Review of Gold Nanoparticles in Surface Plasmon-Coupled Emission Technology: Effect of Shape, Hollow Nanostructures, Nano-Assembly, Metal-Dielectric and Heterometallic Nanohybrids.

Point-of-care (POC) diagnostic platforms are globally employed in modern smart technologies to detect events or changes in the analyte concentration and provide qualitative and quantitative information in biosensing. Surface plasmon-coupled emission (SPCE) technology has emerged as an effective POC diagnostic tool for developing robust biosensing frameworks. The simplicity, robustness and relevance of the technology has attracted researchers in physical, chemical and biological milieu on account of its unique attributes such as high specificity, sensitivity, low background noise, highly polarized, sharply directional, excellent spectral resolution capabilities. In the past decade, numerous nano-fabrication methods have been developed for augmenting the performance of the conventional SPCE technology. Among them the utility of plasmonic gold nanoparticles (AuNPs) has enabled the demonstration of plethora of reliable biosensing platforms. Here, we review the nano-engineering and biosensing applications of AuNPs based on the shape, hollow morphology, metal-dielectric, nano-assembly and heterometallic nanohybrids under optical as well as biosensing competencies. The current review emphasizes the recent past and evaluates the latest advancements in the field to comprehend the futuristic scope and perspectives of exploiting Au nano-antennas for plasmonic hotspot generation in SPCE technology.

A low-cost optofluidic platform for the colorimetric assessment of bacterial activity in domestic wastewater.

Optofluidic chips represent a cost-effective platform for the development of miniaturized devices to perform biochemical reactions at a microscale. The dye reduction-based electron-transfer activity monitoring (DREAM) assay is a colorimetric approach that has been adopted for the rapid assessment of bacterial activity in bioreactors used in bioremediation and industrial biotechnology. A three-layered PMMA-based optofluidic chip having laser-machined microchannels coupled with a detection system comprising an LED source and a photodiode interfaced with a microcontroller for automation constituted the experimental setup. Data acquisition was executed using a user-friendly graphical user interface (GUI) that enabled real-time monitoring of bacterial activity. A performance comparison study was performed to assess the viability of replacing expensive spectrophotometers with an inexpensive photodiode for optoelectronic automation. Bacterial activity across different growth phases of a bacterial culture, initiated using untreated domestic wastewater, was assessed by the detector on the basis of voltage readings corresponding to the rate of decrease in the blue color intensity. The highest activity observed corresponded to the log phase of the growth curve. The optimal time for measurement of bacterial activity within the log phase of the growth curve was identified using different dilutions of untreated domestic wastewater. Furthermore, the device showed comparable sensitivities for samples from different time points in a bacterial growth curve and for different dilutions of untreated domestic wastewater samples. The device also demonstrated a linear response in the assessment of bacterial activity as a function of the change in strength of untreated domestic wastewater. This is the first report on colorimetric assessment of bacterial activity using a low-cost photodiode-based device at the microscale constructed using off-the-shelf components.

Smartphone-Based Attomolar Cyanide Ion Sensing Using Au-Graphene Oxide Cryosoret Nanoassembly and Benzoxazolium-Based Fluorophore in a Surface Plasmon-Coupled Enhanced Fluorescence Interface.

Photoplasmonic platforms are being demonstrated as excellent means for bridging nanochemistry and biosensing approaches at advanced interfaces, thereby augmenting the sensitivity and quantification of the desired analytes. Although resonantly coupled electromagnetic waves at the surface plasmon-coupled emission (SPCE) interface are investigated with myriad nanomaterials in order to boost the detection limits, rhodamine moieties are ubiquitously used as SPCE reporter molecules in spite of their well-known limitations. In order to overcome this constraint, in this work, a benzoxazolium-based fluorescent molecule, (E)-2-(4-(dimethylamino)styryl)-3-methylbenzo[d]oxazol-3-ium iodide (DSBO), was synthesized to selectively detect the cyanide (CN-) ions in water samples. To this end, the sensitivity of the fabricated SPCE substrates is tested in spacer, cavity, and extended cavity nanointerfaces to rationalize the configurational robustness. The performance of the sensor is further improved with the careful engineering of gold (Au)-graphene oxide (GO) cryosoret nanoassemblies fabricated via an adiabatic cooling technology. The unique dequenching (turn-on) of the quenched (turn-off) fluorescent signal is demonstrated with the hybridized metal-π plasmon synergistic coupling in the nanovoids and nanocavities assisting delocalized Bragg and localized Mie plasmons. The spectro-plasmonic analysis yielded highly directional, polarized (>95%), and enhanced emission attributes with an attomolar limit of detection of 10 aM of CN- ions with high linearity (R2 = 0.996) and excellent reliability, in addition to an exceptional correlation with the theoretically obtained TFclac simulations. The CN- ion sensing is experimentally validated with the smartphone-based cost-effective SPCE detection technology to render the device amenable to resource-limited settings. We believe that the unique fluorophore-cryosoret nanoassemblage presented here encourages development of frugal, unconventional, and highly desirable strategies for the selective quantitation of environmentally and physiologically relevant analytes at trace concentrations for use in point-of-care diagnostics.

Sericin-Based Bio-Inspired Nano-Engineering of Heterometallic AgAu Nanocubes for Attomolar Mefenamic Acid Sensing in the Mobile Phone-Based Surface Plasmon-Coupled Interface.

Engineering photo-plasmonic platforms with heterometallic nanohybrids are of paramount significance for realizing augmented sensitivity in fluorescence-based analytical detection. Although myriad nanomaterials with versatile functionalities have been explored in this regard in the surface plasmon-coupled emission (SPCE) interface, light harvesting using nano-antennas synthesized via sustainable bio-inspired routes still remains a high priority in current research. Our study provides a rational design for in situ fabrication of nanoparticles of silver, gold, and their plasmonic hybrids using biocompatible, non-hazardous sericin protein (obtained Bombyx mori) as the reducing and capping agent. The one-pot, user-eco-friendly technology demonstrated here utilizes UV irradiation to promote the photo-induced electron transfer mechanism, thereby yielding nanomaterials of tunable optoelectronic functionalities. The resulting homometallic and heterometallic nanohybrids with robust localized surface plasmon resonances (LSPR) showed strong light-confining attributes when interfaced with the propagating surface plasmon polaritons (SPPs) of the SPCE platform, thereby yielding tunable, highly directional, polarized, and amplified fluorescence emission. The experimentally obtained emission profiles displayed an excellent correlation with the theoretically obtained dispersion diagrams validating the spectro-plasmonic results. The abundant hotspots from AgAu nanocubes presented in excess of 1300-fold dequenched fluorescence enhancement and were utilized for cost-effective and real-time mobile phone-based sensing of biologically relevant mefenamic acid at an attomolar limit of detection. We believe that this superior biosensing performance accomplished using the frugal bioinspired nano-engineering at hybrid interfaces would open new doors for developing nanofabrication protocols with the quintessential awareness of the principles of green nanotechnology, consequently eliminating hazardous chemicals and solvents in the development of point-of-care diagnostic tools.

Surface Plasmon-Coupled Dual Emission Platform for Ultrafast Oxygen Monitoring after SARS-CoV-2 Infection.

The outbreak of the COVID-19 pandemic has had a major impact on the health and well-being of people with its long-term effect on lung function and oxygen uptake. In this work, we present a unique approach to augment the phosphorescence signal from phosphorescent gold(III) complexes based on a surface plasmon-coupled emission platform and use it for designing a ratiometric sensor with high sensitivity and ultrafast response time for monitoring oxygen uptake in SARS-CoV-2-recovered patients. Two monocyclometalated Au(III) complexes, one having exclusively phosphorescence emission (λPL = 578 nm) and the other having dual emission, fluorescence (λPL = 417 nm) and phosphorescence (λPL = 579 nm), were studied using the surface plasmon-coupled dual emission (SPCDE) platform for the first time, which showed 27-fold and 17-fold enhancements, respectively. The latter complex having the dual emission was then used for the fabrication of a ratiometric sensor for studying the oxygen quenching of phosphorescence emission with the fluorescence emission acting as an internal standard. Low-cost poly (methyl methacrylate) (PMMA) and biodegradable wood were used to fabricate the microfluidic chips for oxygen monitoring. The sensor showed a high sensitivity with a limit of detection ∼ 0.1%. Furthermore, real-time oxygen sensing was carried out and the response time of the sensor was calculated to be ∼0.2 s. The sensor chip was used for monitoring the oxygen uptake in SARS-CoV-2-recovered study participants, to assess their lung function post the viral infection.