain with the experimental Q-factor of ∼18. Taking the advantage of high-Q toroidal line shape and its dependence on the environmental perturbations, we demonstrate that room-temperature toroidal metasurface is a reliable platform for immunosensing applications. As a proof of concept, we utilized our plasmonic metasurface to detect Zika-virus (ZIKV) envelope protein (with diameter of 40 nm) using a specific ZIKV antibody. The sharp toroidal resonant modes of the surface functionalized structures shift as a function of the ZIKV envelope protein for small concentrations (∼pM). The results of sensing experiments reveal rapid, accurate, and quantitative detection of envelope proteins with the limit of detection of ∼24.2 pg/mL and sensitivity of 6.47 GHz/log(pg/mL). We envision that the proposed toroidal metasurface opens new avenues for developing low-cost, and efficient THz plasmonic sensors for infection and targeted bioagent detection.

[1]  N I Zheludev,et al.  Electromagnetic toroidal excitations in matter and free space. , 2016, Nature materials.

[2]  M. Chin,et al.  Asymmetric Fano resonance and bistability for high extinction ratio, large modulation depth, and low power switching. , 2006, Optics express.

[3]  Hatice Altug,et al.  Fano resonant ring/disk plasmonic nanocavities on conducting substrates for advanced biosensing. , 2012, ACS nano.

[4]  W. Fan,et al.  Study of the interaction between graphene and planar terahertz metamaterial with toroidal dipolar resonance. , 2017, Optics letters.

[5]  D. Larkman,et al.  Microstructured magnetic materials for RF flux guides in magnetic resonance imaging. , 2001, Science.

[6]  Sang‐Hyun Oh,et al.  Engineering metallic nanostructures for plasmonics and nanophotonics , 2012, Reports on progress in physics. Physical Society.

[7]  Arash Ahmadivand,et al.  Transition from capacitive coupling to direct charge transfer in asymmetric terahertz plasmonic assemblies. , 2016, Optics letters.

[8]  Jeffrey N. Anker,et al.  Biosensing with plasmonic nanosensors. , 2008, Nature materials.

[9]  Willie J Padilla,et al.  Performance enhancement of terahertz metamaterials on ultrathin substrates for sensing applications , 2010 .

[10]  D. R. Chowdhury,et al.  Excitation of dark plasmonic modes in symmetry broken terahertz metamaterials. , 2014, Optics express.

[11]  R. Vorou Letter to the editor: diagnostic challenges to be considered regarding Zika virus in the context of the presence of the vector Aedes albopictus in Europe. , 2016, Euro surveillance : bulletin Europeen sur les maladies transmissibles = European communicable disease bulletin.

[12]  Arti Vashist,et al.  Electrochemical Biosensors for Early Stage Zika Diagnostics. , 2017, Trends in biotechnology.

[13]  G. N. Afanasiev,et al.  Electromagnetic properties of a toroidal solenoid , 1992 .

[14]  Y. Wang,et al.  Plasmon-induced transparency in metamaterials. , 2008, Physical review letters.

[15]  Pei Ding,et al.  Double Fano resonances due to interplay of electric and magnetic plasmon modes in planar plasmonic structure with high sensing sensitivity. , 2013, Optics express.

[16]  B. Fischer,et al.  Far-infrared vibrational modes of DNA components studied by terahertz time-domain spectroscopy , 2002, Physics in medicine and biology.

[17]  Jong-Gwan Yook,et al.  A planar split-ring resonator-based microwave biosensor for label-free detection of biomolecules , 2012 .

[18]  M. Jarrahi,et al.  Plasmonic photoconductive detectors for enhanced terahertz detection sensitivity. , 2013, Optics express.

[19]  Gennady Shvets,et al.  Fano-resonant asymmetric metamaterials for ultrasensitive spectroscopy and identification of molecular monolayers. , 2012, Nature materials.

[20]  R. J. Bell,et al.  Optical properties of Al, Fe, Ti, Ta, W, and Mo at submillimeter wavelengths. , 1988, Applied optics.

[21]  M. Orrit,et al.  Optical detection of single non-absorbing molecules using the surface plasmon resonance of a gold nanorod. , 2012, Nature nanotechnology.

[22]  N. Pala,et al.  Excitation of Terahertz Charge Transfer Plasmons in Metallic Fractal Structures , 2017 .

[23]  Ke Wu,et al.  Polarization-Independent Metamaterial Analog of Electromagnetically Induced Transparency for a Refractive-Index-Based Sensor , 2012, IEEE Transactions on Microwave Theory and Techniques.

[24]  Paul V. Braun,et al.  High Quality Factor Metallodielectric Hybrid Plasmonic–Photonic Crystals , 2010 .

[25]  M. Först,et al.  THz biosensing devices: fundamentals and technology , 2006 .

[26]  D. P. Tsai,et al.  Resonant Transparency and Non-Trivial Non-Radiating Excitations in Toroidal Metamaterials , 2013, Scientific Reports.

[27]  Ai Qun Liu,et al.  Switchable Magnetic Metamaterials Using Micromachining Processes , 2011, Advanced materials.

[28]  M. Takeda,et al.  Ultrafast optical control of group delay of narrow-band terahertz waves , 2014, Scientific Reports.

[29]  C. Soukoulis,et al.  Low-loss and high-Q planar metamaterial with toroidal moment , 2013 .

[30]  N. Pala,et al.  Tailoring the negative-refractive-index metamaterials composed of semiconductor-metal-semiconductor gold ring/disk cavity heptamers to support strong Fano resonances in the visible spectrum. , 2015, Journal of the Optical Society of America. A, Optics, image science, and vision.

[31]  V. M. Dubovik,et al.  Toroid moments in electrodynamics and solid-state physics , 1990 .

[32]  Benjamin Gallinet,et al.  Influence of electromagnetic interactions on the line shape of plasmonic Fano resonances. , 2011, ACS nano.

[33]  Changzhong Jiang,et al.  Magnetic Iron Oxide Nanoparticles: Synthesis and Surface Functionalization Strategies , 2009 .

[34]  Xi-Cheng Zhang,et al.  Terahertz biosensing technology: frontiers and progress. , 2002, Chemphyschem : a European journal of chemical physics and physical chemistry.

[35]  A. Ashkin,et al.  Optical trapping and manipulation of viruses and bacteria. , 1987, Science.

[36]  Nikolay I. Zheludev,et al.  Toroidal dipolar excitation and macroscopic electromagnetic properties of metamaterials , 2014 .

[37]  Boris N. Chichkov,et al.  Laser fabrication of large-scale nanoparticle arrays for sensing applications. , 2011, ACS nano.

[38]  J. M. Chamberlain,et al.  The interaction between Terahertz radiation and biological tissue. , 2001, Physics in medicine and biology.

[39]  Zhang Xi,et al.  Materials for terahertz science and technology , 2003 .

[40]  Naomi J. Halas,et al.  A plasmonic Fano switch. , 2012, Nano letters.

[41]  B. Xiao,et al.  The magnetic toroidal dipole in steric metamaterial for permittivity sensor application , 2013 .

[42]  Michael G. Mauk,et al.  Instrument-Free Point-of-Care Molecular Detection of Zika Virus , 2016, Analytical chemistry.

[43]  Audrey Berrier,et al.  Selective detection of bacterial layers with terahertz plasmonic antennas , 2012, Biomedical optics express.

[44]  S. J. Park,et al.  Detection of microorganisms using terahertz metamaterials , 2014, Scientific Reports.

[45]  A. Requicha,et al.  Plasmonics—A Route to Nanoscale Optical Devices , 2001 .

[46]  Yibin Ying,et al.  Gold Nanoparticle-Based Terahertz Metamaterial Sensors: Mechanisms and Applications , 2016 .

[47]  Lloyd A. Currie,et al.  Detection and quantification limits: origins and historical overview , 1997 .

[48]  N. Zheludev,et al.  From metamaterials to metadevices. , 2012, Nature materials.

[49]  X. Zhang,et al.  Enhanced sensing performance by the plasmonic analog of electromagnetically induced transparency in active metamaterials , 2010, 1101.0738.

[50]  A. E. Cetin,et al.  Seeing protein monolayers with naked eye through plasmonic Fano resonances , 2011, Proceedings of the National Academy of Sciences.

[51]  A. Miroshnichenko,et al.  Efficient excitation and tuning of toroidal dipoles within individual homogenous nanoparticles. , 2015, Optics express.

[52]  C. Keitel,et al.  Lorentz Meets Fano in Spectral Line Shapes: A Universal Phase and Its Laser Control , 2013, Science.

[53]  Derek Abbott,et al.  Label-free bioaffinity detection using terahertz technology. , 2002, Physics in medicine and biology.

[54]  Jochen Feldmann,et al.  Label-free biosensing based on single gold nanostars as plasmonic transducers. , 2010, ACS nano.

[55]  V. Kravets,et al.  Singular phase nano-optics in plasmonic metamaterials for label-free single-molecule detection. , 2013, Nature materials.

[56]  Manoj Gupta,et al.  Toroidal versus Fano Resonances in High Q planar THz Metamaterials , 2016 .

[57]  D. Musso,et al.  Detection of Zika virus in saliva. , 2015, Journal of clinical virology : the official publication of the Pan American Society for Clinical Virology.

[58]  S. Saxena,et al.  Zika virus outbreak: an overview of the experimental therapeutics and treatment , 2016, VirusDisease.