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.

Magnetic-Plasmonic Nanocomposites as Versatile Substrates for Surface-enhanced Raman Scattering (SERS) Spectroscopy.

Surface-enhanced Raman scattering (SERS) spectroscopy, a highly sensitive technique for detecting trace-level analytes, relies on plasmonic substrates. The choice of substrate, its morphology, and the excitation wavelength are crucial in SERS applications. To address advanced SERS requirements, the design and use of efficient nanocomposite substrates have become increasingly important. Notably, magnetic-plasmonic (MP) nanocomposites, which combine magnetic and plasmonic properties within a single particle system, stand out as promising nanoarchitectures with versatile applications in nanomedicine and SERS spectroscopy. In this review, we present an overview of MP nanocomposite fabrication methods, explore surface functionalization strategies, and evaluate their use in SERS. Our focus is on how different nanocomposite designs, magnetic and plasmonic properties, and surface modifications can significantly influence their SERS-related characteristics, thereby affecting their performance in specific applications such as separation, environmental monitoring, and biological applications. Reviewing recent studies highlights the multifaceted nature of these materials, which have great potential to transform SERS applications across a range of fields, from medical diagnostics to environmental monitoring. Finally, we discuss the prospects of MP nanocomposites, anticipating favorable developments that will make substantial contributions to various scientific and technological areas.

Balancing Near-Field Enhancement and Hot Carrier Injection: Plasmonic Photocatalysis in Energy-Transfer Cascade Assemblies.

Photocatalysis stands as a very promising alternative to photovoltaics in exploiting solar energy and storing it in chemical products through a single-step process. A central obstacle to its broad implementation is its low conversion efficiency, motivating research in different fields to bring about a breakthrough in this technology. Using plasmonic materials to photosensitize traditional semiconductor photocatalysts is a popular strategy whose full potential is yet to be fully exploited. In this work, we use CdS quantum dots as a bridge system, reaping energy from Au nanostructures and delivering it to TiO2 nanoparticles serving as catalytic centers. The quantum dots can do this by becoming an intermediate step in a charge-transfer cascade initiated in the plasmonic system or by creating an electron-hole pair at an improved rate due to their interaction with the enhanced near-field created by the plasmonic nanoparticles. Our results show a significant acceleration in the reaction upon combining these elements in hybrid colloidal photocatalysts that promote the role of the near-field enhancement effect, and we show how to engineer complexes exploiting this approach. In doing so, we also explore the complex interplay between the different mechanisms involved in the photocatalytic process, highlighting the importance of the Au nanoparticles' morphology in their photosensitizing capabilities.

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.

Composite nanoparticle-metal-organic frameworks for SERS sensing.

In recent years, metal-organic frameworks, in general, and zeolitic imidazolate frameworks, in special, had become popular due to their large surface area, pore homogeneity, and easy preparation and integration with plasmonic nanoparticles to produce optical sensors. Herein, we summarize the late advances in the use of these hybrid composites in the field of surface-enhanced Raman scattering and their future perspectives.

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.

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.

Design and fabrication of bimetallic plasmonic colloids through cold nanowelding.

The integration of Au and Ag into nanoalloys has emerged as an intriguing strategy to further tailor and boost the plasmonic properties of optical substrates. Conventional approaches for fabricating these materials via chemical reductions of metal salts in solution suffer from some limitations, such as the possibility of retaining the original morphology of the monometallic substrate. Spontaneous nanowelding at room temperature has emerged as an alternative route to tailor Au/Ag nanomaterials. Herein, we perform a thorough study on the cold-welding process of silver nanoparticles onto gold substrates to gain a better understanding of the role of different variables in enabling the formation of well-defined bimetallic structures that retain the original gold substrate morphology. To this end, we systematically varied the size of silver nanoparticles, dimensions and geometries of gold substrates, solvent polarity and structural nature of the polymeric coating. A wide range of optical and microscopy techniques have been used to provide a complementary and detailed description of the nanowelding process. We believe this extensive study will provide valuable insights into the optimal design and engineering of bimetallic plasmonic Ag/Au structures for application in nanodevices.

Plasmonic Azobenzene Chemoreporter for Surface-Enhanced Raman Scattering Detection of Biothiols.

Low molecular weight thiols (biothiols) are highly active compounds extensively involved in human physiology. Their abnormal levels have been associated with multiple diseases. In recent years, major efforts have been devoted to developing new nanosensing methods for the low cost and fast quantification of this class of analytes in minimally pre-treated samples. Herein, we present a novel strategy for engineering a highly efficient surface-enhanced Raman scattering (SERS) spectroscopy platform for the dynamic sensing of biothiols. Colloidally stable silver nanoparticles clusters equipped with a specifically designed azobenzene derivative (AzoProbe) were generated as highly SERS active substrates. In the presence of small biothiols (e.g., glutathione, GSH), breakage of the AzoProbe diazo bond causes drastic spectral changes that can be quantitatively correlated with the biothiol content with a limit of detection of ca. 5 nM for GSH. An identical response was observed for other low molecular weight thiols, while larger macromolecules with free thiol groups (e.g., bovine serum albumin) do not produce distinguishable spectral alterations. This indicates the suitability of the SERS sensing platform for the selective quantification of small biothiols.

SERS optical accumulators as unified nanoplatforms for tear sampling and sensing in soft contact lenses.

Tear analysis has become an invaluable asset in clinical research in order to identify and quantify novel biomarkers for a wide array of conditions. The present work is intended to take this area of study one step further by implementing an innovative sensing platform through which exploration of low-molecular-weight compounds is conducted outperforming traditional analytical technologies. With this aim, carefully engineered plasmonic nanoassemblies have been synergistically combined with molecular-sieving materials giving rise to size-selective samplers with SERS detection capabilities. These architectures have been then integrated onto hydrogel-based contact lenses and tested in simulated tear fluids in order to evidence their operational features. Through this approach, a prolonged analyte accumulation can be realized, thus providing a competitive advantage in those scenarios where concentration of biomarkers is typically low or minimum sample volumes are not met. Additionally, quenching of metabolic flux and analyte extraction protocols can be circumvented, hence preventing the intrinsic physical and chemical interferences stemming from these procedures. The obtained results render these sensing platforms as promising medical devices, and constitute a great opportunity in order to expand the clinical toolkit in tear analysis.

Widefield SERS for High-Throughput Nanoparticle Screening.

Surface-enhanced Raman scattering (SERS) imaging is a powerful technology with unprecedent potential for ultrasensitive chemical analysis. Point-by-point scanning and often excessively long spectral acquisition-times hamper the broad exploitation of the full analytical potential of SERS. Here, we introduce large-scale SERS particle screening (LSSPS), a multiplexed widefield screening approach to particle characterization, which is 500-1000 times faster than typical confocal Raman implementations. Beyond its higher throughput, LSSPS simultaneously quantifies both the sample's Raman and Rayleigh scattering to directly quantify the fraction of SERS-active particles which allows for an unprecedented correlation of SERS activity with particle size. .

Targets and Tools: Nucleic Acids for Surface-Enhanced Raman Spectroscopy.

Surface-enhanced Raman spectroscopy (SERS) merges nanotechnology with conventional Raman spectroscopy to produce an ultrasensitive and highly specific analytical tool that has been exploited as the optical signal read-out in a variety of advanced applications. In this feature article, we delineate the main features of the intertwined relationship between SERS and nucleic acids (NAs). In particular, we report representative examples of the implementation of SERS in biosensing platforms for NA detection, the integration of DNA as the biorecognition element onto plasmonic materials for SERS analysis of different classes of analytes (from metal ions to microorgniasms) and, finally, the use of structural DNA nanotechnology for the precise engineering of SERS-active nanomaterials.

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.

Spontaneous and stimulated electron-photon interactions in nanoscale plasmonic near fields.

The interplay between free electrons, light, and matter offers unique prospects for space, time, and energy resolved optical material characterization, structured light generation, and quantum information processing. Here, we study the nanoscale features of spontaneous and stimulated electron-photon interactions mediated by localized surface plasmon resonances at the tips of a gold nanostar using electron energy-loss spectroscopy (EELS), cathodoluminescence spectroscopy (CL), and photon-induced near-field electron microscopy (PINEM). Supported by numerical electromagnetic boundary-element method (BEM) calculations, we show that the different coupling mechanisms probed by EELS, CL, and PINEM feature the same spatial dependence on the electric field distribution of the tip modes. However, the electron-photon interaction strength is found to vary with the incident electron velocity, as determined by the spatial Fourier transform of the electric near-field component parallel to the electron trajectory. For the tightly confined plasmonic tip resonances, our calculations suggest an optimum coupling velocity at electron energies as low as a few keV. Our results are discussed in the context of more complex geometries supporting multiple modes with spatial and spectral overlap. We provide fundamental insights into spontaneous and stimulated electron-light-matter interactions with key implications for research on (quantum) coherent optical phenomena at the nanoscale.

Silver melamine thin film as a flexible platform for SERS analysis.

New SERS detection platforms are required for the quick and easy preparation of sensing devices for food, agriculture, and environmental science. For quantitative sensing, it is important that a sensing material, in addition to efficient sensing, provides extraction and concentration of the target molecules such as toxic pesticides or healthy vitamins. We design such films adopting the Liesegang rings formation process that includes the reaction-diffusion of silver nitrate and melamine followed by the precipitation of different intermediates and their reduction by light in a pectin medium. Surprisingly, we find that the presence of melamine provides an excellent substrate for the extraction of pollutants at the solid-liquid interface giving rise to a powerful but easy and fast method for the quantification of fruits' quality. The complex silver and melamine containing films show high sensitivity even at relatively low silver concentrations.

X-ray-Based Techniques to Study the Nano-Bio Interface.

X-ray-based analytics are routinely applied in many fields, including physics, chemistry, materials science, and engineering. The full potential of such techniques in the life sciences and medicine, however, has not yet been fully exploited. We highlight current and upcoming advances in this direction. We describe different X-ray-based methodologies (including those performed at synchrotron light sources and X-ray free-electron lasers) and their potentials for application to investigate the nano-bio interface. The discussion is predominantly guided by asking how such methods could better help to understand and to improve nanoparticle-based drug delivery, though the concepts also apply to nano-bio interactions in general. We discuss current limitations and how they might be overcome, particularly for future use in vivo.

Gold-spiked coating of silver particles through cold nanowelding.

Herein, we present a method to obtain particles composed of a segregated alloy of silver coated with gold. These particles are achieved through the controlled Ostwald ripening of small gold nanoparticles (NPs) on the surfaces of larger silver particles. The prepared segregated nanoalloyed colloids benefit from the advantages of gold and silver with none of their drawbacks. These platforms provide optical efficiencies which are superior to those of silver with the chemical resistance and biocompatibility of gold.

Plasmonic foam platforms for air quality monitoring.

Plasmonic reversible gas sensors are of paramount importance for the monitoring of indoor environments. Herein, we design and engineer a plasmonic foam, with a high surface area, confined inside a capillary glass tube for the live monitoring of carbon monoxide (CO) in closed environments using surface-enhanced resonance Raman scattering. The illumination of the sensor with light during the flow of air allows the live monitoring of the concentration of atmospheric CO through surface-enhanced resonance Raman scattering. The sensor was prepared with a detection range from 10 to 40 ppm, due to health needs. The results show a sensitive, selective, reversible and robust sensor applicable to the monitoring of CO levels but also to other gas species upon appropriate functionalization.