Plasmon-mediated photocatalytic conversion in Au or Ag nanorod aggregates by surface-enhanced Raman spectroscopy.

Plasmonic nanoparticles (NPs) hold considerable potential as photocatalysts owing to their robust light-matter interactions across diverse electromagnetic wavelengths, which significantly influence the photophysical characteristics of the adjacent molecular entities. Despite the widespread use of noble-metal NPs in surface-enhanced Raman scattering (SERS) applications, little is known about the kinetics of nanoparticle aggregation and how it affects their configurations. This study investigates the plasmon-driven photochemical conversion of 4-nitrobenzenethiol (NBT) to 4,4'-dimercaptoazobenzene (DMAB) on Au and Ag nanorods (NRs) through SERS. Significantly, photoconversion phenomena were observed on Ag NRs but not on Au NRs upon laser excitation at 633 nm. Finite-difference time-domain simulations revealed the presence of stronger electromagnetic fields on Ag NRs than on Au NRs. The aspect ratios and gaps between individual NPs in dimer configurations were determined to elucidate their effects on electromagnetic fields. The Ag NR dimer with an end-to-end configuration, an aspect ratio of 3.3, and a 1-nm gap exhibited the highest enhancement factor of 1.05 × 1012. Our results demonstrate that the primary contribution from diverse configurations in NR aggregates is the end-to-end configuration. The proposed NP design with adjustable parameters is expected to advance research in plasmonics, sensing, and wireless communications. These findings also contribute to the understanding of plasmon-driven photochemical processes in metallic nanostructures.

Unveiling Spatial and Temporal Dynamics of Plasmon-Enhanced Localized Fields in Metallic Nanoframes through Ultrafast Electron Microscopy.

Plasmonic nanomaterials, particularly noble metal nanoframes (NFs), are important for applications such as catalysis, biosensing, and energy harvesting due to their ability to enhance localized electric fields and atomic efficiency via localized surface plasmon resonance (LSPR). Yet the fundamental structure-function relationships and plasmonic dynamics of the NFS are difficult to study experimentally and thus far rely predominately on computational methodologies, limiting their utilization. This study leverages the capabilities of ultrafast electron microscopy (UEM), specifically photon-induced near-field electron microscopy (PINEM), to probe the light-matter interactions within plasmonic NF structures. The effects of shape, size, and plasmonic coupling of Pt@Au core-shell NFs on spatial and temporal characteristics of plasmon-enhanced localized electric fields are explored. Importantly, time-resolved PINEM analysis reveals that the plasmonic fields around hexagonal NF prisms exhibit a spatially dependent excitation and decay rate, indicating a nuanced interplay between the spatial geometry of the NF and the temporal evolution of the localized electric field. These results and observations uncover nanophotonic energy transfer dynamics in NFs and highlight their potential for applications in biosensing and photocatalysis.

Swiss roll nanoarrays for chiral plasmonic photocatalysis.

Manipulating the chirality at nanoscale has drawn great attention among scientists, considering its pivotal role in various applications of current interest, including nano-optics, biomedicine, and photocatalysis. In this work, we delve into this arena by fabricating chiral Swiss roll nanoarray (SRNA) continuous films employing colloidal lithography. The technique permits the dimension of Swiss roll metamaterials to reduce to nanoscale, thus achieving chiroptical response (circular dichroism (CD)) in the visible region. The interplay between the CD signals and plasmon resonance modes is revealed through theoretical simulations, enabling a deep understanding of chiral plasmonic metamaterials. The polarization-sensitive photocatalytic activity of chiral SRNAs is investigated, noting a marked increase in the reaction rate when the chirality of SRNAs matches with the handedness of circularly polarized light (CPL). Notably, the SRNA continuous films based on substrate possess integration and reusability without complex recycling process, enhancing their practicality in applications like sensing and plasmonic nanochemistry, particularly toward polarization-dependent photocatalysis.

Thermoplasmonic Effect Enables Indirect ON-OFF Control over the Z-E Isomerization of Azobenzene-Based Photoswitch.

Proper formulation of systems containing plasmonic and photochromic units, such as gold nanoparticles and azobenzene derivatives, yields materials and interfaces with synergic functionalities. Moreover, gold nanoparticles are known to accelerate the Z-E isomerization of azobenzene molecules in the dark. However, very little is known about the light-driven, plasmon-assisted Z-E isomerization of azobenzene compounds. Additionally, most of the azobenzene-gold hybrids are prepared with nanoparticles of small, isotropic shapes and azobenzene ligands covalently linked to the surface of nanostructures. Herein, a formulation of an innovative system combining azobenzene derivative, gold nanorods, and cellulose nanofibers is proposed. The system's structural integrity relies on electrostatic interactions among components instead of covalent linkage. Cellulose, a robust scaffold, maintains the material's functionality in water and enables monitoring of the material's plasmonic-photochromic properties upon irradiation and at elevated temperatures without gold nanorods aggregation. Experimental evidence supported by statistical analysis suggests that the optical properties of plasmonic nanometal enable indirect control over the Z-E isomerization of the photochromic component with near-infrared irradiation by triggering the thermoplasmonic effect. The proposed hybrid material's dual plasmonic-photochromic functionality, versatility, and ease of processing render a convenient starting point for further advanced azobenzene-related research and 3D printing of macroscopic light-responsive structures.

Plasmonic Particle Integration into Near-Infrared Photodetectors and Photoactivated Gas Sensors: Toward Sustainable Next-Generation Ubiquitous Sensing.

Current challenges in environmental science, medicine, food chemistry as well as the emerging use of artificial intelligence for solving problems in these fields require distributed, local sensing. Such ubiquitous sensing requires components with 1) high sensitivity, 2) power efficiency, 3) miniaturizability, and 4) the ability to directly interface with electronic circuitry, i.e., electronic readout of sensing signals. Over the recent years, several nanoparticle-based approaches have found their way into this field and have demonstrated high performance. However, challenges remain, such as the toxicity of many of today's narrow bandgap semiconductors for NIR detection and the high energy consumption as well as low selectivity of state-of-the-art commercialized gas sensors. With their unique light-matter interaction and ink-based fabrication schemes, plasmonic nanostructures provide potential technological solutions to these challenges, leading also to better environmental performance. In this perspective recent approaches of using plasmonic nanoparticles are discussed for the fabrication of NIR photodetectors and light-activated, energy-efficient gas sensing devices. In addition, new strategies implying computational approaches are pointed out for miniaturizable spectrometers, exploiting the wide spectral tunability of plasmonic nanocomposites, and for selective gas sensors, utilizing dynamic light activation. The benefits of colloidal approaches for device fabrication are discussed with regard to technological advantages and environmental aspects, which are barely considered so far.

Multispectral Molecular Chiral Barcoding.

More than half of pharmaceutical drugs in use are chiral, necessitating accurate techniques for their characterization. Enantiomers, molecules with mirrored symmetry, often exhibit similar physical traits but possess distinct chemical and biological implications. This study harnesses the strong light-matter interaction induced by "superchiral" light to perform Surface-Enhanced Infrared Absorption (SEIRA) induced vibrational circular dichroism measurements in the mid-infrared spectral region. Utilizing a nanopatterned pixelated array of achiral plasmonic nanostructures, the system allows unique identification of enantiomers and biomolecules. Tunability of plasmon resonance facilitates spectral variation of the optical chirality over a wide infrared range, enabling development of a unique chiral "barcoding" scheme to distinguish chiral molecules based on their infrared fingerprint. This simple, yet robust sensor presents a low-cost solution for chiral mapping of drugs and biomolecules.

A tunable narrow single-mode bandpass filter using graphene nanoribbons for THz applications.

This paper presents a tunable, single-mode narrowband optical filter designed for terahertz applications utilizing graphene nanoribbons. To attain optimal conditions, the filter was devised in three steps. It is composed of two input and output waveguides and a T-shaped resonator with nanoscale dimensions. The transmission spectrum analysis employs the three-dimensional finite difference time domain and coupled mode theory methods. Tunability is achieved through the adjustment of the nanoribbon size and the chemical potential of graphene. The filter demonstrates remarkable performance metrics, including a maximum transmission spectrum efficiency of 99%, a full width at half maximum (FWHM) of 0.115 THz, a quality factor (Q-factor) of 100, and a free spectral range (FSR) of 45 THz. The presented structure holds significant promise for integrated optical components and compact optical devices, showcasing its applicability in the terahertz frequency range. Furthermore, the inherent sensitivity of this structure to changes in the refractive index of the substrate positions it as a potential sensor.

Unraveling the Origin of Reverse Plasmonic Circular Dichroism from Discrete Bichiral Au Nanoparticles.

Bichiral plasmonic nanoparticles exhibited intriguing geometry-dependent circular dichroism (CD) reversal; however, the crucial factor that dominates the plasmonic CD is still unclear. Combined with CD spectroscopy and theoretical multipole analysis, we demonstrate that plasmonic CD originates from the excitation of electric quadrupolar plasmons. Moreover, a comparative study of two distinct quadrupolar modes reveals the correlation between the sign of the CD and the local geometric handedness at the plasmonic hotspots, thereby establishing a structure-property relationship in bichiral nanoparticles. The reverse CD is attributed to the opposite directions of the wavelength shift of the two plasmon modes upon changing the particle geometry. By finely tuning the size of bichiral nanoparticles, we can further reveal that the dependence of plasmonic CD on the electric quadrupolar plasmons. Our work sheds light on the physical origin of plasmonic CD and provides important guidelines for the design of chiral plasmonic nanoparticles toward chirality-dependent applications.

Infrared Spectroscopy of Live Cells Using High-Aspect-Ratio Metal-on-Dielectric Metasurfaces.

Fourier transform infrared (FTIR) spectroscopy is widely used for molecular analysis. However, for the materials situated in an aqueous environment, a precondition for live biological objects such as cells, transmission-based FTIR is prevented by strong water absorption of mid-infrared (MIR) light. Reflection-based cellular assays using internal reflection elements (IREs) such as high-index prisms or flat plasmonic metasurfaces mitigate these issues but suffer from a shallow probing volume localized near the plasma membrane. Inspired by the recent introduction of high-aspect-ratio nanostructures as a novel platform for manipulating cellular behavior, we demonstrate that the integration of plasmonic metasurfaces with tall dielectric nanostructures dramatically enhances the sensing capabilities of FTIR spectroscopy. We also demonstrate the ability of a metal-on-dielectric metasurface to transduce intracellular processes, such as protein translocation to high-curvature membrane regions during cell adhesion, into interpretable spectral signatures of the reflected light.

All-Optical Trapping and Programmable Transport of Gold Nanorods with Simultaneous Orientation and Spinning Control.

Gold nanorods (GNRs) are of special interest in nanotechnology and biomedical applications due to their biocompatibility, anisotropic shape, enhanced surface area, and tunable optical properties. The use of GNRs, for example, as sensors and mechanical actuators, relies on the ability to remotely control their orientation as well as their translational and rotational motion, whether individually or in groups. Achieving such particle control by using optical tools is challenging and exceeds the capabilities of conventional laser tweezers. We present a tool that addresses this complex manipulation problem by using a curve-shaped laser trap, enabling the optical capture and programmable transport of single and multiple GNRs along any trajectory. This type of laser trap combines confinement and propulsion optical forces with optical torque to transport the GNRs while simultaneously controlling their rotation (spinning) and orientation. The proposed system facilitates the light-driven control of GNRs and the quantitative characterization of their motion dynamics including transport speed, spinning frequency, orientation, and confinement strength. We experimentally demonstrate that remote control of the GNRs can be achieved both near a substrate surface (2D trapping) and deep within the sample (3D all-optical trapping). The motion dynamics of two sets of off-resonant GNRs, possessing similar aspect ratios but different resonance wavelengths, are analyzed to highlight the role played by their optical and mechanical properties in the optical manipulation process. The experimental results are supported by a theoretical model describing the observed motion dynamics of the GNRs. This optical manipulation tool can significantly facilitate applications of light-driven nanorods.

Transformative nanobioplasmonic effects: Toxicological implications of plasmonic silver nanoparticles in aquatic biological models.

Silver nanoparticles (AgNPs) present unique properties, such as the induced localized surface plasmon resonance (LSPR) provoked under illumination with a proper wavelength, allowing these nanomaterials to be applied in fields such as catalysis and biomedicine. The study of AgNPs is also highly relevant from the environmental pollution viewpoint due to their high production and application in commercial products. Consequently, AgNPs reach aquatic environments and can be plasmonically stimulated under natural light conditions. This study investigates the toxic effects promoted by AgNPs under plasmonic excitation on the survival and physiology of the crustacean Daphnia similis. Two AgNP shapes (spherical and triangular) with plasmon bands absorbing in different spectral regions in the visible range were studied. The organisms were exposed to different AgNP concentrations under five different light conditions. Survival and changes in enzymatic biomarkers of oxidative stress and lipid storage were evaluated. Under LSPR conditions, we observed increased lethality for both AgNP shapes. LSPR effects of AgNPs showed mortality 2.6 and 1.7 times higher than the treatment under dark conditions for spherical and triangular morphologies respectively. The enzymatic assays demonstrated that plasmonic treatments triggered physiological responses. Significantly decreased activities were observed exclusively under LSPR conditions for both AgNP shapes. Considering all treatments, spherical AgNPs showed lower LC50 values than triangular ones, indicating their higher toxic potential. Our results demonstrate that LSPR AgNPs can induce biological responses associated with oxidative stress and survival. Therefore, this study highlights the potential risks of environmental contamination by plasmonically active metallic nanomaterials. These materials can enhance their toxicity when light-excited, yet the results also indicate promising opportunities for light-based therapies.

Selective and Tunable Absorption of Twisted Light in Achiral and Chiral Plasmonic Metasurfaces.

The symmetry of achiral metasurfaces suggests selective absorption is nonexistent when irradiated either by circularly polarized Gaussian or twisted light beams carrying orbital angular momentum (OAM). In chiral metasurfaces, the lack of symmetry leads to differential absorption when probed with chiral light either in the form of circular polarization (circular dichroism) or helical phase fronts (helical dichroism). Here, we demonstrate differential absorption of asymmetric twisted light beams, known as helical dichroism, which exist in an array and a single achiral structure and can be controlled. When extended to chiral structures, these asymmetrical chiral light modes enable to enhance and tune chiroptical sensitivity. Our technique offers more control parameters than just changing the OAM value, as presented in previous studies. Selective response to asymmetric helical light beams is qualitatively explained in terms of induced multipole moments. The presence of dichroism in achiral nanostructures offers a significant fabrication advantage over complex chiral structures and enables the development of next-generation plasmonic-based chiroptical spectroscopy and molecular sensing.

A disposable fiber-optic plasmonic sensor for chemical sensing.

The integration of fiber optics and plasmonic sensors is promising to improve the practical usability over conventional bulky sensors and systems. To achieve high sensitivity, it typically requires fabrication of well-defined plasmonic nanostructures on optical fibers, which greatly increases the cost and complexity of the sensors. Here, we present a fiber-optic sensor system by using chemical absorption of gold nanoparticles and a replaceable configuration. By functioning gold nanoparticles with aptamers or antibodies, we demonstrate the applications in chemical sensing using two different modes. Measuring shift in resonance wavelength enables the Pb2+ detection with a high linearity and a limit of detection of 0.097 nM, and measuring absorption peak amplitude enables the detection of E. coli in urinary tract infection with a dynamic range between 103 to 108 CFU/mL. The high sensitivity, simple fabrication and disposability of this sensing approach could pave the way for point-of-care testing with fiber-optic plasmonic sensors.

Localized Plasmonic Structured Illumination Microscopy Using Hybrid Inverse Design.

Super-resolution fluorescence imaging has offered unprecedented insights and revolutionized our understanding of biology. In particular, localized plasmonic structured illumination microscopy (LPSIM) achieves video-rate super-resolution imaging with ∼50 nm spatial resolution by leveraging subdiffraction-limited nearfield patterns generated by plasmonic nanoantenna arrays. However, the conventional trial-and-error design process for LPSIM arrays is time-consuming and computationally intensive, limiting the exploration of optimal designs. Here, we propose a hybrid inverse design framework combining deep learning and genetic algorithms to refine LPSIM arrays. A population of designs is evaluated using a trained convolutional neural network, and a multiobjective optimization method optimizes them through iteration and evolution. Simulations demonstrate that the optimized LPSIM substrate surpasses traditional substrates, exhibiting higher reconstruction accuracy, robustness against noise, and increased tolerance for fewer measurements. This framework not only proves the efficacy of inverse design for tailoring LPSIM substrates but also opens avenues for exploring new plasmonic nanostructures in imaging applications.

Plasmonic-Enhanced Colorimetric Lateral Flow Immunoassays Using Bimetallic Silver-Coated Gold Nanostars.

The colorimetric lateral flow immunoassay (cLFIA) has gained widespread attention as a point-of-care testing (POCT) technique due to its low cost, short analysis time, portability, and capability of being performed by unskilled operators with minimal requirement of reagents. However, the low analytical sensitivity of conventional LFIA based on colloidal gold nanospheres limits their applications for sensitive detection of trace amounts of target analytes. In this study, we introduced a novel plasmonic-enhanced colorimetric LFIA (PE-cLFIA) platform featuring bimetallic silver-coated gold nanostars (BGNS) with exceptional optical properties, leading to ultrahigh visual color brightness. The BGNS-based PE-cLFIA was successfully applied to detect a model analyte, low-calcium response V (LcrV), a virulence protein factor found in Yersinia pestis, the causative agent of bubonic plague. The PE-cLFIA sensing using BGNS-3 composed of 45 nm silver thickness showed a high visual colorimetric sensitivity with a detection limit as low as 13.7 pg/mL, which was around 50 times more sensitive than that of a traditional gold nanoparticle-based LFIA. In addition, the antibody-conjugated BGNS-3 showed excellent stability over 6 months. To illustrate the potential for clinical applications, we demonstrated that our LFIA platform for detecting LcrV spiked in human serum without any sample preprocessing exhibited a detection limit of 22.8 pg/mL. These results open up new opportunities for developing hybrid nanoparticle systems for sensitive POCT PE-cLFIA screening for infectious disease detection.

Intraoperative assessment of microimplantation-induced acute brain inflammation with titanium oxynitride-based plasmonic biosensor.

Implantable devices for brain-machine interfaces and managing neurological disorders have experienced rapid growth in recent years. Although functional implants offer significant benefits, issues related to transient trauma and long-term biocompatibility and safety are of significant concern. Acute inflammatory reaction in the brain tissue caused by microimplants is known to be an issue but remains poorly studied. This study presents the use of titanium oxynitride (TiNO) nanofilm with defined surface plasmon resonance (SPR) properties for point-of-care characterizing of acute inflammatory responses during robot-controlled micro-neuro-implantation. By leveraging surface-enriched oxynitride, TiNO nanofilms can be biomolecular-functionalized through silanization. This label-free TiNO-SPR biosensor exhibits a high sensitivity toward the inflammatory cytokine interleukin-6 with a detection limit down to 6.3 fg ml-1 and a short assay time of 25 min. Additionally, intraoperative monitoring of acute inflammatory responses during microelectrode implantation in the mice brain has been accomplished using the TiNO-SPR biosensors. Through intraoperative cerebrospinal fluid sampling and point-of-care plasmonic biosensing, the rhythm of acute inflammatory responses induced by the robot-controlled brain microelectrodes implantation has been successfully depicted, offering insights into intraoperative safety assessment of invasive brain-machine interfaces.

Nanoplasmonic Rapid Antimicrobial-Resistance Point-of-Care Identification Device: RAPIDx.

The emergence of antibiotic resistance has become a global health crisis, and everyone must arm themselves with wisdom to effectively combat the "silent tsunami" of infections that are no longer treatable with antibiotics. However, the overuse or inappropriate use of unnecessary antibiotics is still routine for administering them due to the unavailability of rapid, precise, and point-of-care assays. Here, a rapid antimicrobial-resistance point-of-care identification device (RAPIDx) is reported for the accurate and simultaneous identification of bacterial species (genotype) and target enzyme activity (phenotype). First, a contamination-free active target enzyme is extracted via the photothermal lysis of preconcentrated bacteria cells on a nanoplasmonic functional layer on-chip. Second, the rapid, precise identification of pathogens is achieved by the photonic rolling circle amplification of DNA on a chip. Third, the simultaneous identification of bacterial species (genotype) and target enzyme activity (phenotype) is demonstrated within a sample-to-answer 45 min operation via the RAPIDx. It is believed that the RAPIDx will be a valuable method for solving the bottleneck of employing on-chip nanotechnology for antibiotic-resistant bioassay and other infectious diseases.

Potential of plasmonics and nanoscale light-matter interactions for the next generation of optical neural interfaces.

Within the realm of optical neural interfaces, the exploration of plasmonic resonances to interact with neural cells has captured increasing attention among the neuroscience community. The interplay of light with conduction electrons in nanometer-sized metallic nanostructures can induce plasmonic resonances, showcasing a versatile capability to both sense and trigger cellular events. We describe the perspective of generating propagating or localized surface plasmon polaritons on the tip of an optical neural implant, widening the possibility for neuroscience labs to explore the potential of plasmonic neural interfaces.

Broadband Enhancement of Magneto-Optical Effects in Hybrid Waveguide-Plasmonic Surfaces for Sensing.

Conventional magnetophotonic nanostructures typically function within narrow wavelength and incident angle ranges, where resonance is observed and magneto-optical (MO) effects are amplified. Expanding these operational ranges may allow for improved applications, including in (bio)sensing devices. In this study, we describe a hybrid magnetoplasmonic waveguide grating (HMPWG) in which the coupling of plasmonic resonances and waveguide modes leads to enhanced MO effects and sensitivity, according to full-wave electromagnetic simulations. High transverse magneto-optical Kerr effect (TMOKE) signals were observed for the full range of wavelengths and angles investigated, i.e., for θinc ≥ 1° and 500 nm ≤ λ ≤ 850 nm. As a proof-of-concept we verified that using the HMPWG nanostructure with an aqueous solution as superstrate one may obtain a sensitivity in variation of the refractive index unit (RIU) of S = 166°/RIU and S = 230 nm/RIU in angle and wavelength interrogation modes, respectively. Upon comparing with conventional magnetoplasmonic gratings, which only enable excitation of plasmonic resonances, we demonstrate that HMPWG nanostructures can be further optimized to reach not only high sensitivity but also high resolution in sensing and biosensing.

Polaritonic Chemistry Enabled by Non-Local Metasurfaces.

Vibrational strong coupling can modify chemical reaction pathways in unconventional ways. Thus far, Fabry-Perot cavities formed by pairs of facing mirrors have been mostly utilized to achieve vibrational strong coupling. In this study, we demonstrate the application of non-local metasurfaces that can sustain surface lattice resonances, enabling chemical reactions under vibrational strong coupling. We show that the solvolysis kinetics of para-nitrophenyl acetate can be accelerated by a factor of 2.7 by strong coupling to the carbonyl bond of the solvent and the solute with a surface lattice resonance. Our work introduces a new platform to investigate polaritonic chemical reactions. In contrast to Fabry-Perot cavities, metasurfaces define open optical cavities with single surfaces, which removes alignment hurdles, facilitating polaritonic chemistry across large areas.