Toward Nano- and Microplastic Sensors: Identification of Nano- and Microplastic Particles via Artificial Intelligence Combined with a Plasmonic Probe Functionalized with an Estrogen Receptor.

Nano- and microplastic particles are a global and emerging environmental issue that might pose potential threats to human health. The present work exploits artificial intelligence (AI) to identify nano- and microplastics in water by monitoring the interaction of the sample with a sensitive surface. An estrogen receptor (ER) grafted onto a gold surface, realized on a nonexpensive and easy-to-produce plastic optical fiber (POF) platform in order to excite a surface plasmon resonance (SPR) phenomenon, has been developed in order to carry out a "smart" sensitive interface (ER-SPR-POF interface). The ER-SPR-POF interface offers output data useful for exploiting a machine learning-based approach to achieve nano- and microplastic particle sensors. This work developed a proof-of-concept sensor through a training phase carried out by different particles, in terms of materials and size. The experimental results have demonstrated that the proposed "smart" ER-SPR-POF interface combined with AI can be used to identify the kind of particles in terms of the materials (polystyrene; poly(methyl methacrylate)) and size (20 µm; 100 nm) with an accuracy of 90.3%.

Hybrid BOFDA/BOCDA system for distributed static and dynamic strain measurements.

We present a distributed optical fiber sensor based on a hybrid Brillouin optical frequency/correlation-domain analysis (BOFDA/BOCDA) configuration for both static and dynamic strain measurements. Distributed static strain (or temperature) measurements are realized using the conventional BOFDA method, i.e., acquiring the baseband transfer function of the fiber through a vector network analyzer (VNA). With little modifications, the same setup can perform dynamic, position-selective measurements synthesizing a correlation peak through a frequency modulation of the laser source while operating the VNA at a single modulation frequency. Experimental tests, carried out at a sampling frequency up to 40 Hz and a spatial resolution of ≈5 cm, demonstrate the validity of the proposed approach.

Distributed Temperature Sensing through Network Analysis Frequency-Domain Reflectometry.

In this paper, we propose and demonstrate a network analysis optical frequency domain reflectometer (NA-OFDR) for distributed temperature measurements at high spatial (down to ≈3 cm) and temperature resolution. The system makes use of a frequency-stepped, continuous-wave (cw) laser whose output light is modulated using a vector network analyzer. The latter is also used to demodulate the amplitude of the beat signal formed by coherently mixing the Rayleigh backscattered light with a local oscillator. The system is capable of attaining high measurand resolution (≈50 mK at 3-cm spatial resolution) thanks to the high sensitivity of coherent Rayleigh scattering to temperature. Furthermore, unlike the conventional optical-frequency domain reflectometry (OFDR), the proposed system does not rely on the use of a tunable laser and therefore is less prone to limitations related to the laser coherence or sweep nonlinearity. Two configurations are analyzed, both numerically and experimentally, based on either a double-sideband or single-sideband modulated probe light. The results confirm the validity of the proposed approach.

3D-printed biosensors in biomedical applications exploiting plasmonic phenomena and antibody self-assembled monolayers.

In this work, a 3D-printed plasmonic chip based on a silver-gold bilayer was developed in order to enhance the optical response of the surface plasmon resonance (SPR) probe. More specifically, numerical and experimental results were obtained on the 3D-printed SPR platform based on a silver-gold bilayer. Then, the optimized probe's gold plasmonic interface was functionalized with a specific antibody directed against the p27Kip1 protein (p27), an important cell cycle regulator. The 3D-printed plasmonic biosensor was tested for p27 detection with good selectivity and a detection limit of 55 pM. The biosensor system demonstrated performance similar to commercially available ELISA (enzyme-linked immunoassay) kits, with several advantages, such as a wide detection range and a modular and simple-based architecture. The proposed biosensing technology offers flexible deployment options that are useful in disposable, low-cost, small-size, and simple-to-use biochips, envisaging future applications in experimental and biomedical research.

Plasmonic immunosensors based on spoon-shaped waveguides for fast and on-site ultra-low detection of ochratoxin A in coffee samples.

The high toxicity and occurrence of ochratoxin A (OTA) in grains and foods has been a growing concern due to the impacts on health and the economy in many countries. In this sense, simplified devices with high sensitivity and specificity for local monitoring are enthusiastically pursued. In this work, we report for the first time the detection of ochratoxin A in coffee samples using a spoon-shaped waveguide immunosensor. The biosensor was built with the surface of the spoon-shaped waveguide covered by a 60 nm layer of gold to enable the SPR phenomenon. The measurements indicated a linear relationship between the change in the SPR phenomenon values and the OTA concentration in the range from 0.2 ppt to 5 ppt. When analyzed in coffee samples, the biosensor was highly selective and did not suffer matrix interference. The developed biosensor represents a promising analytical device for coffee quality analyses, as it is portable, simple, and suitable for onsite detection of target analytes.

Plasmon resonance biosensor for interleukin-1ß point-of-care determination: A tool for early periodontitis diagnosis.

Among pro-inflammatory cytokines, Interleukin-1ß is crucially involved in several inflammatory-based diseases and even cancer. Increased Interleukin-1ß levels in oral fluids have been proposed as an early marker of periodontitis, a broadly diffused chronic inflammatory condition of periodontal-supporting tissues, leading eventually to tooth loss. We describe the development of a portable surface-plasmon-resonance-based optical fiber probe suitably coated with an anti-Interleukin-1ß antibody monolayer. A pico-nanomolar linear range of determination was obtained in both buffer solution and saliva with a rapid (3 min) incubation and high selectivity in presence of interferents. Higher Interleukin-1ß concentration in the saliva of a periodontitis patient compared to a healthy control was determined. These measurements were validated by an automated ELISA system. Our results sustain the potential applicability of the proposed SPR-POF as diagnostic point-of-care device for real-time monitoring of salivary Interleukin-1ß, that can support early detection of oral inflammatory-based pathologies and rapid and timely therapeutic decisions.

A novel plasmonic optical-fiber-based point-of-care test for periodontal MIP-1α detection.

The analysis of salivary biomarkers as expression of periodontal health conditions has been proposed as a useful aid to conventional diagnostic approaches. In this study, we present a point-of-care test (POCT) exploiting a surface plasmon resonance (SPR)-based optical biosensor to detect salivary macrophage inflammatory protein (MIP)-1α, a promising marker of periodontitis. A plastic optical fiber (POF) was suitably modified and functionalized by an antibody self-assembled monolayer against MIP-1α for plasmonic detection. The proposed SPR-POF biosensor showed high selectivity and very low limit of detection for MIP-1α of 129 fM (1.0 pg/mL) in phosphate-buffered saline and 346 fM (2.7 pg/mL) in saliva. As a proof of concept, this POCT was also able to discriminate between a periodontitis patient and a healthy subject. The obtained results support the future application of this technology for an on-site detection and real-time monitoring of periodontal health conditions for diagnostic and therapeutic purposes.

Immuno-SPR biosensor for the detection of Brucella abortus.

A proof of principle biosensor for the Brucella abortus recognition onsite is presented. The system is based on a plasmonic optical fiber probe functionalized with an oriented antibody layer immobilized on a short polyethyleneglycol (PEG) interface through carbodiimide chemistry and protein G as an intermediate layer. The biosensor is inserted in a holder built in 3D printing technology, obtaining a custom holder useful for housing the sample to be measured and the equipment. The removable sensor chip is a low-cost Surface Plasmon Resonance (SPR) platform based on D-shaped plastic optical fibers (POFs), built-in in 3D printed connectors, used here for the first time to detect bacteria via a bio-receptor layer specific for its membrane protein. The performances of the biosensor in Brucella abortus recognition are tested by using two different SPR-POF probes combined with the same bio-receptor layer. The best sensor configuration has presented a sensitivity at low concentrations of one order of magnitude greater than the other. A limit of detection (LoD) of 2.8 bacteria/mL is achieved well competitive with other systems but without the need for amplification or special sample treatments. Specificity has been tested using Salmonella bacteria, and reproducibility, regenerability and stability are moreover evaluated. These experimental results pave the way for building an efficient and specific biosensor system for Brucella abortus detection onsite and in a few minutes. Moreover, the proposed POF-based SPR biosensor device, with respect to the already available technologies, could be a Point-of-care-test (POCT), simple to use, small-size and portable, low-cost, don't necessary of a microfluidic system, and can be connected to the Internet (IoT).

Optimization of the immunorecognition layer towards Brucella sp. on gold surface for SPR platform.

A successful immunosensor is characterized by a proper antibody immobilization and orientation in order to enhance the antigen recognition. In this work, a thorough characterization of the antibody functionalized gold surface is performed to set up the best conditions to implement in an optical platform for the detection of Brucella sp. Two different strategies are evaluated, based on a random immobilization and on an oriented one: a direct antibody immobilization on carboxylic mixed polyethylene (PEG) self-assembled monolayer (SAM) or only carboxylic PEG SAM interface is compared to an oriented immobilization on a layer of protein G on the same PEG SAM interfaces. X-ray Photoelectron Spectroscopy (XPS), Time of Flight Secondary Ion Mass Spectrometry (ToF-SIMS) and contact angle (CA) are used to chemically characterize the gold functionalized surface and ToF-SIMS is also used to confirm the right antibody orientation. Optical characterization is applied to monitor the functionalization steps and fluorescence measurements are used to set up the proper experimental conditions and also to detect Brucella bacteria on the surface. Best results are obtained with a 10 ng/µl incubation solution of antibody immobilized, in an oriented way, on a mixed PEG SAM interface.

Sensing Approaches Exploiting Molecularly Imprinted Nanoparticles and Lossy Mode Resonance in Polymer Optical Fibers.

In this work, two different lossy mode resonance (LMR) platforms based on plastic optical fibers (POFs) are developed and tested in a biochemical sensing scenario. The LMR platforms are based on the combination of two metal oxides (MOs), i.e., zirconium oxide (ZrO2) and titanium oxide (TiO2), and deposited on the exposed core of D-shaped POF chips. More specifically, two experimental sensor configurations were obtained by swapping the mutual position of the Mos films over to the core of the D-shaped POF probe. The POF-LMR sensors were first characterized as refractometers, proving the bulk sensitivities. Then, both the POF-LMR platforms were functionalized using molecularly imprinted nanoparticles (nanoMIPs) specific for human transferrin (HTR) in order to carry out binding tests. The achieved results report a bulk sensitivity equal to about 148 nm/RIU in the best sensor configuration, namely the POF-TiO2-ZrO2. In contrast, both optical configurations combined with nanoMIPs showed an ultra-low detection limit (fM), demonstrating excellent efficiency of the used receptor (nanoMIPs) and paving the way to disposable POF-LMR biochemical sensors that are easy-to-use, low-cost, and highly sensitive.

Polymer Doping as a Novel Approach to Improve the Performance of Plasmonic Plastic Optical Fibers Sensors.

In this work, Fe2O3 was investigated as a doping agent for poly(methyl methacrylate) (PMMA) in order to enhance the plasmonic effect in sensors based on D-shaped plastic optical fibers (POFs). The doping procedure consists of immerging a premanufactured POF sensor chip in an iron (III) solution, avoiding repolymerization and its related disadvantages. After treatment, a sputtering process was used to deposit a gold nanofilm on the doped PMMA in order to obtain the surface plasmon resonance (SPR). More specifically, the doping procedure increases the refractive index of the POF's PMMA in contact with the gold nanofilm, improving the SPR phenomena. The doping of the PMMA was characterized by different analyses in order to determine the effectiveness of the doping procedure. Moreover, experimental results obtained by exploiting different water-glycerin solutions have been used to test the different SPR responses. The achieved bulk sensitivities confirmed the improvement of the plasmonic phenomenon with respect to a similar sensor configuration based on a not-doped PMMA SPR-POF chip. Finally, doped and non-doped SPR-POF platforms were functionalized with a molecularly imprinted polymer (MIP), specific for the bovine serum albumin (BSA) detection, to obtain dose-response curves. These experimental results confirmed an increase in binding sensitivity for the doped PMMA sensor. Therefore, a lower limit of detection (LOD), equal to 0.04 µM, has been obtained in the case of the doped PMMA sensor when compared to the one calculated for the not-doped sensor configuration equal to about 0.09 µM.

A Novel Approach to Realize Plasmonic Sensors via Multimode Optical Waveguides: A Review.

In recent decades, the Surface Plasmon Resonance (SPR) phenomenon has been utilized as an underlying technique in a broad range of application fields. Herein, a new measuring strategy which harnesses the SPR technique in a way that is different from the classical methodology was explored by taking advantage of the characteristics of multimode waveguides, such as plastic optical fibers (POFs) or hetero-core fibers. The sensor systems based on this innovative sensing approach were designed, fabricated, and investigated to assess their ability to measure various physical features, such as magnetic field, temperature, force, and volume, and to realize chemical sensors. In more detail, a sensitive patch of fiber was used in series with a multimodal waveguide where the SPR took place, to alter the mode profile of the light at the input of the waveguide itself. In fact, when the changes of the physical feature of interest acted on the sensitive patch, a variation of the incident angles of the light launched in the multimodal waveguide occurred, and, as a consequence, a shift in resonance wavelength took place. The proposed approach permitted the separation of the measurand interaction zone and the SPR zone. This meant that the SPR zone could be realized only with a buffer layer and a metallic film, thus optimizing the total thickness of the layers for the best sensitivity, regardless of the measurand type. The proposed review aims to summarize the capabilities of this innovative sensing approach to realize several types of sensors for different application fields, showing the high performances obtained by exploiting a simple production process and an easy experimental setup.

Soft molecularly imprinted nanoparticles with simultaneous lossy mode and surface plasmon multi-resonances for femtomolar sensing of serum transferrin protein.

The simultaneous interrogation of both lossy mode (LMR) and surface plasmon (SPR) resonances was herein exploited for the first time to devise a sensor in combination with soft molecularly imprinting of nanoparticles (nanoMIPs), specifically entailed of the selectivity towards the protein biomarker human serum transferrin (HTR). Two distinct metal-oxide bilayers, i.e. TiO2-ZrO2 and ZrO2-TiO2, were used in the SPR-LMR sensing platforms. The responses to binding of the target protein HTR of both sensing configurations (TiO2-ZrO2-Au-nanoMIPs, ZrO2-TiO2-Au-nanoMIPs) showed femtomolar HTR detection, LODs of tens of fM and KDapp ~ 30 fM. Selectivity for HTR was demonstrated. The SPR interrogation was more efficient for the ZrO2-TiO2-Au-nanoMIPs configuration (sensitivity at low concentrations, S = 0.108 nm/fM) than for the TiO2-ZrO2-Au-nanoMIPs one (S = 0.061 nm/fM); while LMR was more efficient for TiO2-ZrO2-Au-nanoMIPs (S = 0.396 nm/fM) than for ZrO2-TiO2-Au-nanoMIPs (S = 0.177 nm/fM). The simultaneous resonance monitoring is advantageous for point of care determinations, both in terms of measurement's redundancy, that enables the cross-control of the measure and the optimization of the detection, by exploiting the individual characteristics of each resonance.

Analysis of Plasmonic Sensors Performance Realized by Exploiting Different UV-Cured Optical Adhesives Combined with Plastic Optical Fibers.

Polymer-based surface plasmon resonance (SPR) sensors can be used to realize simple, small-size, disposable, and low-cost biosensors for application in several fields, e.g., healthcare. The performance of SPR sensors based on optical waveguides can be changed by tuning several parameters, such as the dimensions and the shape of the waveguides, the refractive index of the core, and the metal nanofilms used to excite the SPR phenomenon. In this work, in order to develop, experimentally test, and compare several polymer-based plasmonic sensors, realized by using waveguides with different core refractive indices, optical adhesives and 3D printed blocks with a trench inside have been used. In particular, the sensors are realized by filling the blocks' trenches (with two plastic optical fibers located at the end of these) with different UV-cured optical adhesives and then covering them with the same bilayer to excite the SPR phenomenon. The developed SPR sensors have been characterized by numerical and experimental results. Finally, in order to propose photonic solutions for healthcare, a comparative analysis has been reported to choose the best sensor configuration useful for developing low-cost biosensors.

Tuning of the Brillouin scattering properties in microstructured optical fibers by liquid infiltration.

We demonstrate the possibility to modify the Brillouin scattering properties of a microstructured pure-silica core optical fiber, by infiltrating a liquid inside its holes. In particular, we show that the dependence of the Brillouin frequency shift (BFS) on the temperature can be reduced by infiltration, owing to the large negative thermo-optic coefficient of the liquid. Infiltrating a chloroform-acetonitrile mixture with a refractive index of 1.365 inside the holes of a suspended-core fiber with a core diameter of 3 µm, the BFS temperature sensing coefficient is reduced by ≈ 21%, while the strain sensitivity remains almost unaltered. Besides tuning the temperature sensing coefficient, the proposed platform could find other applications in Brillouin sensing, such as distributed electrical and magnetic measurements, or enhanced Brillouin gain in fibers infiltrated with high nonlinear optical media.

An optical fiber-based point-of-care test for periodontal MMP-8 detection: A proof of concept.

OBJECTIVES: The evaluation of salivary biomarkers has been proposed as a simple and non-invasive aid to the conventional periodontal diagnosis based on clinical-radiographic parameters. Matrix metalloproteinase-8 (MMP-8), especially in its active form, is considered one of the most reliable biomarkers of periodontitis, and point-of-care tests (POCTs) have been proposed for its clinical monitoring. In this proof-of-concept study, a novel highly sensitive POCT based on a plastic optical fiber (POF) biosensor exploiting surface plasmon resonance (SPR) to detect salivary MMP-8 is described. METHODS: A SPR-POF biosensor was functionalized with a specific antibody to develop a surface-assembled monolayer (SAM) for the detection of total MMP-8. A white light source and a spectrometer connected to the biosensor were used to quantify MMP-8 level in both buffer and real matrix (saliva) by analysing the shift of the resonance wavelength determined by the specific antigen-antibody binding upon the SAM. RESULTS: Dose-response curves by serial dilutions of human recombinant MMP-8 were realized, obtaining a limit of detection (LOD) of 40 pM (1.76 ng/ml) in buffer and 225 pM (9.9 ng/ml) in saliva and high selectivity compared to interferent analytes (MMP-2 and IL-6). CONCLUSIONS: The proposed optical fiber-based POCT was able to detect and measure total MMP-8 with high selectivity and very low LOD in both buffer and saliva. CLINICAL SIGNIFICANCE: The SPR-POF technology may be employed to create highly sensitive biosensors to monitor salivary MMP-8 levels. The possibility of specifically detecting its active, rather than total, form need to be further investigated. If confirmed and clinically validated, such a device may represent a promising tool to make an immediate, highly sensitive and reliable diagnosis of periodontitis, and to carry out a timely and targeted therapy, possibly helping to prevent the onset of local and systemic periodontitis-related complications.

Estradiol Detection for Aquaculture Exploiting Plasmonic Spoon-Shaped Biosensors.

In this work, a surface plasmon resonance (SPR) biosensor based on a spoon-shaped waveguide combined with an estrogen receptor (ERα) was developed and characterized for the detection and the quantification of estradiol in real water samples. The fabrication process for realizing the SPR platform required a single step consisting of metal deposition on the surface of a polystyrene spoon-shaped waveguide featuring a built-in measuring cell. The biosensor was achieved by functionalizing the bowl sensitive surface with a specific estrogen receptor (ERα) that was able to bind the estradiol. In a first phase, the biosensor tests were performed in a phosphate buffer solution obtaining a limit of detection (LOD) equal to 0.1 pM. Then, in order to evaluate the biosensor's response in different real matrices related to aquaculture, its performances were examined in seawater and freshwater. The experimental results support the possibility of using the ERα-based biosensor for the screening of estradiol in both matrices.

Innovative Photonic Sensors for Safety and Security, Part II: Aerospace and Submarine Applications.

The employability of photonics technology in the modern era's highly demanding and sophisticated domain of aerospace and submarines has been an appealing challenge for the scientific communities. In this paper, we review our main results achieved so far on the use of optical fiber sensors for safety and security in innovative aerospace and submarine applications. In particular, recent results of in-field applications of optical fiber sensors in aircraft monitoring, from a weight and balance analysis to vehicle Structural Health Monitoring (SHM) and Landing Gear (LG) monitoring, are presented and discussed. Moreover, underwater fiber-optic hydrophones are presented from the design to marine application.

Innovative Photonic Sensors for Safety and Security, Part I: Fundamentals, Infrastructural and Ground Transportations.

Our group, involving researchers from different universities in Campania, Italy, has been working for the last twenty years in the field of photonic sensors for safety and security in healthcare, industrial and environment applications. This is the first in a series of three companion papers. In this paper, we introduce the main concepts of the technologies employed for the realization of our photonic sensors. Then, we review our main results concerning the innovative applications for infrastructural and transportation monitoring.

Innovative Photonic Sensors for Safety and Security, Part III: Environment, Agriculture and Soil Monitoring.

In order to complete this set of three companion papers, in this last, we focus our attention on environmental monitoring by taking advantage of photonic technologies. After reporting on some configurations useful for high precision agriculture, we explore the problems connected with soil water content measurement and landslide early warning. Then, we concentrate on a new generation of seismic sensors useful in both terrestrial and under water contests. Finally, we discuss a number of optical fiber sensors for use in radiation environments.