Splitter-Based Sensors Realized via POFs Coupled by a Micro-Trench Filled with a Molecularly Imprinted Polymer.

An optical-chemical sensor based on two modified plastic optical fibers (POFs) and a molecularly imprinted polymer (MIP) is realized and tested for the detection of 2-furaldehyde (2-FAL). The 2-FAL measurement is a scientific topic of great interest in different application fields, such as human health and life status monitoring in power transformers. The proposed sensor is realized by using two POFs as segmented waveguides (SW) coupled through a micro-trench milled between the fibers and then filled with a specific MIP for the 2-FAL detection. The experimental results show that the developed intensity-based sensor system is highly selective and sensitive to 2-FAL detection in aqueous solutions, with a limit of detection of about 0.04 mg L-1. The proposed sensing approach is simple and low-cost, and it shows performance comparable to that of plasmonic MIP-based sensors present in the literature for 2-FAL detection.

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.

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.

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.

Exploiting Plasmonic Phenomena in Polymer Optical Fibers to Realize a Force Sensor.

In this work, a novel sensing approach to realize a force optical fiber sensor is designed, developed, and experimentally tested. The proposed sensing methodology exploits the effects of deformation due to an applied force on a patch of plastic optical fiber (POF) connected at the input of a surface plasmon resonance (SPR) sensor realized in a D-shaped POF. Therefore, the proposed force sensor system consists of an SPR D-shaped POF sensor, connected to a spectrometer, within input of a POF patch, connected to a light source used for interacting with the applied force. When the applied force on the patch changes, the mode profile of the light in the multimode POF patch and the SPR-POF sensor change too, so the SPR spectra shift. The obtained experimental results demonstrate that the proposed sensor has a resolution of the force sensor equal to about 22 mN and an excellent linear response in the range from 0 N to 0.5 N.

Non-Specific Responsive Nanogels and Plasmonics to Design MathMaterial Sensing Interfaces: The Case of a Solvent Sensor.

The combination of non-specific deformable nanogels and plasmonic optical probes provides an innovative solution for specific sensing using a generalistic recognition layer. Soft polyacrylamide nanogels that lack specific selectivity but are characterized by responsive behavior, i.e., shrinking and swelling dependent on the surrounding environment, were grafted to a gold plasmonic D-shaped plastic optical fiber (POF) probe. The nanogel-POF cyclically challenged with water or alcoholic solutions optically reported the reversible solvent-to-phase transitions of the nanomaterial, embodying a primary optical switch. Additionally, the non-specific nanogel-POF interface exhibited more degrees of freedom through which specific sensing was enabled. The real-time monitoring of the refractive index variations due to the time-related volume-to-phase transition effects of the nanogels enabled us to determine the environment's characteristics and broadly classify solvents. Hence the nanogel-POF interface was a descriptor of mathematical functions for substance identification and classification processes. These results epitomize the concept of responsive non-specific nanomaterials to perform a multiparametric description of the environment, offering a specific set of features for the processing stage and particularly suitable for machine and deep learning. Thus, soft MathMaterial interfaces provide the ground to devise devices suitable for the next generation of smart intelligent sensing processes.

Detection of 2-Furaldehyde in Milk by MIP-Based POF Chips Combined with an SPR-POF Sensor.

An innovative optical-chemical sensor has been used to detect the 2-furaldehyde (2-FAL) in milk. The proposed sensing approach exploits the refractive index changing in a microstructured chip based on a plastic optical fiber (POF) with orthogonal micro-holes containing a specific molecularly imprinted polymer (MIP). This POF-MIP chemical chip modifies the surface plasmon resonance (SPR) phenomena excited in another sensor chip realized in POFs (SPR-POF) and connected in series. The proposed sensor configuration exploits MIP receptors avoiding any modification of the gold film of the SPR platform. This work reports the performance, particularly the high sensitivity and low detection limit, in complex matrices such as buffalo milk fortified with 2-FAL and in different commercial kinds of cow milk thermally treated for pasteurization. The measurements were carried out in about ten minutes by dropping the solution under-test on the planar D-shaped POF surface of the chemical chip. In contrast, on the gold surface of the SPR-POF platform, a water drop is always placed to excite the SPR phenomenon, which is modulated by the chemical chip via MIP-2-FAL binding. Furthermore, the experimental results demonstrated the pros and cons of the proposed sensor system. Thanks to the high sensitivity of the sensor system, the detection of 2-FAL in the diluted milk sample (1:50) was achieved. The dilution is required to reduce the interferent effect of the complex matrix.

Automatic traffic monitoring by ϕ-OTDR data and Hough transform in a real-field environment.

In this paper, we demonstrate automatic vehicle detection and counting by processing data acquired using a phase-sensitive optical time-domain reflectometer (ϕ-OTDR) distributed optical fiber sensor. The acquired data are processed using the Hough transform, which detects the lines in the images formed by representing the acquired data in the space-time domain. A rough classification of the vehicles (heavy versus light vehicles) is also proposed, based on the amplitude of the vibration data along the detected lines. The method has been experimentally tested by performing ϕ-OTDR measurements along a telecommunication fiber cable running in a buried conduit along the state road SS18 (province of Salerno, Italy), opened to normal traffic. Comparison with ground-truth data, manually generated by inspecting video recordings, allowed us to estimate a vehicle detection success rate up to 73%, while heavy vehicles were fully detected.

The Role of Tapered Light-Diffusing Fibers in Plasmonic Sensor Configurations.

In this work, we experimentally analyzed the effect of tapering in light-diffusing optical fibers (LDFs) when employed as surface plasmon resonance (SPR)-based sensors. Although tapering is commonly adopted to enhance the performance of plasmonic optical fiber sensors, we have demonstrated that in the case of plasmonic sensors based on LDFs, the tapering produces a significant worsening of the bulk sensitivity (roughly 60% in the worst case), against a slight decrease in the full width at half maximum (FWHM) of the SPR spectra. Furthermore, we have demonstrated that these aspects become more pronounced when the taper ratio increases. Secondly, we have established that a possible alternative exists in using the tapered LDF as a modal filter after the sensible region. In such a case, we have determined that a good trade-off between the loss in sensitivity and the FWHM decrease could be reached.

Distributed Static and Dynamic Strain Measurements in Polymer Optical Fibers by Rayleigh Scattering.

We demonstrate the use of a graded-index perfluorinated optical fiber (GI-POF) for distributed static and dynamic strain measurements based on Rayleigh scattering. The system is based on an amplitude-based phase-sensitive Optical Time-Domain Reflectometry (ϕ-OTDR) configuration, operated at the unconventional wavelength of 850 nm. Static strain measurements have been carried out at a spatial resolution of 4 m and for a strain up to 3.5% by exploiting the increase of the backscatter Rayleigh coefficient consequent to the application of a tensile strain, while vibration/acoustic measurements have been demonstrated for a sampling frequency up to 833 Hz by exploiting the vibration-induced changes in the backscatter Rayleigh intensity time-domain traces arising from coherent interference within the pulse. The reported tests demonstrate that polymer optical fibers can be used for cost-effective multiparameter sensing.

A Surface Plasmon Resonance Plastic Optical Fiber Biosensor for the Detection of Pancreatic Amylase in Surgically-Placed Drain Effluent.

Postoperative pancreatic fistula (POPF), the major driver of morbidity and mortality following pancreatectomy, is caused by an abnormal communication between the pancreatic ductal epithelium and another epithelial surface containing pancreas-derived, enzyme-rich fluid. There is a strong correlation between the amylase content in surgically-placed drains early in the postoperative course and the development of POPF. A simple and cheap method to determine the amylase content from the drain effluent has been eagerly advocated. Here, we developed an amylase optical biosensor, based on a surface plasmon resonance (SPR) plastic optical fiber (POF), metallized with a 60 nm layer of gold and interrogated with white light. The sensor was made specific by coupling it with an anti-amylase antibody. Each surface derivatization step was optimized and studied by XPS, contact angle, and fluorescence. The POF-biosensor was tested for its response to amylase in diluted drain effluents. The volume of sample required was 50 µL and the measurement time was 8 min. The POF-biosensor showed selectivity for amylase, a calibration curve log-linear in the range of 0.8-25.8 U/L and a limit of detection (LOD) of ~0.5 U/L. In preliminary tests, the POF-biosensor allowed for the measurement of the amylase content of diluted surgically-placed drain effluents with an accuracy of >92% with respect to the gold standard. The POF-biosensor allows for reliable measurement and could be implemented to allow for a rapid bedside assessment of amylase value in drains following pancreatectomy.

Proof of Concept for a Quick and Highly Sensitive On-Site Detection of SARS-CoV-2 by Plasmonic Optical Fibers and Molecularly Imprinted Polymers.

The rapid spread of the Coronavirus Disease 2019 (COVID-19) pandemic, caused by the Severe Acute Respiratory Syndrome Coronavirus 2 (SARS-CoV-2) pathogen has generated a huge international public health emergency. Currently the reference diagnostic technique for virus determination is Reverse Transcription Polymerase Chain Reaction (RT-PCR) real time analysis that requires specialized equipment, reagents and facilities and typically 3-4 h to perform. Thus, the realization of simple, low-cost, small-size, rapid and point-of-care diagnostics tests has become a global priority. In response to the current need for quick, highly sensitive and on-site detection of the SARS-CoV-2 virus in several aqueous solutions, a specific molecularly imprinted polymer (MIP) receptor has been designed, realized, and combined with an optical sensor. More specifically, the proof of concept of a SARS-CoV-2 sensor has been demonstrated by exploiting a plasmonic plastic optical fiber sensor coupled with a novel kind of synthetic MIP nano-layer, especially designed for the specific recognition of Subunit 1 of the SARS-CoV-2 Spike protein. First, we have tested the effectiveness of the developed MIP receptor to bind the Subunit 1 of the SARS-CoV-2 spike protein, then the results of preliminary tests on SARS-CoV-2 virions, performed on samples of nasopharyngeal (NP) swabs in universal transport medium (UTM) and physiological solution (0.9% NaCl), were compared with those obtained with RT-PCR. According to these preliminary results, the sensitivity of the proposed optical-chemical sensor proved to be higher than the RT-PCR one. Furthermore, a relatively fast response time (about 10 min) to the virus was obtained without the use of additional reagents.

Sensing by Molecularly Imprinted Polymer: Evaluation of the Binding Properties with Different Techniques.

The possibility of investigating the binding properties of the same molecularly imprinted polymer (MIP), most probably heterogeneous, at various concentration levels by different methods such as batch equilibration and sensing, is examined, considering two kinds of sensors, based respectively on electrochemical and surface plasmon resonance (SPR) transduction. As a proof of principle, the considered MIP was obtained by non-covalent molecular imprinting of 2-furaldehyde (2-FAL). It has been found that different concentration ranges of 2-FAL in aqueous matrices can be measured by the two sensing methods. The SPR sensor responds in a concentration range from 1 × 10-4 M down to about 1 × 10-7 M, while the electrochemical sensor from about 5 × 10-6 M up to about 9 × 10-3 M. The binding isotherms have been fit to the Langmuir adsorption model, in order to evaluate the association constant. Three kinds of sites with different affinity for 2-FAL have been detected. The sites at low affinity are similar to the interaction sites of the corresponding NIP since they have a similar association constant. This is near to the affinity evaluated by batch equilibration too. The same association constant has been evaluated in the same concentration range. The sensing methods have been demonstrated to be very convenient for the characterization of the binding properties of MIP in comparison to the batch equilibration, in terms of reproducibility and low amount of material required for the investigation.

An Eco-Friendly Disposable Plasmonic Sensor Based on Bacterial Cellulose and Gold.

In several application fields, plasmonic sensor platforms combined with bio-receptors are intensively used to obtain biosensors. Most of these commercial devices are based on a disposable chip. Usually a gold chip, functionalized with a specific bio-receptor, inside a costly sensor system, is used. In this work, we propose a low-cost and small-size sensor system, used for monitoring a disposable plasmonic chip, based on an innovative optical waveguide made of bacterial cellulose (BC). In particular, we have sputtered gold on the green slab waveguide that is able to excite localized surface plasmon resonance (LSPR). Experimental results are presented on the capabilities of using the BC-based composite as an eco-friendly plasmonic sensor platform, which could be exploited for realizing disposable biosensors. The sensor has been used with optical fibers and simple equipment. More specifically, the fibers connect the green disposable LSPR sensor with a light source and with a spectrometer. The novel plasmonic sensing approach has been tested using two different optical waveguide configurations of BC, with and without ions inside BC.

An Optical Fiber Chemical Sensor for the Detection of Copper(II) in Drinking Water.

Highly sensitive plasmonic optical fiber platforms combined with receptors have been recently used to obtain selective sensors. A low-cost configuration can be obtained exploiting a D-shaped plastic optical fiber covered with a multilayer sensing surface. The multilayer consists of a gold film, functionalized with a specific receptor, where the surface plasmon resonance (SPR) occurs. The signal is produced by the refractive index variation occurring as a consequence of the receptor-to analyte binding. In this work, a selective sensor for copper(II) detection in drinking water, exploiting a self-assembled monolayer (SAM) of d,l-penicillamine as the sensing layer, has been developed and tested. Different concentrations of copper(II) in NaCl 0.1 M solutions at different pH values and in a real matrix (drinking water) have been considered. The results show that the sensor is able to sense copper(II) at concentrations ranging from 4 × 10-6 M to 2 × 10-4 M. The use of this optical chemical sensor is a very attractive perspective for fast, in situ and low-cost detection of Cu(II) in drinking water for human health concerns. Furthermore, the possibility of remote control is feasible as well, because optical fibers are employed.

D-Shaped POF Sensors for Refractive Index Sensing-The Importance of Surface Roughness.

In this study the influence of the surface roughness on the transmission capacities of D-shaped plastic optical fibers (POFs) and sensors performance was investigated. Five D-shaped POF sensors were produced and characterized for refractive index sensing between 1.33 and 1.41. The sensors were characterized using a low-cost optical sensing system based on the variation of the transmitted light though the POF with refractive index changes (RI). Higher surface roughness increases the scattering losses through the POF and influences the sensors' performance; therefore, a balance must be attained. Generally, the best performance was achieved when the sensing region was polished with P600 sandpaper as a final polishing step. Polishing with sandpapers of lower grit size resulted in lower scattering, higher linearity of the sensor response and generally lower performance for RI sensing. A sensor resolution of 10-3-10-4 RIU, dependent on the value of the external refractive index, was obtained through simple and low-cost manufacturing procedures. The obtained results show the importance of surface roughness in the development of POF sensors which can be used in several applications, such as for water quality assessment.

A Simple and Low-Cost Optical Fiber Intensity-Based Configuration for Perfluorinated Compounds in Water Solution.

We present a very simple approach for the detection of the Perfluorinated Alkylated Substances (PFAs) in water solution. Perfluorooctanesulfonate (PFOS) and Perfluorooctanoate (PFOA) are the most extensively investigated perfluoroalkyl and polyfluoroalkyl substances in water because human exposition can occur through different pathways, even if the dietary intake seems to be their main route of exposure. The developed sensor is based on a specific Molecularly Imprinted Polymer (MIP) receptor deposited on a simple D-shaped Plastic Optical Fiber (POF) platform. This novel chemical sensor has been characterized using a very simple and low-cost experimental setup based on an LED and two photodetectors. This optical sensor system is an alternative method to monitor the presence of contaminants with an MIP receptor, instead of a surface plasmon resonance (SPR) sensor in D-shaped POFs. For the sake of comparison, the results obtained exploiting the same MIP for PFAs on a classic SPR-POF sensor have been reported. The experimental results have shown that the actual limit of detection of this new configuration was about 0.5 ppb. It is similar to the one obtained by the configuration based on an SPR-POF with the same MIP receptor.

A Molecularly Imprinted Polymer on a Plasmonic Plastic Optical Fiber to Detect Perfluorinated Compounds in Water.

A novel Molecularly Imprinted Polymer (MIP) able to bind perfluorinated compounds, combined with a surface plasmon resonance (SPR) optical fiber platform, is presented. The new MIP receptor has been deposited on a D-shaped plastic optical fiber (POF) covered with a photoresist buffer layer and a thin gold film. The experimental results have shown that the developed SPR-POF-MIP sensor makes it possible to selectively detect the above compounds. In this work, we present the results obtained with perfluorooctanoate (PFOA) compound, and they hold true when obtained with a perfluorinated alkylated substances (PFAs) mixture sample. The sensor's response is the same for PFOA, perfluorooctanesulfonate (PFOS) or PFA contaminants in the C4⁻C11 range. We have also tested a sensor based on a non-imprinted polymer (NIP) on the same SPR in a D-shaped POF platform. The limit of detection (LOD) of the developed chemical sensor was 0.13 ppb. It is similar to the one obtained by the configuration based on a specific antibody for PFOA/PFOS exploiting the same SPR-POF platform, already reported in literature. The advantage of an MIP receptor is that it presents a better stability out of the native environment, very good reproducibility, low cost and, furthermore, it can be directly deposited on the gold layer, without modifying the metal surface by functionalizing procedures.

Slab Waveguide and Optical Fibers for Novel Plasmonic Sensor Configurations.

The use of plasmonic sensor devices often requires replaceable parts and disposable chips for easy, fast and on-site detection analysis. In light of these requests, we propose a novel low-cost surface plasmon resonance sensor platform for possible selective detection of analytes in aqueous solutions. It is based on a Polymethyl methacrylate (PMMA) slab waveguide with a thin gold film on the top surface inserted in a special holder, designed to produce the plasmonic resonance at the gold-dielectric interface. A wide-band light is launched in the PMMA slab waveguide through a trench realized in the holder directly, and illuminated with a PMMA plastic optical fiber (POF) to excite surface Plasmon waves. The output light is then collected by another PMMA POF kept at the end of the slab at an angle of 90° to the trench, and carried to a spectrometer. In this configuration, the trench has been used because a large incident angle is required for surface plasmon resonance excitation. The preliminary results showed that the sensor's performances make it suitable for bio-chemical applications. The easy replacement of the chip allows for the production of an engineered platform by simplifying the measurement procedures.

Refractive Index Sensing with D-Shaped Plastic Optical Fibers for Chemical and Biochemical Applications.

We report the optimization of the length of a D-shaped plastic optical fiber (POF) sensor for refractive index (RI) sensing from a numerical and experimental point of view. The sensing principle is based on total internal reflection (TIR). POFs with 1 mm in diameter were embedded in grooves, realized in planar supports with different lengths, and polished to remove the cladding and part of the core. All D-shaped POF sensors were tested using aqueous medium with different refractive indices (from 1.332 to 1.471) through intensity-based configuration. Results showed two different responses. Considering the refractive index (RI) range (1.33-1.39), the sensitivity and the resolution of the sensor were strongly dependent on the sensing region length. The highest sensitivity (resolution of 6.48 × 10-3 refractive index units, RIU) was obtained with 6 cm sensing length. In the RI range (1.41-1.47), the length of the sensing region was not a critical aspect to obtain the best resolution. These results enable the application of this optical platform for chemical and biochemical evanescent field sensing. The sensor production procedure is very simple, fast, and low-cost.