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Chiral plasmonic nanoparticles (and their assemblies) interact with biomolecules in a variety of different ways, resulting in distinct optical signatures when probed by circular dichroism spectroscopy. These systems show promise for biosensing applications and offer several advantages over achiral plasmonic systems. Arguably the most notable advantage is that chiral nanoparticles can differentiate between molecular enantiomers and can, therefore, act as sensors for enantiomeric purity. Furthermore, chiral nanoparticles can couple more effectively to chiral biomolecules in biological systems if they have a matching handedness, improving their effectiveness as biomedical agents. In this article, we review the different types of interactions that occur between chiral plasmonic nanoparticle systems and biomolecules, and discuss how circular dichroism spectroscopy can probe these interactions and inform how to optimize systems for biosensing and biomedical applications., (© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Surface-enhanced infrared absorption (SEIRA) leads to a largely improved detection of polar molecules, compared to standard infrared absorption. The enhancement principle is based on localized surface plasmon resonances of the substrate, which match the frequency of molecular vibrations in the analyte of interest. Therefore, in practical terms, the SEIRA sensor needs to be tailored to each specific analyte. We review SEIRA sensors based on metal plasmonics for the detection of biomolecules such as DNA, proteins, and lipids. We further focus this review on chemical SEIRA sensors, with potential applications in quality control, as well as on the improvement in sensor geometry that led to the development of multiresonant SEIRA substrates as sensors for multiple analytes. Finally, we give an introduction into the integration of SEIRA sensors with surface-enhanced Raman scattering (SERS).

Regulation of enzymes is highly relevant toward orchestrating cell-free and stepwise biotransformations, thereby maximizing their overall performance. Plasmonic nanomaterials offer a great opportunity to tune the functionality of enzymes through their remarkable optical properties. Localized surface plasmon resonances (LSPR) can be used to modify chemical transformations at the nanomaterial's surface, upon light irradiation. Incident light can promote energetic processes, which may be related to an increase of local temperature (photothermal effects) but also to effects triggered by generated hotspots or hot electrons (photoelectronic effects). As a consequence, light irradiation of the protein-nanomaterial interface affects enzyme functionality. To harness these effects to finely and remotely regulate enzyme activity, the physicochemical features of the nanomaterial, properties of the incident light, and parameters governing molecular interactions must be optimized. In this Perspective, we discuss relevant examples that illustrate the use of plasmonic nanoparticles to control enzyme function through LSPR excitation. Finally, we also highlight the importance of expanding the use of plasmonic nanomaterials to the immobilization of multienzyme systems for light-driven regulation of cell-free biosynthetic pathways. Although this concept is living its infancy, we encourage the scientific community to advance in the development of novel light-controlled biocatalytic plasmonic nanoconjugates and explore their application in biosensing, applied biocatalysis, and biomedicine.

Although metal nanoparticles with various shapes can be prepared in polar organic solvents, little has been advanced toward the shape-controlled synthesis in non-polar solvents. We report a simple method for the synthesis of nearly monodisperse single crystalline silver nanocubes in a non-polar solvent (1,2-dichlorobenzene) by using oleylamine as both a reducing and capping agent. Mechanistic studies based on the time evolution of Ag nanoparticles revealed that multiply twinned nanocrystals form at the beginning of the reaction, which are gradually transformed into single crystalline Ag nanocubes by oxidative etching. Control experiments showed that the solvent plays an important role in the formation of such single crystalline Ag nanocubes. The effects of reaction temperature, oleylamine concentration, solvent, and the nature of the silver ion precursor on the morphology and monodispersity of the nanoparticles were systematically investigated. Additionally, the galvanic replacement reaction with HAuCl4 in an organic medium was implemented to prepare hydrophobic hollow Au-Ag nanocages with tunable localized surface plasmon resonances.

The dependence of the spectral width of the longitudinal localized surface plasmon resonance (LSPR) of individual gold nanorods protected by a silica shell is investigated as a function of their size. Experiments were performed using the spatial modulation spectroscopy technique that permits determination of both the spectral characteristics of the LSPR of an individual nanoparticle and its morphology. The measured LSPR is shown to broaden with reduction of both the nanorod length and its diameter, which is in contrast with the predictions of existing classical and quantum theoretical models. This behavior can be reproduced assuming the LSPR width linearly depends on the inverse of an effective length proportional to the square root of the particle surface with the same slope as that recently determined for silica-coated silver nanospheres.

Plasmonic nanostructures have played a significant role in the field of nanotechnology due to their unprecedented ability to concentrate light at the nanometre scale, which renders them precious for various sensing applications. The adsorption of plasmonic nanoparticles and nanostructures onto solid substrates in a controlled manner is a crucial process for the fabrication of nanoplasmonic devices, in which the nanoparticles amplify the electromagnetic fields for enhanced device performance. In this perspective article we summarize recent developments in the fabrication of flexible nanoplasmonic devices for sensing applications based on surface enhanced Raman scattering (SERS) and localized surface plasmon resonance (LSPR) shifts. We introduce different types of flexible substrates such as filter paper, free-standing nanofibres, elastomers, plastics, carbon nanotubes and graphene, for the fabrication of low-cost flexible nanoplasmonic devices. Various techniques are described that allow impregnation of such flexible substrates with plasmonic nanoparticles, including solution processes, physical vapour deposition and lithographic techniques. From the discussion in this Perspective, it is clear that highly sensitive and reproducible flexible plasmonic devices can currently be fabricated on a large scale at relatively low-cost, toward real-world applications in diagnostics and detection.

Surface-enhanced Raman scattering (SERS) spectroscopy has been applied to detect the interaction of the FtsZ protein from Escherichia coli, an essential component of the bacterial division machinery, with either a soluble variant of the ZipA protein (that provides membrane tethering to FtsZ) or the bacterial membrane (containing the full-length ZipA naturally incorporated), on silver-coated polystyrene micrometer-sized beads. The engineered microbeads were used not only to support the bilayers but also to offer a stable support with a high density of SERS hot spots, allowing the detection of ZipA structural changes linked to the binding of FtsZ. These changes were different upon incubating the coated beads with FtsZ polymers (GTP form) as compared to oligomers (GDP form) and more pronounced when the plasmonic sensors were coated with natural bacterial membranes.

Coupling of localized surface plasmon resonances results in singular effects at the void space between noble metal nanoparticles. However, implementation of practical applications based on plasmon coupling calls for the high yield production of metal nanoparticle clusters (dimers, trimers, tetramers, …) with small gaps. Therefore, controlled assembly using colloid chemistry methods is an emerging and promising field. We present a brief overview over the controlled assembly of plasmonic nanoparticle clusters by colloid chemistry methods, together with a description of their plasmonic properties and some applications, with an emphasis in sensing through surface-enhanced Raman scattering spectroscopy for bio-detection purposes. We point out the important role of separation methods to obtain colloidal clusters in high yield. A special encouragement to explore assembly of anisotropic building blocks is pursued.

We present a theoretical and experimental study involving the sensing characteristics of wavelength-interrogated plasmonic sensors based on surface plasmon polaritons (SPP) in planar gold films and on localized surface plasmon resonances (LSPR) of single gold nanorods. The tunability of both sensing platforms allowed us to analyze their bulk and surface sensing characteristics as a function of the plasmon resonance position. We demonstrate that a general figure of merit (FOM), which is equivalent in wavelength and energy scales, can be employed to mutually compare both sensing schemes. Most interestingly, this FOM has revealed a spectral region for which the surface sensitivity performance of both sensor types is optimized, which we attribute to the intrinsic dielectric properties of plasmonic materials. Additionally, in good agreement with theoretical predictions, we experimentally demonstrate that, although the SPP sensor offers a much better bulk sensitivity, the LSPR sensor shows an approximately 15% better performance for surface sensitivity measurements when its FOM is optimized. However, optimization of the substrate refractive index and the accessibility of the relevant molecules to the nanoparticles can lead to a total 3-fold improvement of the FOM in LSPR sensors.

Chiral plasmonic nanoparticles (and their assemblies) interact with biomolecules in a variety of different ways, resulting in distinct optical signatures when probed by circular dichroism spectroscopy. These systems show promise for biosensing applications and offer several advantages over achiral plasmonic systems. Arguably the most notable advantage is that chiral nanoparticles can differentiate between molecular enantiomers and can, therefore, act as sensors for enantiomeric purity. Furthermore, chiral nanoparticles can couple more effectively to chiral biomolecules in biological systems if they have a matching handedness, improving their effectiveness as biomedical agents. In this article, we review the different types of interactions that occur between chiral plasmonic nanoparticle systems and biomolecules, and discuss how circular dichroism spectroscopy can probe these interactions and inform how to optimize systems for biosensing and biomedical applications. [ABSTRACT FROM AUTHOR]

Controlled assembly of gold nanoparticles (AuNPs) into clusters is a promising avenue for the development of sensitive bioimaging and diagnostic tools based on surface‐enhanced Raman scattering (SERS). However, several challenges, such as biocompatibility or colloidal and structural stability in biological environments, remain before AuNPs can be used as a tool for in vivo bioimaging. A versatile strategy for the preparation of colloidally stable and biocompatible AuNP clusters (AuNPCs) is introduced with high SERS signals, which are used as SERS contrast bioimaging agents (SERS tags). By tuning the ligand ratio of Raman reporter molecules to stabilizing polymer on the surface of each AuNP, aggregation can be carefully controlled. The resulting AuNPCs exhibit redshifted surface plasmon resonances in the near‐infrared (NIR) region, as well as distinct electromagnetic hotspots that give rise to SERS analytical enhancement factors above 104, compared to non‐clustered spherical AuNPs. Thanks to the protective polymer shell, high levels of cellular uptake with low cytotoxicity are observed, allowing 3D SERS mapping of cells with sufficiently high spatial resolution to detect AuNPCs within intracellular organelles. [ABSTRACT FROM AUTHOR]

Lattice plasmons, i.e., diffractively coupled localized surface plasmon resonances, occur in long‐range ordered plasmonic nanostructures such as 1D and 2D periodic lattices. Such far‐field coupled resonances can be employed for ultrasensitive surface‐enhanced Raman spectroscopy (SERS), provided they are spectrally matched to the excitation wavelength. The spectral positions of lattice plasmon modes critically depend on the lattice period and uniformity, owing to their pronounced sensitivity to structural disorder. We report the fabrication of superlattices by templated self‐assembly of gold nanoparticles on a flexible support, with tunable lattice‐plasmon resonances by means of macroscopic strain. We demonstrate that the highest SERS performance is achieved by matching the lattice plasmon mode to the excitation wavelength, by post‐assembly fine‐tuning of long‐range structural parameters. Both asymmetric and symmetric lattice deformations can be used to adapt a single lattice structure to both red‐shifted and blue‐shifted excitation lines, as exemplified by lattice expansion and contraction, respectively. This proof‐of‐principle study represents a basis for alternative designs of adaptive functional nanostructures with mechanically tunable lattice resonances using strain as a macroscopic control parameter. [ABSTRACT FROM AUTHOR]

From a geometrical perspective, a chiral object does not have mirror planes or inversion symmetry. It exhibits the same physical properties as its mirror image (enantiomer), except for the chiroptical activity, which is often the opposite. Recent advancements have identified particularly interesting implications of chirality on the optical properties of metal nanoparticles, which are intimately related to localized surface plasmon resonance phenomena. Although such resonances are usually independent of the circular polarization of light, specific strategies have been applied to induce chirality, both in assemblies and at the single-particle level. In this tutorial review, we discuss the origin of plasmonic chirality, as well as theoretical models that have been proposed to explain it. We then summarise recent developments in the synthesis of discrete nanoparticles with plasmonic chirality by means of wet-chemistry methods. We conclude with a discussion of promising applications for discrete chiral nanoparticles. We expect this tutorial review to be of interest to researchers from a wide variety of disciplines where chiral plasmonics can be exploited at the nanoparticle level, such as chemical sensing, photocatalysis, photodynamic or photothermal therapies, etc. [ABSTRACT FROM AUTHOR]

The influence of four substrates [thin Si3N4, few-layer graphene (FLG), thin h–BN, and monolayer h–BN] on plasmon resonances of metallic nanoparticles was studied using electron energy loss spectroscopy. The h–BN monolayer is an excellent substrate for the study of plasmonic particles due to its large bandgap, negligible charging under electron irradiation, and negligible influence on the plasmon resonance full width at half maximum and peak positions. These effects were evidenced in experiments with gold nanotriangles focusing on dipolar modes. Nanotriangles on h–BN exhibit the lowest influence from the substrate compared to Si3N4 and FLG. In a dataset containing 23 triangles of similar sizes, the dipolar mode was found to have smaller redshifts, sharper peak widths, and higher resonance quality factors on h–BN, showing that it has nearly no effect on the plasmon absorption properties, provided that it is free from carbon contamination. However, light emission (cathodoluminescence) decreases as a function of electron irradiation for triangles on h–BN, even though the electron energy loss signal stays unchanged. This indicates the creation of non-radiative decay channels. [ABSTRACT FROM AUTHOR]

Assemblies of plasmonic nanoparticles enable new modalities for biosensing. Engineered superstructures from metal nanoparticles can enhance the plasmon resonances and chiroptical activity of nanoscale dispersions. Such phenomena are keys to the fabrication of highly sensitive, selective and fast-responding detection platforms, making them promising candidates for clinical applications. This tutorial review summarizes and discusses recent advances in this area. The topics covered in the review include the basic strategies adopted for assembly and engineering of plasmonic nanoparticles, optical properties of the assembled nanostructures and their applications to both in vitro and in vivo detection of biological compounds. We also offer our vision of the future prospects of this field of research. Among emerging applications in this area are novel nanosensors and platforms, for food safety, environmental monitoring, health safeguarding, as well as biodefense. [ABSTRACT FROM AUTHOR]

Abstract: A limiting factor of solvent‐induced nanoparticle self‐assembly is the need for constant sample dilution in assembly/disassembly cycles. Changes in the nanoparticle concentration alter the kinetics of the subsequent assembly process, limiting optical signal recovery. Herein, we show that upon confining hydrophobic nanoparticles in permeable silica nanocapsules, the number of nanoparticles participating in cyclic aggregation remains constant despite bulk changes in solution, leading to highly reproducible plasmon band shifts at different solvent compositions. [ABSTRACT FROM AUTHOR]

Biofilm formation is facilitated by cell–cell communication processes known as quorum sensing, which enable collective behavior and metabolic coordination. Surface topography and chemistry play a significant role in bacterial adhesion and biofilm formation, yet methods for monitoring quorum sensing in situ suffer limitations. Herein we suggest the use of surface-enhanced Raman scattering to study the effects of surface topography and chemistry on quorum sensing signals involved in biofilm growth. [ABSTRACT FROM AUTHOR]

Methods for efficient detachment of cells avoiding damage are required in tissue engineering and regenerative medicine. We introduce a bottom-up approach to build plasmonic substrates using micellar block copolymer nanolithography to generate a 2D array of Au seeds, followed by chemical growth leading to anisotropic nanoparticles. The resulting plasmonic substrates show a broad plasmon band covering a wide part of the visible and near-infrared (NIR) spectral ranges. Both human and murine cells were successfully grown on the substrates. A simple functionalization step of the plasmonic substrates with the cyclic arginylglycylaspartic acid (c-RGD) peptide allowed us to tune the morphology of integrin-rich human umbilical vein endothelial cells (HUVEC). Subsequent irradiation with a NIR laser led to highly efficient detachment of the cells with cell viability confirmed using the MTT assay. We thus propose the use of such plasmonic substrates for cell growth and controlled detachment using remote near-IR irradiation, as a general method for cell culture in biomedical applications. [ABSTRACT FROM AUTHOR]

We report a robust and recyclable ‘dip-catalyst’ based on a gold nanoparticle (Au NP)-loaded filter paper composite, prepared by a simple dip-coating process using concentrated Au NP suspensions in toluene. While acting as catalysts, the composites display excellent surface enhanced Raman scattering (SERS) efficiency, allowing the real-time monitoring of chemical reactions. [ABSTRACT FROM AUTHOR]

Even after more than two decades of intense studies, the research on self‐assembly processes involving supramolecular interactions between nanoparticles (NPs) is continuously expanding. Plasmonic NPs have attracted particular attention due to strong optical, electrical, biological, and catalytic effects they are accompanied with. Surface plasmon resonance characteristics of plasmonic NPs and their assemblies enable fine‐tuning of these effects with unprecedented dynamic range. In turn, the uniquely high polarizability of plasmonic nanostructures and related optical effects exemplified by surface‐enhanced Raman scattering and red–blue color changes give rise to their application to biosensing. Since supramolecular interactions are ubiquitous in nature, scientists have found a spectrum of biomimetic properties of individual and assembled NPs that can be regulated by the layer of surface ligands coating all NPs. This paradigm has given rise to multiple studies from the design of molecular containers and enzyme‐like catalysts to chiroplasmonic assemblies. Computational and theoretical advances in plasmonic effects for geometrically complex structures have made possible the nanoscale engineering of NPs, assemblies, and supramolecular complexes with biomolecules. It is anticipated that further studies in this area will be expanded toward chiral catalysis, environmental monitoring, disease diagnosis, and therapy. [ABSTRACT FROM AUTHOR]

Learning from classics: Crystal growth is a complex process, and there are multiple paths for going from dissolved ions to solid crystals. Highlighted herein is the application of traditional chemistry concepts to new ways for increasing the complexity of nanocrystals while maintaining a high degree of symmetry. [ABSTRACT FROM AUTHOR]

The irradiation of gold nanorod colloids with a femtosecond laser can be tuned to induce controlled nanorod reshaping, yielding colloids with exceptionally narrow localized surface plasmon resonance bands. The process relies on a regime characterized by a gentle multishot reduction of the aspect ratio, whereas the rod shape and volume are barely affected. Successful reshaping can only occur within a narrow window of the heat dissipation rate: Low cooling rates lead to drastic morphological changes, and fast cooling has nearly no effect. Hence, a delicate balance must be achieved between irradiation fluence and surface density of the surfactant on the nanorods. This perfection process is appealing because it provides a simple, fast, reproducible, and scalable route toward gold nanorods with an optical response of exceptional quality, near the theoretical limit. [ABSTRACT FROM AUTHOR]

Abstract: Research on metal nanoparticles has been boosted by a wide variety of applications that often require a precise definition of the morphological features at the nanometer scale. Although the preparation (often based on colloid chemistry) of metal nanoparticles with many different shapes and sizes has been developed and optimized for spheres, rods, cubes, platelets and other shapes, the last few years have seen a rising interest in branched morphologies. This review article describes the main synthetic processes for the fabrication of such branched nanoparticles, often termed as nanostars, as well as some of the principal applications that have been found. A special emphasis is given to optical properties related to localized surface plasmon resonances and surface enhanced spectroscopies, for which nanostars have been predicted and demonstrated to shine brighter than any other shapes, thus opening new avenues for highly sensitive detection or biolabelling, among other applications. [Copyright &y& Elsevier]

Abstract: Silver nanoparticles prepared through a borohydride-reduction method were directly coated with silica by means of a seeded polymerization technique based on the Stöber method. Various amine catalysts were used for initialization of a sol–gel reaction of TEOS with no need for a prior surface modification. Use of dimethylamine (DMA) as a catalyst was found to be necessary to obtain a proper coating. The silica shell thickness was varied from 28 to 76 nm for TEOS concentrations of 1–15 mM at 11.1 M water and 0.8 M DMA. The optical spectra of the core–shell silver–silica composite particles show a qualitative agreement with predictions by Mie theory. [Copyright &y& Elsevier]

Gold nanoparticles prepared through a conventional citrate-reduction method were directly coated with silica by means of a seeded polymerization technique based on the Sto¨ber method. The method required no surface modification. The addition of tetraethylorthosilicate and water prior to ammonia was found to be critical to obtain a proper coating. The silica shell thickness was varied from 30 to 90 nm for TEOS concentrations of 0.0005–0.02 M at 10.9 M of water and 0.4 M of ammonia. The optical spectra of the core–shell gold–silica composite particles agreed with predictions of Mie theory. [Copyright &y& Elsevier]