Comparative SERS Activity of Homometallic and Bimetallic Core-Satellite Assemblies.

The fabrication of core-satellite (CS) assemblies offers a versatile strategy for tailoring the optical properties of plasmonic nanomaterials. In addition to key factors like size, shape, and spatial arrangement of individual components, the combination of plasmonic units with different compositions (e.g., gold and silver) has been demonstrated to produce materials with enhanced properties and functionalities applicable across a range of fields. Notably, several CS assembly variants have emerged as promising substrates for surface-enhanced Raman spectroscopy (SERS). In this study, we address a gap in the knowledge by conducting a systematic cross-comparison of the optical and SERS properties of highly bright homo- and bimetallic CS assemblies. We evaluated the SERS efficiencies of these different superstructures across various excitation wavelengths and supported our findings with numerical simulations. The insights gained from this study offer a valuable foundation for researchers seeking to select and optimize the most suitable CS assemblies for their given SERS application.

Eco-friendly and biocompatible gelatin plasmonic filters for UV-vis-NIR light.

The quest for environmentally sustainable materials spans many fields and applications including optical materials. Here, we present the development of light filters using a gelatin-based nanocomposite. Owing to the plasmonic properties of metallic nanoparticles (NPs), strong light-matter interactions, these filters can be customized across the UV-Visible-NIR spectrum. The filters are designed for modular use, allowing for the addition or removal of desired spectral ranges. Moreover, the nanocomposites are composed of biodegradable and biocompatible materials which highlight the intersection of chemistry and ecological awareness for the exploration of new eco-friendly alternatives. These plasmonic gelatin-based filters block light due to the Localized Surface Plasmon Resonance (LSPR) of the NPs and can be tailored to meet various requirements, akin to a diner selecting options from a menu. This approach is inspired by culinary techniques, and we anticipate it will stimulate further exploration of biomaterials for applications in optics, materials science or electronics.

Exploiting Oriented Field Projectors to Open Topological Gaps in Plasmonic Nanoparticle Arrays.

In the last years there have been multiple proposals in nanophotonics to mimic topological condensed matter systems. However, nanoparticles have degrees of freedom that atoms lack of, like dimensions or shape, which can be exploited to explore topology beyond electronics. Elongated nanoparticles can act like projectors of the electric field in the direction of the major axis. Then, by orienting them in an array the coupling between them can be tuned, allowing to open a gap in an otherwise gapless system. As a proof of the potential of the use of orientation of nanoparticles for topology, we study 1D chains of prolate spheroidal silver nanoparticles. We show that in these arrays spatial modulation of the polarization allows to open gaps, engineer hidden crystalline symmetries and to switch on/off or left/right edge states depending on the polarization of the incident electric field. This opens a path toward exploiting features of nanoparticles for topology to go beyond analogues of condensed matter systems.

Enhanced Photoacoustic Response by Synergistic Ag-Melanin Interplay at the Core of Ternary Biocompatible Hybrid Silica-Based Nanoparticles.

Photoacoustics (PA) is gaining increasing credit among biomolecular imaging methodologies by virtue of its poor invasiveness, deep penetration, high spatial resolution, and excellent endogenous contrast, without the use of any ionizing radiation. Recently, we disclosed the excellent PA response of a self-structured biocompatible nanoprobe, consisting of ternary hybrid nanoparticles with a silver core and a melanin component embedded into a silica matrix. Although preliminary evidence suggested a crucial role of the Ag sonophore and the melanin-containing nanoenvironment, whether and in what manner the PA response is controlled and affected by the self-structured hybrid nanosystems remained unclear. Because of their potential as multifunctional platforms for biomedical applications, a detailed investigation of the metal-polymer-matrix interplay underlying the PA response was undertaken to understand the physical and chemical factors determining the enhanced response and to optimize the architecture, composition, and performance of the nanoparticles for efficient imaging applications. Herein, we provide the evidence for a strong synergistic interaction between eumelanin and Ag which suggests an important role in the in situ-generated metal-organic interface. In particular, we show that a strict ratio between melanin and silver precursors and an accurate choice of metal nanoparticle dimension and the kind of metal are essential for achieving strong enhancements of the PA response. Systematic variation of the metal/melanin component is thus shown to offer the means of tuning the stability and intensity of the photoacoustic response for various biomedical and theranostic applications.

Optical Quantification of Metal Ions Using Plasmonic Nanostructured Microbeads Coated with Metal-Organic Frameworks and Ion-Selective Dyes.

Herein, we designed and synthesized a hybrid material comprising polystyrene submicrobeads coated with silver nanospheres. This material provides a dense collection of electromagnetic hot spots upon illumination with visible light. The subsequent coating with a metal-framework and the adsorption of bathocuproine on it yield an optical sensor for SERS that can specifically detect Cu(II) in a variety of aqueous samples at the ultratrace level. Detection limits with this method are superior to those of induced coupled plasma or atomic absorption and comparable with those obtained with induced coupled plasma coupled with a mass detector.

Yolk-Shell Nanostars@Metal Organic Frameworks as Molecular Sieves for Optical Sensing and Catalysis.

Hybrid composites between nanoparticles and metal organic frameworks (MOFs) have been described as optimal materials for a wide range of applications in optical sensing, drug delivery, pollutant removal or catalysis. These materials are usually core-shell single- or multi-nanoparticles, restricting the inorganic surface available for reaction. Here, we develop a method for the preparation of yolk-shells consisting in a plasmonic gold nanostar coated with MOF. This configuration shows more colloidal stability, can sieve different molecules based on their size or charge, seems to show some interesting synergy with gold for their application in photocatalysis and present strong optical activity to be used as SERS sensors.

Fast decomposed method to devise broadband polarization-conversion metasurface.

Designing a broadband, wide-angle, and high-efficient polarization converter with a simple geometry remains challenging. This work proposes a simple and computationally inexpensive method for devising broadband polarization conversion metasurfaces. We focus on a cross-shape configuration consisting of two bars of different lengths connected at the center. To design the metasurface, we decompose the system into two parts with two orthogonally polarized responses and calculate the response of each part separately. By selecting the parameters with a proper phase difference in the response between the two parts, we can determine the dimensions of the system. For designing broadband polarization conversion metasurfaces, we define a fitness function to optimize the bandwidth of the linear polarization conversion. Numerical results demonstrate that the proposed method can be used to design a metasurface that achieves a relative bandwidth of [Formula: see text] for converting linearly polarized waves into cross-polarized waves. Additionally, the average polarization conversion ratio of the designed metasurface is greater than [Formula: see text] over the frequency range of 10.9-28.5 GHz. This method significantly reduces the computational expense compared to the traditional method and can be easily extended to other complex structures and configurations.

Plasmonic Polarization Rotation in SERS Spectroscopy.

Surface-enhanced Raman optical activity (SEROA) has been extensively investigated due to its ability to directly probe stereochemistry and molecular structure. However, most works have focused on the Raman optical activity (ROA) effect arising from the chirality of the molecules on isotropic surfaces. Here, we propose a strategy for achieving a similar effect: i.e., a surface-enhanced Raman polarization rotation effect arising from the coupling of optically inactive molecules with the chiral plasmonic response of metasurfaces. This effect is due to the optically active response of metallic nanostructures and their interaction with molecules, which could extend the ROA potential to inactive molecules and be used to enhance the sensibility performances of surface-enhanced Raman spectroscopy. More importantly, this technique does not suffer from the heating issue present in traditional plasmonic-enhanced ROA techniques, as it does not rely on the chirality of the molecules.

Direct Modular Printing of Plasmonic Chemosensors.

Here, we present and implement a new approach for producing modular inkjet-printable surface-enhanced Raman scattering (SERS) chemosensors. These sensors, combined with a rapid large field-of-view imaging system allow for fast imaging of the chemical characteristics of a sample. The performance of these materials is illustrated by printing a pH sensor on paper and interrogating aqueous solutions at different pH values. Results show single-shot images exceeding 9 mm2 which are readily read out via SERS imaging.

Negative reflection of nanoscale-confined polaritons in a low-loss natural medium.

Negative reflection occurs when light is reflected toward the same side of the normal to the boundary from which it is incident. This exotic optical phenomenon is not only yet to be visualized in real space but also remains unexplored, both at the nanoscale and in natural media. Here, we directly visualize nanoscale-confined polaritons negatively reflecting on subwavelength mirrors fabricated in a low-loss van der Waals crystal. Our near-field nanoimaging results unveil an unconventional and broad tunability of both the polaritonic wavelength and direction of propagation upon negative reflection. On the basis of these findings, we introduce a device in nano-optics: a hyperbolic nanoresonator, in which hyperbolic polaritons with different momenta reflect back to a common point source, enhancing the intensity. These results pave way to realize nanophotonics in low-loss natural media, providing an efficient route to control nanolight, a key for future on-chip optical nanotechnologies.

Advances and Prospects in Topological Nanoparticle Photonics.

Topological nanophotonics is a new avenue for exploring nanoscale systems from visible to THz frequencies, with unprecedented control. By embracing their complexity and fully utilizing the properties that make them distinct from electronic systems, we aim to study new topological phenomena. In this Perspective, we summarize the current state of the field and highlight the use of nanoparticle systems for exploring topological phases beyond electronic analogues. We provide an overview of the tools needed to capture the radiative, retardative, and long-range properties of these systems. We discuss the application of dielectric and metallic nanoparticles in nonlinear systems and also provide an overview of the newly developed topic of topological insulator nanoparticles. We hope that a comprehensive understanding of topological nanoparticle photonic systems will allow us to exploit them to their full potential and explore new topological phenomena at very reduced dimensions.

Surface-Enhanced Raman Scattering (SERS) Spectroscopy for Sensing and Characterization of Exosomes in Cancer Diagnosis.

Exosomes are emerging as one of the most intriguing cancer biomarkers in modern oncology for early cancer diagnosis, prognosis and treatment monitoring. Concurrently, several nanoplasmonic methods have been applied and developed to tackle the challenging task of enabling the rapid, sensitive, affordable analysis of exosomes. In this review, we specifically focus our attention on the application of plasmonic devices exploiting surface-enhanced Raman spectroscopy (SERS) as the optosensing technique for the structural interrogation and characterization of the heterogeneous nature of exosomes. We summarized the current state-of-art of this field while illustrating the main strategic approaches and discuss their advantages and limitations.

Correction to Graphene Plasmon Cavities Made with Silicon Carbide.

[This corrects the article DOI: 10.1021/acsomega.7b00726.].

Plasmonic linear nanomotor using lateral optical forces.

Optical force is a powerful tool to actuate micromachines. Conventional approaches often require focusing and steering an incident laser beam, resulting in a bottleneck for the integration of the optically actuated machines. Here, we propose a linear nanomotor based on a plasmonic particle that generates, even when illuminated with a plane wave, a lateral optical force due to its directional side scattering. This force direction is determined by the orientation of the nanoparticle rather than a field gradient or propagation direction of the incident light. We demonstrate the arrangements of the particles allow controlling the lateral force distributions with the resolution beyond the diffraction limit, which can produce movements, as designed, of microobjects in which they are embedded without shaping and steering the laser beam. Our nanomotor to engineer the experienced force can open the door to a new class of micro/nanomechanical devices that can be entirely operated by light.

Experimental signature of a topological quantum dot.

Topological insulator nanoparticles (TINPs) host topologically protected Dirac surface states, just like their bulk counterparts. For TINPs of radius <100 nm, quantum confinement on the surface results in the discretization of the Dirac cone. This system of discrete energy levels is referred to as a topological quantum dot (TQD) with energy level spacing on the order of Terahertz (THz), which is tunable with material-type and particle size. The presence of these discretized energy levels in turn leads to a new electron-mediated phonon-light coupling in the THz range, and the resulting mode can be observed in the absorption cross-section of the TINPs. We present the first experimental evidence of this new quantum phenomenon in Bi2Te3 topological quantum dots, remarkably observed at room temperature.

Giant polarization anisotropic optical response from anodic aluminum oxide templates embedded with plasmonic metamaterials.

Plasmonic metamaterials enable extraordinary manipulation of key constitutive properties of light at a subwavelength scale and thus have attracted significant interest. Here, we report a simple and convenient nanofabrication method for a novel meta-device by glancing deposition of gold into anodic aluminum oxide templates on glass substrates. A methodology with the assistance of ellipsometric measurements to examine the anisotropy and optical activity properties is presented. A tunable polarization conversion in both transmission and reflection is demonstrated. Specifically, giant broadband circular dichroism for reflection at visible wavelengths is experimentally realized by oblique incidence, due to the extrinsic chirality resulting from the mutual orientation of the metamaterials and the incident beam. This work paves the way for practical applications for large-area, low-cost polarization modulators, polarization imaging, displays, and bio-sensing.

Boosting the analytical properties of gold nanostars by single particle confinement into yolk porous silica shells.

Herein we illustrate an effective protocol to boost the optical enhancing properties of gold nanostars. By coating single nanostars with a mesoporous silica layer of the appropriate size (yolk capsules), to localize them under optical microscopy, it is possible to enumerate single particles and design SERS quantitative methods with minute amounts of metallic particles.

Extraordinarily transparent compact metallic metamaterials.

The design of achromatic optical components requires materials with high transparency and low dispersion. We show that although metals are highly opaque, densely packed arrays of metallic nanoparticles can be more transparent to infrared radiation than dielectrics such as germanium, even when the arrays are over 75% metal by volume. Such arrays form effective dielectrics that are virtually dispersion-free over ultra-broadband ranges of wavelengths from microns up to millimeters or more. Furthermore, the local refractive indices may be tuned by altering the size, shape, and spacing of the nanoparticles, allowing the design of gradient-index lenses that guide and focus light on the microscale. The electric field is also strongly concentrated in the gaps between the metallic nanoparticles, and the simultaneous focusing and squeezing of the electric field produces strong 'doubly-enhanced' hotspots which could boost measurements made using infrared spectroscopy and other non-linear processes over a broad range of frequencies.

Symmetry-breaking induced magnetic Fano resonances in densely packed arrays of symmetric nanotrimers.

Due to unique properties and great design flexibilities, Fano resonances represent one of the most promising optical features mediated by metallic nanostructures, while the excitation of some Fano modes is impossible due to symmetry reasons. The aim of this work is to show that dense lattice arrangements can have a profound impact on the optical properties of nanostructures and, in particular, can enable the excitation of otherwise dark modes. Here, we demonstrate this concept using the example of rectangular arrays of symmetric trimers packed so densely that the coupling between neighbouring unit cells imposes a symmetry break, enabling the excitation of magnetic Fano resonances. We found that in experiments as well as in simulations, electric and magnetic Fano resonances can be simultaneously formed in cases where the inter-trimer distances are sufficiently small. By analysing the transition from an isolated trimer mode into a regime of strong near-field coupling, we show that by modifying the rectangular unit cell lengths due to the symmetry mismatch between lattice and trimer, two types of Fano resonances can be found, especially magnetic Fano resonances with loop-type magnetic field distributions within the centre of each trimer, which can be either enhanced or suppressed. In addition, the influence of the refractive index environment was measured, showing sensitivity values of approximately 300 nm/RIU. Our work provides fundamental insights into the interaction of the lattice and nanostructure response and paves the way towards the observation of novel optical excitations.

Compact Integration of TiO2 Nanoparticles into the Cross-Points of 3D Vertically Stacked Ag Nanowires for Plasmon-Enhanced Photocatalysis.

The compact integration of semiconductor TiO2 nanoparticles (NPs) into the 3D crossed region of stacked plasmonic Ag nanowires (NWs) enhanced the photocatalytic activities through synergistic effects between the strong localized surface plasmon resonance (LSPR) excitation at the 3D cross-points of the Ag NWs and the efficient hot electron transfer at the interface between the Ag NWs and the TiO2 NPs. This paper explored new hybrid nanostructures based on the selective assembly of TiO2 NPs onto 3D cross-points of vertically stacked Ag NWs. The assembled TiO2 NPs directly contacted the 3D Ag NWs; therefore, charge separation occurred efficiently at the interface between the Ag NWs and the TiO2 NPs. The composite nanomaterials exhibited high extinction across the ultraviolet-visible range, rendering the nanomaterials high-performance photocatalysts across the full (ultraviolet-visible) and the visible spectral regions. Theoretical simulations clearly revealed that the local plasmonic field was highly enhanced at the 3D crossed regions of the vertically stacked Ag NWs. A Raman spectroscopic analysis of probe dye molecules under photodegradation conditions clearly revealed that the nanogap in the 3D crossed region was crucial for facilitating plasmon-enhanced photocatalysis and plasmon-enhanced spectroscopy.