Engineering copper plasmonic chirality via ligand-induced dissolution for enantioselective recognition of amino acids.

The formation of chiral nanosystems and their subsequent enantioselective interaction with chiral amino acids are vital steps in many biological processes. Due to their potential to mimic biological systems, the synthesis of chiral nanomaterials has garnered significant attention over the years. Despite the emergence of diverse nanomaterials showcasing strong chiral responses, the in-depth understanding of the mechanism of plasmonic chirality in copper nanoparticles and their subsequent application in various fields are least explored. Herein, we demonstrate a facile approach for the synthesis of chiral copper nanoparticles using cysteine as a chiral precursor and capping ligand. Ligand-mediated chiral induction, established through experimental findings and a theoretical model, is ascribed as the major contributor to the origin of plasmonic chirality. The enantioselective recognition of chiral copper nanoparticles towards histidine, an amino acid with vast biological functions, was meticulously investigated by leveraging the strong copper-histidine binding ability. Ligand-induced dissolution, a unique phenomenon in nanoparticle reactions, was identified as the underlying mechanism for the nanoparticle-to-complex conversion. Understanding the mechanism of chiral induction in copper nanoparticles coupled with their enantioselective recognition of biomolecules not only holds promise in biomedical research but also sheds light on their potential as catalysts for asymmetric synthesis.

Surfactant Directed Synthesis of Intrinsically Chiral Plasmonic Nanostructures and Precise Tuning of their Optical Activity through Controlled Self-Assembly.

Fabrication and transmission of plasmonic chirality is a rapidly developing area of research. While nanoscale chirality is reasonably well explored, research on intrinsically chiral nanostructures, that has ramifications to origin of homochirality, is still in its infancy. Herein, we report the synthesis of dog-bone shaped chiral gold nanostructures using a chiral cationic surfactant with excess ascorbic acid. Chiral growth is attributed to the specific binding and structure breaking ability of chiral surfactant and ascorbic acid. The controlled assembly of particles facilitated tuning and enhancement of chiral signals. Experimental observations were validated with theoretical simulations modelled in frequency domain with a surface integral-equation parameterization. Work highlighting the generation and tuning of plasmonic chirality provides new insights into the understanding of intrinsic chirality and paves way for their application in enantioselective catalysis and biosensing.

Integrating Plasmonic Supercrystals in Microfluidics for Ultrasensitive, Label-Free, and Selective Surface-Enhanced Raman Spectroscopy Detection.

Surface-enhanced Raman spectroscopy (SERS) microfluidic chips for label-free and ultrasensitive detection are fabricated by integrating a plasmonic supercrystal within microfluidic channels. This plasmonic platform allows the uniform infiltration of the analytes within the supercrystal, reaching the so-called hot spots. Moreover, state-of-the-art simulations performed using large-scale supercrystal models demonstrate that the excellent SERS response is due to the hierarchical nanoparticle organization, the interparticle separation (IPS), and the presence of supercrystal defects. Proof-of-concept experiments confirm the outstanding performance of the microfluidic chips for the ultradetection of (bio)molecules with no metal affinity. In fact, a limit of detection (LOD) as low as 10-19 M was reached for crystal violet. The SERS microfluidic chips show excellent sensitivity in the direct analysis of pyocyanin secreted by Pseudomonas aeruginosa grown in a liquid culture medium. Finally, the further integration of a silica-based column in the plasmonic microchip provides charge-selective SERS capabilities as demonstrated for a mixture of positively and negatively charged molecules.

Micelle-directed chiral seeded growth on anisotropic gold nanocrystals.

Surfactant-assisted seeded growth of metal nanoparticles (NPs) can be engineered to produce anisotropic gold nanocrystals with high chiroptical activity through the templating effect of chiral micelles formed in the presence of dissymmetric cosurfactants. Mixed micelles adsorb on gold nanorods, forming quasihelical patterns that direct seeded growth into NPs with pronounced morphological and optical handedness. Sharp chiral wrinkles lead to chiral plasmon modes with high dissymmetry factors (~0.20). Through variation of the dimensions of chiral wrinkles, the chiroptical properties can be tuned within the visible and near-infrared electromagnetic spectrum. The micelle-directed mechanism allows extension to other systems, such as the seeded growth of chiral platinum shells on gold nanorods. This approach provides a reproducible, simple, and scalable method toward the fabrication of NPs with high chiral optical activity.

Detection of amyloid fibrils in Parkinson's disease using plasmonic chirality.

Amyloid fibrils, which are closely associated with various neurodegenerative diseases, are the final products in many protein aggregation pathways. The identification of fibrils at low concentration is, therefore, pivotal in disease diagnosis and development of therapeutic strategies. We report a methodology for the specific identification of amyloid fibrils using chiroptical effects in plasmonic nanoparticles. The formation of amyloid fibrils based on α-synuclein was probed using gold nanorods, which showed no apparent interaction with monomeric proteins but effective adsorption onto fibril structures via noncovalent interactions. The amyloid structure drives a helical nanorod arrangement, resulting in intense optical activity at the surface plasmon resonance wavelengths. This sensing technique was successfully applied to human brain homogenates of patients affected by Parkinson's disease, wherein protein fibrils related to the disease were identified through chiral signals from Au nanorods in the visible and near IR, whereas healthy brain samples did not exhibit any meaningful optical activity. The technique was additionally extended to the specific detection of infectious amyloids formed by prion proteins, thereby confirming the wide potential of the technique. The intense chiral response driven by strong dipolar coupling in helical Au nanorod arrangements allowed us to detect amyloid fibrils down to nanomolar concentrations.

Reversible Clustering of Gold Nanoparticles under Confinement.

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.

Fast and accurate electromagnetic solutions of finite periodic optical structures.

Electromagnetic applications of periodic materials have become popular in many modern optical and RF applications. The accurate computation of the electromagnetic response of large structures requires solving problems with high number of unknowns. Fast methods are useful to deal with such big problems, but, in general they do not take advantage of the periodicity properties. Based on the behaviour of impedance matrices involved in the solution of the surface integral equations with the Method of Moments, an accelerated solution based on the FFT is implemented. The presented approach slots the original impedance matrix and it applies the FFT to calculate the exact solution of the matrix vector product in an iterative process. The proposed solution achieves a linear memory cost proportional to 𝒪(N) and a computing time of 𝒪(N log N), where N is the problem number of unknowns. Also, in this paper, the advantages of this technique are shown in the developed applications.

Optimization of Nanoparticle-Based SERS Substrates through Large-Scale Realistic Simulations.

Surface-enhanced Raman scattering (SERS) has become a widely used spectroscopic technique for chemical identification, providing unbeaten sensitivity down to the single-molecule level. The amplification of the optical near field produced by collective electron excitations -plasmons- in nanostructured metal surfaces gives rise to a dramatic increase by many orders of magnitude in the Raman scattering intensities from neighboring molecules. This effect strongly depends on the detailed geometry and composition of the plasmon-supporting metallic structures. However, the search for optimized SERS substrates has largely relied on empirical data, due in part to the complexity of the structures, whose simulation becomes prohibitively demanding. In this work, we use state-of-the-art electromagnetic computation techniques to produce predictive simulations for a wide range of nanoparticle-based SERS substrates, including realistic configurations consisting of random arrangements of hundreds of nanoparticles with various morphologies. This allows us to derive rules of thumb for the influence of particle anisotropy and substrate coverage on the obtained SERS enhancement and optimum spectral ranges of operation. Our results provide a solid background to understand and design optimized SERS substrates.

Gold Nanorod-pNIPAM Hybrids with Reversible Plasmon Coupling: Synthesis, Modeling, and SERS Properties.

The thermoresponsive optical properties of Au nanorod-doped poly(N-isopropylacrylamide) (Au NR-pNIPAM) microgels with different Au NR payloads and aspect ratios are presented. Since the volume phase transition of pure pNIPAM microgels is reversible, the optical response reversibility of Au NR-pNIPAM hybrids is systematically analyzed. Besides, extinction cross-section and near-field enhancement simulations for Au NR-microgel hybrids are performed using a new numerical method based on the surface integral equation method of moments formulation (M3 solver). Additionally, the Au NR-microgel hybrid systems are expected to serve as excellent broadband surface-enhanced Raman scattering (SERS) substrates due to the temperature-controlled formation of hot spots and the tunable optical properties. The optical enhancing properties related to SERS are tested with three laser lines, evidencing excitation wavelength-dependent efficiency that can be easily controlled by either the aspect ratio (length/width) of the assembled Au NR or by the Au NR payload per microgel. Finally, the SERS efficiency of the prepared Au NR-pNIPAM hybrids is found to be stable for months.

Radial growth of plasmon coupled gold nanowires on colloidal templates.

The library of plasmonic nanosystems keeps expanding with novel structures with the potential to provide new solutions to old problems in science and technology. We report the synthesis of a novel plasmonic system based on the growth of gold nanowires radially branching from the surface of silica particles. The nanowires length could be controlled by tuning the molar ratio between metal salt and surface-grafted seeds. Electron microscopy characterization revealed that the obtained one-dimensional nanoparticles are polycrystalline but uniformly distributed on the spherical template. The length of the nanowires in turn determines the optical response of the metallodielectric particles, so that longer wires display red-shifted longitudinal plasmon bands. Accurate theoretical modeling of these complex objects revealed that the densely organized nanowires display intrinsically coupled plasmon modes that can be selectively decoupled upon detachment of the nanowires from the surface of the colloidal silica template.

Collective Plasmonic Properties in Few-Layer Gold Nanorod Supercrystals.

Gold nanorod supercrystals have been widely employed for the detection of relevant bioanalytes with detection limits ranging from nano- to picomolar levels, confirming the promising nature of these structures for biosensing. Even though a relationship between the height of the supercrystal (i.e., the number of stacked nanorod layers) and the enhancement factor has been proposed, no systematic study has been reported. In order to tackle this problem, we prepared gold nanorod supercrystals with varying numbers of stacked layers and analyzed them extensively by atomic force microscopy, electron microscopy and surface enhanced Raman scattering. The experimental results were compared to numerical simulations performed on real-size supercrystals composed of thousands of nanorod building blocks. Analysis of the hot spot distribution in the simulated supercrystals showed the presence of standing waves that were distributed at different depths, depending on the number of layers in each supercrystal. On the basis of these theoretical results, we interpreted the experimental data in terms of analyte penetration into the topmost layer only, which indicates that diffusion to the interior of the supercrystals would be crucial if the complete field enhancement produced by the stacked nanorods is to be exploited. We propose that our conclusions will be of high relevance in the design of next generation plasmonic devices.

Toward ultimate nanoplasmonics modeling.

Advances in the field of nanoplasmonics are hindered by the limited capabilities of simulation tools in dealing with realistic systems comprising regions that extend over many light wavelengths. We show that the optical response of unprecedentedly large systems can be accurately calculated by using a combination of surface integral equation (SIE) method of moments (MoM) formulation and an expansion of the electromagnetic fields in a suitable set of spatial wave functions via fast multipole methods. We start with a critical review of volume versus surface integral methods, followed by a short tutorial on the key features that render plasmons useful for sensing (field enhancement and confinement). We then use the SIE-MoM to examine the plasmonic and sensing capabilities of various systems with increasing degrees of complexity, including both individual and interacting gold nanorods and nanostars, as well as large random and periodic arrangements of ∼1000 gold nanorods. We believe that the present results and methodology raise the standard of numerical electromagnetic simulations in the field of nanoplasmonics to a new level, which can be beneficial for the design of advanced nanophotonic devices and optical sensing structures.

Optimization of an optical wireless nanolink using directive nanoantennas.

Optical connects will become a key point in the next generation of integrated circuits, namely the upcoming nanoscale optical chips. In this context, nano-optical wireless links using nanoantennas have been presented as a promising alternative to regular plasmonic waveguide links, whose main limitation is the range propagation due to the metal absorption losses. In this paper we present the complete design of a high-capability wireless nanolink using matched directive nanoantennas. It will be shown how the use of directive nanoantennas clearly enhances the capability of the link, improving its behavior with respect to non-directive nanoantennas and largely outperforming regular plasmonic waveguide connects.