In this manuscript we present the steps required to fabricate, modify, and measure a plasmonic metasurface array for cross-reactive sensing applications. Multiple arrays of gold nanostructures were fabricated using a standard top-down electron-beam lithography process and then enclosed in a microfluidic chamber. Partial-selectivity was then achieved by using different thiol chemistries to modify each array. Finally, measurements of various samples were taken using a custom-built microscope setup.
Extraordinary optical transmission (EOT) in nanohole arrays has proven to be a useful tool for biosensing applications. The enhanced light transmission observed in these structures is due to interactions between propagating surface waves and localised resonances. In this paper we present methods to both optimise the resonance peaks of nanohole array sensors and to tune their resonance wavelength. Sensor performance is enhanced by annealing. Annealing significantly increases the grain size of the gold thin-film, reducing losses and narrowing the resonance width. In addition, we show that by changing the size and arrangement of nanoholes we can control the position of their resonance peak. In doing so, we seek to improve the performance of EOT sensors for cross-reactive sensing applications.
To achieve the UN Sustainable Development Goal of universal access to clean water and sanitation, we need to rethink centralized water systems with global net-zero carbon and sustainability in mind. One approach is to develop scalable off-grid systems that are reliable and easy to use and maintain. A major challenge for such systems is translating the standard laboratory-based monitoring of centralized systems to a more sustainable and scalable model for regularly and routinely monitoring system outputs, which consist of complex mixtures with varying concentrations of molecules and ions in water. Here, we demonstrate a preliminary sensor that, once fully developed, could allow for point-of-use measurements with a single output to monitor. Rather than developing multiple sensors to monitor the levels of each individual component in the water, our label-free, array-based design mimics the biological system of taste. The sensor is comprised of an array of nano-tastebuds made of tailored plasmonic metasurfaces. The combination of different signals from each nano-tastebud to the same sample yields a unique fingerprint for that sample. Through training, these fingerprints build an identification model. By integrating a fully developed sensor into decentralized water systems, we seek to provide non-expert end-users with an easy-to-read output capable of warning of imminent system failures.
Hybrid metal-semiconductor systems are promising substrates for field Raman analysis due to their ability to use both electromagnetic and chemical enhancement pathways for surface enhanced Raman spectroscopy (SERS). Photo-induced Raman spectroscopy (PIERS) has previously been shown to be a promising method utilizing an additional enhancement route through photo-inducing atomic surface oxygen vacancies in photocatalytic metal-oxide semiconductors. The photoinduced vacancies can form vibronic coupling resonances, known as charge transfers, with analyte molecules, enhancing the signal beyond conventional SERS enhancements. However, conventional UV sources most often used for excitation of the PIERS substrate are impractical in combination with portable Raman systems for field analysis. In this work we show how a small UVC LED, centered at 255 nm, can replicate the same results previously reported with the benefit of allowing greater in-situ real time measurements under constant UV exposure. The UV LED source can be controlled more easily and safely, making it a practical UV source for field PIERS analysis.
Enhanced Raman relies heavily on finding ideal hot-spot regions which enable significant enhancement factors. In addition, the termed “chemical enhancement” aspect of SERS is often neglected due to its relatively low enhancement factors, in comparison to those of electromagnetic (EM) nature. Using a metal-semiconductor hybrid system, with the addition of induced surface oxygen vacancy defects, both EM and chemical enhancement pathways can be utilized on cheap reusable surfaces. Two metal-oxide semiconductor thin films, WO3 and TiO2, were used as a platform for investigating size dependent effects of Au nanoparticles (NPs) for SERS (surface enhanced Raman spectroscopy) and PIERS (photo-induced enhanced Raman spectroscopy – UV pre-irradiation for additional chemical enhancement) detection applications. A set concentration of spherical Au NPs (5, 50, 100 and 150 nm in diameter) was drop-cast on preirradiated metal-oxide substrates. Using 4-mercaptobenzoic acid (MBA) as a Raman reporter molecule, a significant dependence on the size of nanoparticle was found. The greatest surface coverage and ideal distribution of AuNPs was found for the 50 nm particles during SERS tests, resulting in a high probability of finding an ideal hot-spot region. However, more significantly a strong dependence on nanoparticle size was also found for PIERS measurements – completely independent of AuNP distribution and orientation affects – where 50 nm particles were also found to generate the largest PIERS enhancement. The position of the analyte molecule with respect to the metal-semiconductor interface and position of generated oxygen vacancies within the hot-spot regions was presented as an explanation for this result.
Fluorescence-guided brain tumour resection, notably using 5-aminolevulinic acid (ALA)-induced protoporphyrin IX (PpIX) for high-grade gliomas, has been demonstrated to provide better tissue differentiation, thereby improving patient outcomes when compared to white-light guidance. Novel fluorescence imaging devices aiming to increase detection specificity and sensitivity and targeting applications beyond high-grade gliomas are typically assessed by measurements using tissue-mimicking optical phantoms. The field currently lacks adequate phantoms with well-characterised tuneable optical properties. In this study, we developed soft tissue-mimicking fluorescence phantoms (TMFP) highly suitable for this purpose. We investigated: 1) the ability to independently tune optical and fluorescent properties; 2) the stability of the fluorescence signal over time; and 3) the potential of the proposed phantoms for imaging device validation. The TMFP is based on gel-wax which is an optically transparent mineral-oil based soft material. We embedded TiO2 as scattering material, carbon black oil-paint as background absorber, and CdTe Quantum Dots (QDs) as fluorophore because of its similar fluorescence spectrum to PpIX. Scattering and absorption properties were measured by a spectrophotometer, while the fluorescence was assessed by a wide-field fluorescence imaging system (WFFI) and a spectrometer. We demonstrated that: 1) the addition of QDs didn’t alter the phantom’s scattering which was only defined by the concentration of TiO2, whereas its absorption was defined by both QDs and colour oil paint; 2) the measured fluorescence intensity was linearlyproportional to the concentration of QDs; 3) the fluorescence intensity was stable over time (up to eight months); and 4) the fluorescence signal measured by the WFFI were strongly correlated to spectrometer measurements.
5-ALA-PpIX fluorescence-guided brain tumour resection can increase the accuracy at which cancerous tissue is removed and thereby improve patient outcomes, as compared with standard white light imaging. Novel optical devices that aim to increase the specificity and sensitivity of PpIX detection are typically assessed by measurements in tissue-mimicking optical phantoms of which all optical properties are defined. Current existing optical phantoms specified for PpIX lack consistency in their optical properties, and stability with respect to photobleaching, thus yielding an unstable correspondence between PpIX concentration and the fluorescence intensity.
In this study, we developed a set of aqueous-based phantoms with different compositions, using deionised water or PBS buffer as background medium, intralipid as scattering material, bovine haemoglobin as background absorber, and either PpIX dissolved in DMSO or a novel nanoparticle with similar absorption and emission spectrum to PpIX as the fluorophore. We investigated the phantom stability in terms of aggregation and photobleaching by comparing with different background medium and fluorophores, respectively. We characterised the fluorescence intensity of the fluorescent nanoparticle in different concentration of intralipid and haemoglobin and its time-dependent stability, as compared to the PpIX-induced fluorescence. We corroborated that the background medium was essential to prepare a stable aqueous phantom. The novel fluorescent nanoparticle used as surrogate fluorophore of PpIX presented an improved temporal stability and a reliable correspondence between concentration and emission intensity. We proposed an optimised phantom composition and recipe to produce reliable and repeatable phantom for validation of imaging device.
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