Enhanced spectroelectrochemistry with lossy-mode resonance optical fiber sensor.

Spectroelectrochemical (SEC) measurements play a crucial role in analytical chemistry, utilizing transparent or semitransparent electrodes for optical analysis of electrochemical (EC) processes. The EC readout provides information about the electrode's state, while changes in the transmitted optical spectrum help identify the products of EC reactions. To enhance SEC measurements, this study proposes the addition of optical monitoring of the electrode. The setup involves using a polymer-clad silica multimode fiber core coated with indium tin oxide (ITO), which serves as both the electrode and an optical fiber sensor. The ITO film is specifically tailored to exhibit the lossy-mode resonance (LMR) phenomenon, allowing for simultaneous optical monitoring alongside EC readouts. The LMR response depends on the properties of the ITO and the surrounding medium's optical properties. As a result, the setup offers three types of interrogation readouts: EC measurements, optical spectrum analysis corresponding to the volume of the analyte (similar to standard SEC), and LMR spectrum analysis reflecting the state of the sensor/electrode surface. In each interrogation path, cyclic voltammetry (CV) experiments were conducted individually with two oxidation-reduction reaction (redox) probes: potassium ferricyanide and methylene blue. Subsequently, simultaneous measurements were performed during chronoamperometry (CA) with the sensor, and the cross-correlation between the readouts was examined. Overall, this study presents a novel and enhanced SEC measurement approach that incorporates optical monitoring of the electrode. It provides a comprehensive understanding of EC processes and enables greater insights into the characteristics of the analyte.

Enhancement of lossy mode resonance sensing properties by the introduction of an intermediate low-refractive-index layer.

Devices based on the lossy mode resonance (LMR) effect have found numerous sensing applications. Herein, the enhancement of the sensing properties by the introduction of an intermediate layer between the substrate and the LMR-supporting film is discussed. Experimental results for a silicon oxide (SiO2) layer of tuned thickness between a glass slide substrate and a thin film of titanium oxide (TiO2) prove the possibility of significantly increasing the LMR depth and the figure of merit (FoM) for refractive index sensing applications, which is supported by a numerical analysis using the plane wave method for a one-dimensional multilayer waveguide. The application of the intermediate layer allows the introduction of a new, to the best of our knowledge, degree of freedom into the design of LMR-based sensors, resulting in improved performance for demanding fields such as chemical sensing or biosensing.

Low-volume label-free SARS-CoV-2 detection with the microcavity-based optical fiber sensor.

Accurate and fast detection of viruses is crucial for controlling outbreaks of many diseases; therefore, to date, numerous sensing systems for their detection have been studied. On top of the performance of these sensing systems, the availability of biorecognition elements specific to especially the new etiological agents is an additional fundamental challenge. Therefore, besides high sensitivity and selectivity, such advantages as the size of the sensor and possibly low volume of analyzed samples are also important, especially at the stage of evaluating the receptor-target interactions in the case of new etiological agents when typically, only tiny amounts of the receptor are available for testing. This work introduces a real-time, highly miniaturized sensing solution based on microcavity in-line Mach-Zehnder interferometer (µIMZI) induced in optical fiber for SARS-CoV-2 virus-like particles detection. The assay is designed to detect conserved regions of the SARS-CoV-2 viral particles in a sample with a volume as small as hundreds of picoliters, reaching the detection limit at the single ng per mL level.

A D-Shaped Polymer Optical Fiber Surface Plasmon Resonance Biosensor for Breast Cancer Detection Applications.

Fiber-optic biosensors have garnered significant attention and witnessed rapid development in recent years owing to their remarkable attributes such as high sensitivity, immunity to electromagnetic interference, and real-time monitoring. They have emerged as a potential tool in the realm of biomarker detection for low-concentration and small molecules. In this paper, a portable and cost-effective optical fiber biosensor based on surface plasmon resonance for the early detection of breast cancer is demonstrated. By utilizing the aptamer human epidermal growth factor receptor 2 (HER2) as a specific biomarker for breast cancer, the presence of the HER2 protein can be detected through an antigen-antibody binding technique. The detection method was accomplished by modifying a layer of HER2 aptamer on the flat surface of a gold-coated D-shaped polymer optical fiber (core/cladding diameter 120/490 µm), of which the residual thickness after side-polishing was about 245 µm, the thickness of the coated gold layer was 50 nm, and the initial wavelength in pure water was around 1200 nm. For low-concentration detection of the HER2 protein, the device exhibited a wavelength shift of ~1.37 nm with a concentration of 1 µg/mL (e.g., 5.5 nM), which corresponded to a limit of detection of ~5.28 nM. Notably, the response time of the biosensor was measured to be as fast as 5 s. The proposed biosensor exhibits the potential for early detection of HER2 protein in initial cancer serum and offers a pathway to early prevention of breast cancer.

Life in an optical fiber: Monitoring of cell cultures with microcavity in-line Mach-Zehnder interferometer.

Monitoring cell adhesion and growth are crucial for various applications involving drug screening, cytotoxicity, and cytocompatibility studies. However, acquiring accurate information about the growing state and responsiveness to a treatment of a cell system in a real-time and label-free manner is still a challenge. This work presents the first research on direct, real-time, and label-free adherent cell culture monitoring using a microcavity in-line Mach-Zehnder interferometer (µIMZI) fabricated in an optical fiber. The sensing solution based on µIMZI offers a great advantage over many other monitoring concepts tracking the changes taking place on the microcavity's bottom surface and within its volume, thus offering a greater penetration depth. In this study, we verified performance of the approach using a non-cancer bone marrow stromal cell line HS-5. The results demonstrate that the changes of the acquired signal are closely related to the different states of cells' adhesion, proliferation, morphology, and variation of mass. Thus, this label-free, real-time µIMZI-based monitoring technique gives a great promise to the analysis or monitoring of relevant new treatments in future scientific, as well as clinical applications.

Effect of Various Surface Treatments on Wettability and Morphological Properties of Titanium Oxide Thin Films.

The effect of three popular surface activation methods for a titanium oxide (titania) surface was thoroughly investigated to identify the most effective protocol for the enhancement of hydrophilicity. All the methods, namely H2O2 activation, UV irradiation and oxygen plasma treatment resulted in an enhanced hydrophilic titania surface, which was evidenced by the reduced contact angle values. To study in detail the chemical and morphological features responsible for the increased hydrophilicity, the treated surfaces were submitted to inspection with atomic force microscopy and X-ray photoelectron spectroscopy. The correlation between the treatment and titania surface hydroxylation as well as hydrophilic behavior have been discussed.

Electrochemistry in an optical fiber microcavity - optical monitoring of electrochemical processes in picoliter volumes.

In this work, we demonstrate a novel method for multi-domain analysis of properties of analytes in volumes as small as picoliters, combining electrochemistry and optical measurements. A microcavity in-line Mach-Zehnder interferometer (µIMZI) obtained in a standard single-mode optical fiber using femtosecond laser micromachining was able to accommodate a microelectrode and optically monitor electrochemical processes inside the fiber. The interferometer shows exceptional sensitivity to changes in the optical properties of analytes in the microcavity. We show that the optical readout follows the electrochemical reactions. Here, the redox probe (ferrocenedimethanol) undergoing reactions of oxidation and reduction changes the optical properties of the analyte (refractive index and absorbance) that are monitored using the µIMZI. Measurements have been supported by numerical analysis of both optical and electrochemical phenomena. On top of the capability of the approach to perform analysis on a microscale, the difference between oxidized and reduced forms in the near-infrared region can be measured using the µIMZI, which is hardly possible using other optical techniques. The proposed multi-domain concept is a promising approach for highly reliable and ultrasensitive chemo- and biosensing.

Use of machine learning to efficiently predict the confinement loss in anti-resonant hollow-core fiber.

The fundamental mode confinement loss (CL) of anti-resonant hollow-core fiber (ARF) is efficiently predicted by a classification task of machine learning. The structure-parameter vector is utilized to define the sample space of ARFs. The CL of labeled samples at 1550 nm is numerically calculated via the finite element method (FEM). The magnitude of CL is obtained by a classification task via a decision tree and k-nearest neighbors algorithms with the training and test sets generated by 290700 and 32300 labeled samples. The test accuracy, confusion matrices, and the receiver operating characteristic curves have shown that our proposed method is effective for predicting the magnitude of CL with a short computation runtime compared to FEM simulation. The feasibility of predicting other performance parameters by the extension of our method, as well as its ability to generalize outside the tested sample space, is also discussed. It is likely that the proposed sample definition and the use of a classification approach can be adopted for design application beyond efficient prediction of ARF CL and inspire artificial intelligence and data-driven-based research of photonic structures.

Real-time isothermal DNA amplification monitoring in picoliter volumes using an optical fiber sensor.

Rolling circle amplification (RCA) of DNA can be considered as a great alternative to the gold standard polymerase chain reaction (PCR), especially during this pandemic period, where rapid, sensitive, and reliable test results for hundreds of thousands of samples are required daily. This work presents the first research to date on direct, real-time and label-free isothermal DNA amplification monitoring using a microcavity in-line Mach-Zehnder interferometer (µIMZI) fabricated in an optical fiber. The solution based on µIMZI offers a great advantage over many other sensing concepts - making possible optical analysis in just picoliter sample volumes. The selectivity of the biosensor is determined by DNA primers immobilized on the microcavity's surface that act as selective biorecognition elements and trigger initiation of the DNA amplification process. In this study, we verified the sensing concept using circular DNA designed to target the H5N1 influenza virus. The developed biosensor exhibits an ultrahigh refractive index sensitivity reaching 14 000 nm per refractive index unit and a linear detection range between 9.4 aM and 94 pM of the target DNA sequence. Within a 30 min period, the amplification of as little as 9.4 aM DNA can be effectively detected, with a calculated limit of detection of as low as 0.2 aM DNA, suggesting that this methodology holds great promise in practical disease diagnosis applications in the future.

Antiresonant fibers with single- and double-ring capillaries for optofluidic applications.

In this work we discuss the effect of infiltration of different antiresonant fibers with low-refractive-index liquids, such as water and ethanol, on their optical properties. The fibers with single- and double-ring capillaries have been designed to show broad transmission bands in visible and near infrared range as it is required for optofluidics, in particular spectrophotometric applications. We show experimentally that their transmission windows shift toward shorter wavelengths and only modestly reduce their width. The transmission bands are located in the wavelength ranges of 533-670 nm and 707-925 nm, for the fibers when infiltrated with water. The two types of analyzed antiresonant fibers infiltrated with the liquids show similar light guidance properties when they are straight, but significantly lower bending loss can be achieved for the double-ring than for the single-ring antiresonant fiber. For this reason, the double-ring antiresonant fibers are more suitable as a compact solution for optofluidic applications, although transmission windows are reduced due to broader resonance peaks.

Long-Period Gratings and Microcavity In-Line Mach Zehnder Interferometers as Highly Sensitive Optical Fiber Platforms for Bacteria Sensing.

Selected optical fiber sensors offer extraordinary sensitivity to changes in external refractive (RI), which make them promising for label-free biosensing. In this work the most sensitive ones, namely long-period gratings working at (DTP-LPG) and micro-cavity in-line Mach-Zehnder interferometers (µIMZI) are discussed for application in bacteria sensing. We describe their working principles and RI sensitivity when operating in water environments, which is as high as 20,000 nm/RIU (Refractive index unit) for DTP-LPGs and 27,000 nm/RIU for µIMZIs. Special attention is paid to the methods to enhance the sensitivity by etching and nano-coatings. While the DTP-LPGs offer a greater interaction length and sensitivity to changes taking place at their surface, the µIMZIs are best suited for investigations of sub-nanoliter and picoliter volumes. The capabilities of both the platforms for bacteria sensing are presented and compared for strains of Escherichia coli, lipopolysaccharide E. coli, outer membrane proteins of E. coli, and Staphylococcus aureus. While DTP-LPGs have been more explored for bacteria detection in 102-106 Colony Forming Unit (CFU)/mL for S. aureus and 103-109 CFU/mL for E. coli, the µIMZIs reached 102-108 CFU/mL for E. coli and have a potential for becoming picoliter bacteria sensors.

Electrochemically directed biofunctionalization of a lossy-mode resonance optical fiber sensor.

In this work, we present a direct electrochemical biofunctionalization of an indium-tin-oxide-coated lossy-mode resonance optical fiber sensor. The functionalization using a biotin derivative was performed by cyclic voltammetry in a 10 mM biotin hydrazide solution. All stages of the experiment were simultaneously verified with optical and electrochemical techniques. Performed measurements indicate the presence of a poly-biotin layer on the sensor's surface. Furthermore, dual-domain detection of 0.01 and 0.1 mg/mL of avidin confirms the sensor's viability for label-free detection.

Combined Long-Period Fiber Grating and Microcavity In-Line Mach-Zehnder Interferometer for Refractive Index Measurements with Limited Cross-Sensitivity.

This work discusses sensing properties of a long-period grating (LPG) and microcavity in-line Mach-Zehnder interferometer (µIMZI) when both are induced in the same single-mode optical fiber. LPGs were either etched or nanocoated with aluminum oxide (Al2O3) to increase its refractive index (RI) sensitivity up to ≈2000 and 9000 nm/RIU, respectively. The µIMZI was machined using a femtosecond laser as a cylindrical cavity (d = 60 µm) in the center of the LPG. In transmission measurements for various RI in the cavity and around the LPG we observed two effects coming from the two independently working sensors. This dual operation had no significant impact on either of the devices in terms of their functional properties, especially in a lower RI range. Moreover, due to the properties of combined sensors two major effects can be distinguished-sensitivity to the RI of the volume and sensitivity to the RI at the surface. Considering also the negligible temperature sensitivity of the µIMZI, it makes the combination of LPG and µIMZI sensors a promising approach to limit cross-sensitivity or tackle simultaneous measurements of multiple effects with high efficiency and reliability.

Simultaneous optical and electrochemical label-free biosensing with ITO-coated lossy-mode resonance sensor.

In this work we discuss a new label-free biosensing device based on indium tin oxide (ITO) overlaid section of a multimode optical fiber fused silica core. The sensor has been used to optical measurements also simultaneously interrogated electrochemically (EC). Due to optimized thickness and optical properties of ITO film, a lossy-mode resonance (LMR) could be observed in the optical domain, where electrical properties of the film allowed for application of the sensor as a working electrode in an EC setup. It has been confirmed that the LMR response depends on optical properties of the external medium, as well as potential applied to the electrode during cyclic voltammetry. After the ITO surface functionalization with amine groups and covalently attached biotin, the device has been applied for label-free biosensing of avidin in both the domains simultaneously. On the example of biotin-avidin detection system it was demonstrated that when avidin concentration increases a decrease in current and increase in LMR wavelength shift were recorded in EC and optical domain, respectively. Both optical and EC responses follow the protein interaction process, and thus can be used as cross-verification of the readouts. Moreover, an extended information has been achieved comparing to solely EC interrogation, i.e., the grafting process of biotin and avidin was directly monitored optically displaying individual steps of an incubation procedure.

Immunosensor Based on Long-Period Fiber Gratings for Detection of Viruses Causing Gastroenteritis.

Since the norovirus is the main cause of acute gastroenteritis all over the world, its fast detection is crucial in medical diagnostics. In this work, a rapid, sensitive, and selective optical fiber biosensor for the detection of norovirus virus-like particles (VLPs) is reported. The sensor is based on highly sensitive long-period fiber gratings (LPFGs) coated with antibodies against the main coat protein of the norovirus. Several modification methods were verified to obtain reliable immobilization of protein receptors on the LPFG surface. We were able to detect 1 ng/mL norovirus VLPs in a 40-min assay in a label-free manner. Thanks to the application of an optical fiber as the sensor, there is a possibility to increase the user's safety by separating the measurement point from the signal processing setup. Moreover, our sensor is small and light, and the proposed assay is straightforward. The designed LPFG-based biosensor could be applied in both fast norovirus detection and in vaccine testing.

Ultrasensitive tantalum oxide nano-coated long-period gratings for detection of various biological targets.

In this work we discussed a label-free biosensing application of long-period gratings (LPGs) optimized in refractive index (RI) sensitivity by deposition of thin tantalum oxide (TaOx) overlays. Comparing to other thin film and materials already applied for maximizing the RI sensitivity, TaOx offers good chemical and mechanical stability during its surface functionalization and other biosensing experiments. It was shown theoretically and experimentally that when RI of the overlay is as high as 2 in IR spectral range, for obtaining LPGs ultrasensitive to RI, the overlay's thickness must be determined with subnanometer precision. In this experiment the TaOx overlays were deposited using Atomic Layer Deposition method that allowed for achieving overlays with exceptionally well-defined thickness and optical properties. The TaOx nano-coated LPGs show RI sensitivity determined for a single resonance exceeding 11,500 nm/RIU in RI range nD= 1.335-1.345 RIU, as expected for label-free biosensing applications. Capability for detection of various in size biological targets, i.e., proteins (avidin) and bacteria (Escherichia coli), with TaOx-coated LPGs was verified using biotin and bacteriophage adhesin as recognition elements, respectively. It has been shown that functionalization process, as well as type of recognition elements and target analyte must be taken into consideration when the LPG sensitivity is optimized. In this work optimized approach made possible detection of small in size biological targets such as proteins with sensitivity reaching 10.21 nm/log(ng/ml).

Live E. coli bacteria label-free sensing using a microcavity in-line Mach-Zehnder interferometer.

The paper presents the first study to date on selective label-free biosensing with a microcavity in-line Mach-Zehnder interferometer induced in an optical fiber. The sensing structures were fabricated in a single-mode fiber by femtosecond laser micromachining. In contrast to other studies of this sensing scheme, where only the sensitivity to refractive index changes in the cavity was investigated, this research used chemical surface treatment of the sensor to ensure detection specificity. Immobilized MS2 bacteriophages were applied as recognition elements specifically targeting live E. coli C3000 bacteria. It is shown that the sensor allows for real-time monitoring of biological phenomena taking place on the surface of the microcavity. The developed biosensor exhibits ultrahigh refractive index sensitivity of 15,000 nm/RIU and is capable of detecting live E. coli bacteria concentrations as low as 100 colony forming units (CFU)/mL in liquid volume as low as picoliters.

Optical Detection of Ketoprofen by Its Electropolymerization on an Indium Tin Oxide-Coated Optical Fiber Probe.

In this work an application of optical fiber sensors for real-time optical monitoring of electrochemical deposition of ketoprofen during its anodic oxidation is discussed. The sensors were fabricated by reactive magnetron sputtering of indium tin oxide (ITO) on a 2.5 cm-long core of polymer-clad silica fibers. ITO tuned in optical properties and thickness allows for achieving a lossy-mode resonance (LMR) phenomenon and it can be simultaneously applied as an electrode in an electrochemical setup. The ITO-LMR electrode allows for optical monitoring of changes occurring at the electrode during electrochemical processing. The studies have shown that the ITO-LMR sensor’s spectral response strongly depends on electrochemical modification of its surface by ketoprofen. The effect can be applied for real-time detection of ketoprofen. The obtained sensitivities reached over 1400 nm/M (nm·mg−1·L) and 16,400 a.u./M (a.u.·mg−1·L) for resonance wavelength and transmission shifts, respectively. The proposed method is a valuable alternative for the analysis of ketoprofen within the concentration range of 0.25⁻250 μg mL−1, and allows for its determination at therapeutic and toxic levels. The proposed novel sensing approach provides a promising strategy for both optical and electrochemical detection of electrochemical modifications of ITO or its surface by various compounds.

Transition between bulk and surface refractive index sensitivity of micro-cavity in-line Mach-Zehnder interferometer induced by thin film deposition.

In this work we discuss the refractive index (RI) sensitivity of a micro-cavity in-line Mach-Zehnder interferometer in the form of a cylindrical hole (40-50 µm in diameter) fabricated in a standard single-mode optical fiber using a femtosecond laser. The surface of the micro-cavity was coated with up to 400 nm aluminum oxide thin film using the atomic layer deposition method. Next, the film was progressively chemically etched and the influence on changes in the RI of liquid in the micro-cavity was determined at different stages of the experiment, i.e., at different thicknesses of the film. An effect of transition between sensitivity to the film thickness (surface) and the RI of liquid in the cavity (bulk) is demonstrated for the first time. We have found that depending on the interferometer working conditions determined by thin film properties, the device can be used for investigation of phenomena taking place at the surface, such as in case of specific label-free biosensing applications, or for small-volume RI analysis as required in analytical chemistry.

Towards refractive index sensitivity of long-period gratings at level of tens of µm per refractive index unit: fiber cladding etching and nano-coating deposition.

In this work we report experimental results on optimizing the refractive index (RI) sensitivity of long-period gratings (LPGs) by fiber cladding etching and thin aluminum oxide (Al2O3) overlay deposition. The presented LPG takes advantage of work in the dispersion turning point (DTP) regime as well as the mode transition (MT) effect for higher-order cladding modes (LP09 and LP010). The MT was obtained by depositing Al2O3 overlays with single-nanometer precision using the Atomic Layer Deposition method (ALD). Etching of both the overlay and the fiber cladding was performed using hydrofluoric acid (HF). For shallow etching of the cladding, i.e., DTP observed at next = 1.429 and 1.439 RIU for an LPG with no overlay, followed by deposition of an overlay of up to 167 nm in thickness, HF etching allowed for post-deposition fine-tuning of the overlay thickness resulting in a significant increase in RI sensitivity mainly at the DTP of the LP09 cladding mode. However, at an external RI (next) above 1.39 RIU, the DTP of LP010 was noticed, and its RI sensitivity exceeded 9,000 nm/RIU. Deeper etching of the cladding, i.e., DTP observed for next above 1.45 RIU, followed by the deposition of thicker overlays (up to 201 nm in thickness) allowed the sensitivity to reach values of over 40,000 nm/RIU in a narrow RI range. Sensitivity exceeding 20,000 nm/RIU was obtained in an RI range suitable for label-free biosensing applications.