Nanoplastics Detected in Commercial Sea Salt.

People of all ages consume salt every day, but is it really just salt? Plastic nanoparticles [nanoplastics (NPs)] pose an increasing environmental threat and have begun to contaminate everyday salt in consumer goods. Herein, we developed a combined surface enhanced Raman scattering (SERS) and stimulated Raman scattering (SRS) approach that can realize the filtration, enrichment, and detection of NPs in commercial salt. The Au-loaded (50 nm) anodic alumina oxide substrate was used as the SERS substrate to explore the potential types of NP contaminants in salts. SRS was used to conduct imaging and quantify the presence of the NPs. SRS detection was successfully established through standard plastics, and NPs were identified through the match of the hydrocarbon group of the nanoparticles. Simultaneously, the NPs were quantified based on the high spatial resolution and rapid imaging of the SRS imaging platform. NPs in sea salts produced in Asia, Australasia, Europe, and the Atlantic were studied. We estimate that, depending on the location, an average person could be ingesting as many as 6 million NPs per year through the consumption of sea salt alone. The potential health hazards associated with NP ingestion should not be underestimated.

Dense Arrays of Nanohelices: Raman Scattering from Achiral Molecules Reveals the Near-Field Enhancements at Chiral Metasurfaces.

Against the background of the current healthcare and climate emergencies, surface enhanced Raman scattering (SERS) is becoming a highly topical technique for identifying and fingerprinting molecules, e.g., within viruses, bacteria, drugs, and atmospheric aerosols. Crucial for SERS is the need for substrates with strong and reproducible enhancements of the Raman signal over large areas and with a low fabrication cost. Here, dense arrays of plasmonic nanohelices (≈100 nm in length), which are of interest for many advanced nanophotonics applications, are investigated, and they are shown to present excellent SERS properties. As an illustration, two new ways to probe near-field enhancement generated with circular polarization at chiral metasurfaces are presented, first using the Raman spectra of achiral molecules (crystal violet) and second using a single, element-specific, achiral molecular vibrational mode (i.e., a single Raman peak). The nanohelices can be fabricated over large areas at a low cost and they provide strong, robust and uniform Raman enhancement. It is anticipated that these advanced materials will find broad applications in surface enhanced Raman spectroscopies and material science.

SERS-based antibiotic susceptibility testing: Towards point-of-care clinical diagnosis.

Emerging antibiotic resistant bacteria constitute one of the biggest threats to public health. Surface-enhanced Raman scattering (SERS) is highly promising for detecting such bacteria and for antibiotic susceptibility testing (AST). SERS is fast, non-destructive (can probe living cells) and it is technologically flexible (readily integrated with robotics and machine learning algorithms). However, in order to integrate into efficient point-of-care (PoC) devices and to effectively replace the current culture-based methods, it needs to overcome the challenges of reliability, cost and complexity. Recently, significant progress has been made with the emergence of both new questions and new promising directions of research and technological development. This article brings together insights from several representative SERS-based AST studies and approaches oriented towards clinical PoC biosensing. It aims to serve as a reference source that can guide progress towards PoC routines for identifying antibiotic resistant pathogens. In turn, such identification would help to trace the origin of sporadic infections, in order to prevent outbreaks and to design effective medical treatment and preventive procedures.

Second harmonic Rayleigh scattering optical activity of single Ag nanohelices in a liquid.

Determining the chirality of molecules and nanoparticles often relies on circular dichroism and optical rotation: two chiral optical (chiroptical) effects in the linear optical regime. Although these linear effects are weak compared to nonlinear chiroptical effects, they have the advantage of being measured in isotropic liquids - free from the complications of anisotropy. Recently, a nonlinear effect: hyper-Rayleigh scattering optical activity (HRS OA) has been shown to reliably distinguish between the two chiral forms of Ag nanohelices, suspended in isotropic liquids. However, this first demonstration of HRS OA also opened new questions. For instance, at a fundamental level, it is not clear what the role of interactions between nanoparticles is. Moreover, the influence of the ultrafast pulse chirp is unknown. Here, we demonstrate HRS OA from well below two Ag nanohelices in the illumination volume, precluding any interactions. Additionally, we performed the first measurements of HRS depolarization ratios in this system and find a value of ≈1. We also show that HRS is highly robust against the chirp of the ultrafast pulses. An important reason for the strong (down to single nanohelix) sensitivity of our experiments is the large chiroptical interaction at the fundamental frequency; this point is illustrated with two sets of numerical simulations of the electromagnetic near-fields. Our results highlight HRS OA as a highly sensitive experimental method for characterization of chiral solutions/suspensions, in tiny illumination volumes.

Correction: Surface-enhanced Raman spectroscopy for bioanalysis and diagnosis.

Correction for 'Surface-enhanced Raman spectroscopy for bioanalysis and diagnosis' by Muhammad Ali Tahir et al., Nanoscale, 2021, 13, 11593-11634, DOI: .

Surface-enhanced Raman spectroscopy for bioanalysis and diagnosis.

In recent years, bioanalytical surface-enhanced Raman spectroscopy (SERS) has blossomed into a fast-growing research area. Owing to its high sensitivity and outstanding multiplexing ability, SERS is an effective analytical technique that has excellent potential in bioanalysis and diagnosis, as demonstrated by its increasing applications in vivo. SERS allows the rapid detection of molecular species based on direct and indirect strategies. Because it benefits from the tunable surface properties of nanostructures, it finds a broad range of applications with clinical relevance, such as biological sensing, drug delivery and live cell imaging assays. Of particular interest are early-stage-cancer detection and the fast detection of pathogens. Here, we present a comprehensive survey of SERS-based assays, from basic considerations to bioanalytical applications. Our main focus is on SERS-based pathogen detection methods as point-of-care solutions for early bacterial infection detection and chronic disease diagnosis. Additionally, various promising in vivo applications of SERS are surveyed. Furthermore, we provide a brief outlook of recent endeavours and we discuss future prospects and limitations for SERS, as a reliable approach for rapid and sensitive bioanalysis and diagnosis.

Klarite as a label-free SERS-based assay: a promising approach for atmospheric bioaerosol detection.

Detecting atmospheric bioaerosols in a quantitative way is highly desirable for public health and safety. This work demonstrates that surface-enhanced Raman spectroscopy (SERS) is a simple and rapid analytical technique for the detection of atmospheric bioaerosols, on a Klarite substrate. For both simulated and ambient bioaerosols, this detection assay results in an increase in the enhancement factor of the Raman signal. We report a strong SERS signal generated by bioaerosols containing living Escherichia coli deposited on Klarite. Furthermore, we demonstrate that SERS mapping can be used to estimate the percentage of airborne, living Escherichia coli. Moreover, Klarite provides differently distinct SERS spectra at different bacterial growth phases, indicating its potential to identify changes occurring in the bacterial envelope. Finally, we applied SERS for the rapid detection of Escherichia coli in ambient bioaerosols without using time-consuming and laborious culture processes. Our results represent rapid, culture-free and label-free detection of airborne bacteria in the real-world environment.

Cu/Ag Sphere Segment Void Array as Efficient Surface Enhanced Raman Spectroscopy Substrate for Detecting Individual Atmospheric Aerosol.

Surface enhanced Raman spectroscopy (SERS) shows great promise in studying individual atmospheric aerosol. However, the lack of efficient, stable, uniform, large-array, and low-cost SERS substrates constitutes a major roadblock. Herein, a new SERS substrate is proposed for detecting individual atmospheric aerosol particles. It is based on the sphere segment void (SSV) structure of copper and silver (Cu/Ag) alloy. The SSV structure is prepared by an electrodeposition method and presents a uniform distribution, over large 2 cm2 arrays and at low cost. The substrate offers a high SERS enhancement factor (due to Ag) combined with lasting stability (due to Cu). The SSV structure of the arrays generates a high density of SERS hotspots (1.3 × 1014/cm2), making it an excellent substrate for atmospheric aerosol detection. For stimulated sulfate aerosols, the Raman signal is greatly enhanced (>50 times), an order of magnitude more than previously reported substrates for the same purpose. For ambient particles, collected and studied on a heavy haze day, the enhanced Raman signal allows ready observation of morphology and identification of chemical components, such as nitrates and sulfates. This work provides an efficient strategy for developing SERS substrate for detecting individual atmospheric aerosol.

Raman Techniques: Fundamentals and Frontiers.

Driven by applications in chemical sensing, biological imaging and material characterisation, Raman spectroscopies are attracting growing interest from a variety of scientific disciplines. The Raman effect originates from the inelastic scattering of light, and it can directly probe vibration/rotational-vibration states in molecules and materials. Despite numerous advantages over infrared spectroscopy, spontaneous Raman scattering is very weak, and consequently, a variety of enhanced Raman spectroscopic techniques have emerged. These techniques include stimulated Raman scattering and coherent anti-Stokes Raman scattering, as well as surface- and tip-enhanced Raman scattering spectroscopies. The present review provides the reader with an understanding of the fundamental physics that govern the Raman effect and its advantages, limitations and applications. The review also highlights the key experimental considerations for implementing the main experimental Raman spectroscopic techniques. The relevant data analysis methods and some of the most recent advances related to the Raman effect are finally presented. This review constitutes a practical introduction to the science of Raman spectroscopy; it also highlights recent and promising directions of future research developments.

Atomic dispensers for thermoplasmonic control of alkali vapor pressure in quantum optical applications.

Alkali metal vapors enable access to single electron systems, suitable for demonstrating fundamental light-matter interactions and promising for quantum logic operations, storage and sensing. However, progress is hampered by the need for robust and repeatable control over the atomic vapor density and over the associated optical depth. Until now, a moderate improvement of the optical depth was attainable through bulk heating or laser desorption - both time-consuming techniques. Here, we use plasmonic nanoparticles to convert light into localized thermal energy and to achieve optical depths in warm vapors, corresponding to a ~16 times increase in vapor pressure in less than 20 ms, with possible reload times much shorter than an hour. Our results enable robust and compact light-matter devices, such as efficient quantum memories and photon-photon logic gates, in which strong optical nonlinearities are crucial.

Excitation-Energy-Dependent Molecular Beacon Detects Early Stage Neurotoxic Aß Aggregates in the Presence of Cortical Neurons.

There is now crucial medical importance placed on understanding the role of early stage, subvisible protein aggregation, particularly in neurodegenerative disease. While there are strategies for detecting such aggregates in vitro, there is no approach at present that can detect these toxic species associated with cells and specific subcellular compartments. We have exploited excitation-energy-dependent fluorescence edge-shift of recombinant protein labeled with a molecular beacon, to provide a sensitive read out for the presence of subvisible protein aggregates. To demonstrate the potential utility of the approach, we examine the major peptide associated with the initiation of Alzheimer's disease, amyloid ß-protein (Aß) at a patho-physiologically relevant concentration in mouse cortical neurons. Using our approach, we find preliminary evidence that subvisible Aß aggregates are detected at specific subcellular regions and that neurons drive the formation of specific Aß aggregate conformations. These findings therefore demonstrate the potential of a novel fluorescence-based approach for detecting and imaging protein aggregates in a cellular context, which can be used to sensitively probe the association of early stage toxic protein aggregates within subcellular compartments.

Second Harmonic Spectroscopy of Surface Lattice Resonances.

Because of their large figures of merit, surface lattice resonances (SLRs) in metal nanoparticle arrays are very promising for chemical and biomolecular sensing in both liquid and gas media. SLRs are sensitive to refractive index changes both near the surface of the nanoparticles (surface sensitivity) and in the volume between them (bulk sensitivity). Because of its intrinsic surface-sensitivity and a power law dependence on electric fields, second harmonic generation (SHG) spectroscopy can improve upon both the surface and volume sensitivities of SLRs. In this report on SHG spectroscopy of plasmonic nanoparticles, we show that the SHG signal is greatly increased (up to 450 times) by the SLRs. We also demonstrate very narrow resonances in SHG intensity (∼5 nm fwhm). We illustrate how the SHG resonances are highly sensitive to SLRs by varying the fundamental wavelength, angle of incidence, nanoparticle material, and lattice constant of the arrays. Finally, we identify an SHG resonance (10 nm fwhm) that is electric dipole forbidden and can be attributed to higher-order multipoles, enhanced by the strong near-fields of SLRs. Our results open up new and very promising avenues for chemical and biomolecular sensing based on SHG spectroscopy of SLRs.

Circular Dichroism and Isotropy - Polarity Reversal of Ellipticity in Molecular Films of 1,1'-Bi-2-Naphtol.

We have studied the circular dichroism (CD), in the ultraviolet and visible regions, of the transparent, chiral molecule 1,1'-Bi-2-naphtol (BINOL) in 1.5 µm thick films. The initial transparent film shows an additional negative cotton effect in the CD compared to solution. With time under room temperature the film undergoes a structural phase transition. This goes hand in hand with a cotton effect at the low energy absorption band which inverts with opposite propagation direction of light through the film which is revealed as a polarity reversal of ellipticity (PRE). After completion of the phase transition the film exhibits circular differential scattering throughout the visible range which also shows PRE. The structure change was studied with Raman, microscopy under cross polarization conditions and nonlinear second-harmonic generation circular dichroism (SHG-CD). The superposition of the optical activity of individual molecules and isotropy effects makes an interpretation challenging. Yet overcoming this challenge by finding a suitable model structural information can be derived from CD measurements.

Second-Harmonic Generation Optical Rotation Solely Attributable to Chirality in Plasmonic Metasurfaces.

Chiral plasmonic nanostructures, those lacking mirror symmetry, can be designed to manipulate the polarization of incident light resulting in chiroptical (chiral optical) effects such as circular dichroism (CD) and optical rotation (OR). Due to high symmetry sensitivity, corresponding effects in second-harmonic generation (SHG-CD and SHG-OR) are typically much stronger in comparison. These nonlinear effects have long been used for chiral molecular analysis and characterization; however both linear and nonlinear optical rotation can occur even in achiral structures, if the structure is birefringent due to anisotropy. Crucially, chiroptical effects resulting from anisotropy typically exhibit a strong dependence on structural orientation. Here we report a large second-harmonic generation optical rotation of ±45°, due to intrinsic chirality in a highly anisotropic helical metamaterial. The SHG intensity is found to strongly relate to the structural anisotropy; however, the angle of SHG-OR is invariant under sample rotation. We show that by tuning the geometry of anisotropic nanostructures, the interaction between anisotropy, chirality, and experimental geometry can allow even greater control over the chiroptical properties of plasmonic metamaterials.

Surface-Enhanced Raman Spectroscopy: A Facile and Rapid Method for the Chemical Component Study of Individual Atmospheric Aerosol.

A simple and rapid method for detecting chemical components of individual aerosol particles on Klarite substrate with surface-enhanced Raman spectroscopy (SERS) is described. For both single simulated aerosol particles and ambient atmospheric particles, this new analytical method promotes the enhancement factor of the Raman signal. The spectra of ammonium sulfate and naphthalene particles at the microscopic level are enhanced by a factor of 6 and therefore greatly improve the detection of the chemical composition of an individual aerosol particle. When aerosol particles are found over a microscopic domain, a set of Raman spectra with chemical information can be obtained via SERS mapping. The maps illustrate the distribution of organic or inorganic species on the SERS substrate. This constitutes a facile and rapid method to study aerosol particles. This new method allows the analysis of chemical composition in single aerosol particles, demonstrating the power of SERS to probe the ambient atmospheric particles and to study the formation of aerosol particles.

Strong Rotational Anisotropies Affect Nonlinear Chiral Metamaterials.

Masked by rotational anisotropies, xthe nonlinear chiroptical response of a metamaterial is initially completely inaccessible. Upon rotating the sample the chiral information emerges. These results highlight the need for a general method to extract the true chiral contributions to the nonlinear optical signal, which would be hugely valuable in the present context of increasingly complex chiral meta/nanomaterials.

Chiral light intrinsically couples to extrinsic/pseudo-chiral metasurfaces made of tilted gold nanowires.

Extrinsic or pseudo-chiral (meta)surfaces have an achiral structure, yet they can give rise to circular dichroism when the experiment itself becomes chiral. Although these surfaces are known to yield differences in reflected and transmitted circularly polarized light, the exact mechanism of the interaction has never been directly demonstrated. Here we present a comprehensive linear and nonlinear optical investigation of a metasurface composed of tilted gold nanowires. In the linear regime, we directly demonstrate the selective absorption of circularly polarised light depending on the orientation of the metasurface. In the nonlinear regime, we demonstrate for the first time how second harmonic generation circular dichroism in such extrinsic/pseudo-chiral materials can be understood in terms of effective nonlinear susceptibility tensor elements that switch sign depending on the orientation of the metasurface. By providing fundamental understanding of the chiroptical interactions in achiral metasurfaces, our work opens up new perspectives for the optimisation of their properties.

Light-induced actuating nanotransducers.

Nanoactuators and nanomachines have long been sought after, but key bottlenecks remain. Forces at submicrometer scales are weak and slow, control is hard to achieve, and power cannot be reliably supplied. Despite the increasing complexity of nanodevices such as DNA origami and molecular machines, rapid mechanical operations are not yet possible. Here, we bind temperature-responsive polymers to charged Au nanoparticles, storing elastic energy that can be rapidly released under light control for repeatable isotropic nanoactuation. Optically heating above a critical temperature [Formula: see text] = 32 °C using plasmonic absorption of an incident laser causes the coatings to expel water and collapse within a microsecond to the nanoscale, millions of times faster than the base polymer. This triggers a controllable number of nanoparticles to tightly bind in clusters. Surprisingly, by cooling below [Formula: see text] their strong van der Waals attraction is overcome as the polymer expands, exerting nanoscale forces of several nN. This large force depends on van der Waals attractions between Au cores being very large in the collapsed polymer state, setting up a tightly compressed polymer spring which can be triggered into the inflated state. Our insights lead toward rational design of diverse colloidal nanomachines.

Optical response of threaded chain plasmons: from capacitive chains to continuous nanorods.

We present a detailed theoretical analysis of the optical response of threaded plasmonic nanoparticle strings, chains of metallic nanoparticles connected by cylindrical metallic bridges (threads), based on full-electrodynamic calculations. The extinction spectra of these complex metallic nanostructures are dominated by large resonances in the near infrared, which are associated with charge transfer along the entire string. By analysing contour plots of the electric field amplitude and phase we show that such strings can be interpreted as an intermediate situation between metallic nanoparticle chains and metallic nanorods, exhibiting characteristics of both. Modifying the dielectric environment, the number of nanoparticles within the strings, and the dimensions of the threads, allows for tuning the optical response of the strings within a very broad region in the visible and near infrared.