Plasmonic Nanoplatforms for Biochemical Sensing and Medical Applications

Plasmonics, the science of the excitation of surface plasmon polaritons (SPP) at the metal-dielectric interface under intense beam radiation, has been studied for its immense potential for developing numerous nanophotonic devices, optical circuits and lab-on-a-chip devices. The key feature, which makes the plasmonic structures promising is the ability to support strong resonances with different behaviors and tunable localized hotspots, excitable in a wide spectral range. Therefore, the fundamental understanding of light-matter interactions at subwavelength nanostructures and use of this understanding to tailor plasmonic nanostructures with the ability to sustain high-quality tunable resonant modes are essential toward the realization of highly functional devices with a wide range of applications from sensing to switching. We investigated the excitation of various plasmonic resonance modes (i.e. Fano resonances, and toroidal moments) using both optical and terahertz (THz) plasmonic metamolecules. By designing and fabricating various nanostructures, we successfully predicted, demonstrated and analyzed the excitation of plasmonic resonances, numerically and experimentally. A simple comparison between the sensitivity and lineshape quality of various optically driven resonances reveals that nonradiative toroidal moments are exotic plasmonic modes with strong sensitivity to environmental perturbations. Employing toroidal plasmonic metasurfaces, we demonstrated ultrafast plasmonic switches and highly sensitive sensors. Focusing on the biomedical applications of toroidal moments, we developed plasmonic metamaterials for fast and cost-effective infection diagnosis using the THz range of the spectrum. We used the exotic behavior of toroidal moments for the identification of Zika-virus (ZIKV) envelope proteins as the infectious nano-agents through two protocols: 1) direct biding of targeted biomarkers to the plasmonic metasurfaces, and 2) attaching gold nanoparticles to the plasmonic metasurfaces and binding the proteins to the particles to enhance the sensitivity. This led to developing ultrasensitive THz plasmonic metasensors for detection of nanoscale and low-molecular-weight biomarkers at the picomolar range of concentration. In summary, by using high-quality and pronounced toroidal moments as sensitive resonances, we have successfully designed, fabricated and characterized novel plasmonic toroidal metamaterials for the detection of infectious biomarkers using different methods. The proposed approach allowed us to compare and analyze the binding properties, sensitivity, repeatability, and limit of detection of the metasensing device

Plasmonics and its Applications

Plasmonics is a rapidly developing field that combines fundamental research and applications ranging from areas such as physics to engineering, chemistry, biology, medicine, food sciences, and the environmental sciences. Plasmonics appeared in the 1950s with the discovery of surface plasmon polaritons. Plasmonics then went through a novel propulsion in the mid-1970s, when surface-enhanced Raman scattering was discovered. Nevertheless, it is in this last decade that a very significant explosion of plasmonics and its applications has occurred. Thus, this book provides a snapshot of the current advances in these various areas of plasmonics and its applications, such as engineering, sensing, surface-enhanced fluorescence, catalysis, and photovoltaic devices

Latest Advances in Nanoplasmonics and Use of New Tools for Plasmonic Characterization

Nanoplasmonics is an area that uses light to couple electrons in metals, and can break the diffraction limit for light confinement into subwavelength zones, allowing for strong field enhancements. In the last two decades, there has been a resurgence of this research topic and its applications. Thus, this Special Issue presents a collection of articles and reviews by international researchers and is devoted to the recent advances in and insights into this research topic, including plasmonic devices, plasmonic biosensing, plasmonic photocatalysis, plasmonic photovoltaics, surface-enhanced Raman scattering, and surface plasmon resonance spectroscopy

Present and future of surface-enhanced Raman scattering

The discovery of the enhancement of Raman scattering by molecules adsorbed on nanostructured metal surfaces is a landmark in the history of spectroscopic and analytical techniques. Significant experimental and theoretical effort has been directed toward understanding the surface-enhanced Raman scattering (SERS) effect and demonstrating its potential in various types of ultrasensitive sensing applications in a wide variety of fields. In the 45 years since its discovery, SERS has blossomed into a rich area of research and technology, but additional efforts are still needed before it can be routinely used analytically and in commercial products. In this Review, prominent authors from around the world joined together to summarize the state of the art in understanding and using SERS and to predict what can be expected in the near future in terms of research, applications, and technological development. This Review is dedicated to SERS pioneer and our coauthor, the late Prof. Richard Van Duyne, whom we lost during the preparation of this article

Micro-Resonators: The Quest for Superior Performance

Microelectromechanical resonators are no longer solely a subject of research in university and government labs; they have found a variety of applications at industrial scale, where their market is predicted to grow steadily. Nevertheless, many barriers to enhance their performance and further spread their application remain to be overcome. In this Special Issue, we will focus our attention to some of the persistent challenges of micro-/nano-resonators such as nonlinearity, temperature stability, acceleration sensitivity, limits of quality factor, and failure modes that require a more in-depth understanding of the physics of vibration at small scale. The goal is to seek innovative solutions that take advantage of unique material properties and original designs to push the performance of micro-resonators beyond what is conventionally achievable. Contributions from academia discussing less-known characteristics of micro-resonators and from industry depicting the challenges of large-scale implementation of resonators are encouraged with the hopes of further stimulating the growth of this field, which is rich with fascinating physics and challenging problems

Fabrication of Nano-Pattern Libraries and their Applications in Mode-Selective SERS

Patterned arrays of metallic nanostructures are commonly used in photonics, electronics, as well as functional materials and biotechnology because of their unique electronic and optical properties. Although great effort has been devoted to the development of nano-patterning techniques in the past decades, there are still existing challenges for nano-fabrication to achieve fine resolution and complex features over macroscopic areas in a reasonable time period. Herein, we devise two versatile patterning strategies, namely indentation colloidal lithography (ICL) and oblique colloidal lithography (OCL), for the stepwise patterning of planar substrates with numerous complex and unique designs. Those strategies combine colloidal self-assembly, imprint molding in conjunction with capillary force lithography and reactive ion etching, all of which are simple and straightforward. Hexagonal arrays of symmetric and nonconcentric gold features are fabricated on glass substrates with highly controllable geometric parameters. The width, size and asymmetry of each surface structure could be tuned down to the ~10 nm level while the scale of the patterned area could exceed 1 cm^(2). Moreover, our technique also leads to the ability to develop an enormous variety of patterns through stepwise amplification of feature types. In particular, some of the features are fabricated for the first time, including target-triangle, hexagram, hexagram-dot and triangle-dot. Distinctive surface plasmon resonance (SPR) properties, such as higher order surface plasmon modes and Fano resonances are both observed from our patterns, which would be highly desired forthe study of plasmonic coupling. In addition, we have demonstrated a surface orientation dependent Raman selectivity on two nano-structures for the first time. Molecular vibrations with opposite symmetries can be selectively enhanced on different substrates. As a demonstration, this property is applied to the odd-even effect of n-alkanethiol self-assembly monolayers (SAMs) on the gold surface. The alternative alternation of the intensity ratios of two vibration pairs have been shown by surface enhanced Raman spectroscopy (SERS) as a function of the number of carbon atoms. The results obtained exhibit high sensitivity and excellent agreement with previous publications

Plasmon-exciton coupling for signal amplification and biosensing : fundamentals and application

Surface plasmon resonance (SPR) is the collective oscillation of frequency-matched free-space photons and surface electrons at a metal/dielectric interface. Their inherent sensitivity to refractive index changes and ability to couple with exciton species and enhance light-matter interaction make them ideal candidates for low-concentration analyte detection compared to conventional biosensors. The use of metal nanostructures and nanomaterials to excite SPR represents the current state-of-the-art. However, the challenges associated with repeatable synthesis of uniform nanomaterials, complex nanostructure fabrication, low SPR generation efficiency and limited understanding of the mechanism of plasmon-exciton coupling for signal amplification have motivated the search for alternative architectures and procedures. The uniform and repeatable gold nanoslit (NS) and nanoledge (NL) array architectures offers a promising route towards addressing the above issues, and hence this research attempts to take advantage of these platforms to achieve efficient SPR generation and exciton coupling for biosensing applications. The overarching scope of this dissertation extends to the design, fabrication, and optimization of metal NS and NL structures for SPR generation and sensing applications. Emphasis is placed on investigating the mechanism of optical signal enhancement arising from plasmon-exciton coupling (PEC) with particular focus on (a) exploring the role of geometry and size of the nanostructures (b) examining the influence of SPR spectral mode overlap with exciton’s absorption and/or emission energies on the overall optical signal in a NS or NL system, and (c) investigating the analytical sensitivity and signal transduction of the PEC system to biomolecular interactions. The nanoimprinting technique based on soft lithography for NS fabrication, which is used in this work for NS array fabrication, required addressing a critical issue, namely PDMS diffusion into nanoscale patterns for high aspect ratio realization. This was mitigated by curing temperature variation and incubation time to achieve 50 nm-130 nm width NS arrays with an intense, broad spectral response that red-shifts and diminishes with increasing NS width. The 50 nm width structure exhibited ~57× optical enhancement when coupled with acridine orange, a fluorescence dye, whose absorption and emission spectra closely overlaps with plasmonic spectra. A sensitive assay for detecting DNA hybridization was generated using the interaction of the selected SARS-CoV-2 ssDNA and dsDNA with AO to trigger the metachromatic behaviour of the dye to produce a strong optical signal amplification on the formation of AO-ssDNA complex and a quenched signal upon hybridization to the complementary target DNA along with a blue shift in the fluorescence of AO-dsDNA. The SARS-CoV-2 DNA hybridization assay, based on the PEC exhibited 0.21 nM sensitivity to complementary strand target, distinguished 1-, 2-, and 3-base mismatched DNA targets, reusability of ~6 x with 96% signal recovery, stable for up to 10 days at room temperature. Regarding the NL sensing platform, the principle of the sensing mechanism is based on plasmon-mediated extraordinary optical transmission (EOT) whose wavelength red-shifts with increase in refractive index (RI) at near-metal surface. The NL plasmonic-based biosensor fabricated using a patented E-beam writing method exhibited ~ 384.08 nm/RIU sensitivity, limit of detection to cardiac troponin I (TnI) at 0.079 ng/mL, 0.084 ng/mL and 0.097 ng/mL in PBS buffer, human serum, and human blood, respectively. The direct measurement of TnI in whole human blood without any purification or sample preparation step highlights the significance of the sensing platform for point-of-care detection. Thus, this work innovates (a) a tunable SPR to meet the requirement for plasmon-exciton spectral overlap for optical signal amplification, (b) the mechanism of optical enhancements due to PEC in NS arrays, and (c) a new application of PEC in NS and EOT in NL for the sensitive detection of SARS-CoV-2 DNA hybridization and cardiovascular biomarker TnI in human blood, respectively. The enhanced light-matter interactions have a broader impact beyond healthcare to light harvesting for solar cells, heat generation for cancer therapy, and photocatalysis for nanoscale reactions like water splitting