Arrays of metal nano-holes have proved to be among of the most promising structures for applications in the field of nano-photonics and optoelectronics. Supporting both localized and propagating surface plasmons resonances, they are characterized by very high versatility thanks to the tunability of these modes, by means of the change of their periodicity, the size of the holes and metal composition. The interaction between different optical features can be exploited to modulate electromagnetic field distribution leading various hot-spots excitations on the metal surfaces. In this work, long range ordered arrays of nano-holes in thin gold films, with different geometrical characteristics, were fabricated by a modified nano-sphere lithography protocol, which allows precise control on holes’ dimensions together with the preservation of the order and of the pristine periodicity of the array. An in-depth analysis of the correlation between surface plasmon modes interference and its effect on electromagnetic field distribution is proposed, both by numerical simulations and experimentally. Finally, metal nano-holes arrays are exploited for surface enhanced Raman experiments, evaluating and comparing their performances by the estimation of the enhancement factor. Values close to the single molecule detection are obtained for most of the samples, proving their potentialities in surface enhanced spectroscopy applications.
Functionalized plasmonic nanostructure platforms are widely used for developing optical biosensors and SERS assays. In this work, we present a low-cost and scalable surface-enhanced Raman scattering (SERS) system based on an innovative optical transducer comprising gold nanoparticles (AuNPs) embedded in nano-fibrillated bacterial cellulose (BC). The AuNPs@BC composite leverages the unique nanofibrillar architecture of bacterial cellulose, which provides a high surface area, flexibility, and uniform nanoparticle distribution, enabling the formation of numerous electromagnetic “hot spots”. This structure excites localized surface plasmon resonance (LSPR), as demonstrated by a bulk sensitivity of 72 nm/RIU, and supports enhanced Raman signal amplification. The eco-friendly and disposable AuNPs@BC platform was tested for agrifood applications, focusing on the detection of thiram pesticide. The system achieved a detection limit of 0.24 ppm (1 µM), meeting the sensitivity requirements for regulatory compliance in food safety. A strong linear correlation (R2 ≈ 0.99) was observed between the SERS peak intensity at 1370 cm−1 and thiram concentrations, underscoring its potential for quantitative analysis. The combination of high sensitivity, reproducibility, and environmental sustainability makes the AuNPs@BC platform a promising solution for developing cost-effective, flexible, and portable sensors for pesticide monitoring and other biosensing applications.
Conventional nano-sphere lithography techniques have been extended to the fabrication of highly periodic arrays of sub-wavelength nanoholes in a thin metal film. By combining the dry etching processes of self-assembled monolayers of polystyrene colloids with metal physical deposition, the complete transition from increasing size triangular nanoprism to hexagonally distributed nanoholes array onto thin metal film has been gradually explored. The investigated nano-structured materials exhibit interesting plasmonic properties which can be precisely modulated in a desired optical spectral region. An interesting approach based on optical absorbance measurements has been adopted for rapid and non-invasive inspections of the nano-sphere monolayer after the ion etching process. By enabling an indirect and accurate evaluation of colloid dimensions in a large area, this approach allows the low-cost and reproducible fabrication of plasmonic materials with specifically modulated optical properties suitable for many application in biosensing devices or Raman enhanced effects.
Plasmonic nanostructures with tunable optical properties can have many different applications, including high-sensitivity optical sensing for biological and chemical analyses in different field such as medical, environmental and food safety. The realization of an optimized sensing platform is closely related to the ability to finely control optical properties of nanostructures, which are, in turn, intimately linked to their geometrical and compositional characteristics. In this paper, an efficient and reproducible fabrication protocol, based on nanosphere lithography, for the realization of metal nanostructures with tunable plasmonic features is presented. In particular, the relationships between the geometric characteristics of different types of nanostructures with related optical phenomena such as enhanced absorption or extraordinary transmission are investigated in detail. These properties, together with electric field enhancement and confinement, are characterized and optimized in view of the employment of the fabricated nanostructures as optical transducers in nanoplasmonic chemosensor platforms working in the UV-VIS spectral range.
Lipopolysaccharides (LPS) from Gram-negative bacteria represent a significant challenge across various industries due to their prevalence and pathogenicity and the limitations of existing detection methods. Traditional approaches, such as the rabbit pyrogen test (RPT) and the Limulus Amebocyte Lysate (LAL) assay, have served as gold standards for endotoxin detection. However, these methods are constrained by high costs, lengthy processing times, environmental concerns, and the need for significant reagent volumes, which limit their scalability and application in resource-limited settings. In this study, we introduce an innovative microfluidic platform that integrates the LAL assay within microdroplets, addressing the critical limitations of traditional techniques. By leveraging the precise fluid control and reaction isolation offered by microdroplet technology, the system reduces reagent consumption, enhances sensitivity, and enables high-throughput analysis. Calibration tests were performed to validate the platform’s ability to detect LPS, using colorimetric measurements. Results demonstrated comparable or improved performance relative to traditional systems, achieving lower detection limits and greater accuracy. This work demonstrates a proof-of-concept miniaturisation of the pharmacopoeial LAL assay. The method yielded low intra-assay variability (σ ≈ 0.002 OD; CV ≈ 0.9% over n = 50 droplets per point) and a LOD estimated from calibration statistics after path-length normalisation. Broader adoption will require additional comparative validation and standardisation. This scalable, cost-effective, and environmentally sustainable approach offers a practical solution for endotoxin detection in clinical diagnostics, biopharmaceutical production, and environmental monitoring. The proposed technology paves the way for advanced LPS detection methods that meet stringent safety standards while improving efficiency, affordability, and adaptability for diverse applications.