The evolution of optical fiber technology has revolutionized a variety of fields, from optical transmission to environmental monitoring and biomedicine, given their unique properties and versatility. ...For biosensing purposes, the light guided in the fiber core is exposed to the surrounding media where the analytes of interest are detected by different techniques, according to the optical fiber configuration and biofunctionalization strategy employed. These configurations differ in manufacturing complexity, cost and overall performance. The biofunctionalization strategies can be carried out directly on bare fibers or on coated fibers. The former relies on interactions between the evanescent wave (EW) of the fiber and the analyte of interest, whereas the latter can comprise plasmonic methods such as surface plasmon resonance (SPR) and localized SPR (LSPR), both originating from the interaction between light and metal surface electrons. This review presents the basics of optical fiber immunosensors for a broad audience as well as the more recent research trends on the topic. Several optical fiber configurations used for biosensing applications are highlighted, namely uncladded, U-shape, D-shape, tapered, end-face reflected, fiber gratings and special optical fibers, alongside practical application examples. Furthermore, EW, SPR, LSPR and biofunctionalization strategies, as well as the most recent advances and applications of immunosensors, are also covered. Finally, the main challenges and an outlook over the future direction of the field is presented.
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Reversible addition fragmentation chain transfer (RAFT) - assisted encapsulating emulsion polymerization (REEP) has received considerable attention as an efficient strategy to prepare ...colloidal stable shell@core nanoparticles. Generally, amphipathic macroRAFT agents are used but the effect of working above or below the critical micelle concentration (CMC) of macroRAFT agents needs to be addressed. Hence, it is necessary to understand if this parameter has an impact not only on the stability of the colloids but also on the molecular mass of the polymer shell.
Here, the CMC of three different macroRAFT agent was determined and the effect of macroRAFT agents concentration on the colloidal stability of gold nanoparticles coated with macroRAFT agents (macroRAFT@Au) assessed. The subsequent chain extension from macroRAFT@Au NPs, resulting in encapsulated Au nanoparticles (copolymer@Au), has also been systematically studied.
Using the REEP approach it was possible to obtain stable encapsulated Au NPs. Moreover, this strategy opens the possibility of adjusting the macroRAFT agents concentration to tune the length of the polymer chains grown around Au cores which is of major interest for the design of biosensors based on responsive polymer shells, such as pH, temperature and photoluminescence quenching.
Optical fiber technology has rapidly progressed over the years, providing valuable benefits for biosensing purposes such as sensor miniaturization and the possibility for remote and real-time ...monitoring. In particular, tilted fiber Bragg gratings (TFBGs) are extremely sensitive to refractive index variations taking place on their surface. The present work comprises a case-study on the impact of different methods of analysis applied to decode spectral variations of bare and plasmonic TFBGs during the detection of N-terminal B-type natriuretic peptide (NT-proBNP), a heart failure biomarker, namely by following the most sensitive mode, peaks of the spectral envelopes, and the envelopes' crossing point and area. Tracking the lower envelope resulted in the lowest limits of detection (LOD) for bare and plasmonic TFBGs, namely, 0.75 ng/mL and 0.19 ng/mL, respectively. This work demonstrates the importance of the analysis method on the outcome results, which is crucial to attain the most reliable and sensitive method with lower LOD sensors. Furthermore, it makes the scientific community aware to take careful attention when comparing the performance of different biosensors in which different analysis methods were used.
•Cortisol detection based on surface plasmon resonance (SPR) using an unclad plastic optical fiber (POF).•High sensitivity and low limit of detection (LOD).•Selectivity of the proposed sensor for ...stress hormone was performed showing high specificity.•Optical sensor solution with relatively low-cost interrogation method, straightforward signal processing.•Interesting working range (0.005−10 ng/mL) for different biological samples from human or marine life.
This paper presents the development and feasibility tests of a cortisol immunosensor. The sensor is based on surface plasmon resonance (SPR) using an unclad plastic optical fiber (POF) in which the SPR is used as sensitivity enhancer, promoted by a gold/palladium (AuPd) alloy coating. The AuPd coated fibers were functionalized with an anti-cortisol antibody and passivated with bovine serum albumin (BSA) to be tested in the presence of cortisol as target analyte. The antibody-antigen binding reaction caused a variation of the refractive index on the surface of the AuPd coating, which leads to a shift of the SPR signature wavelength. The sensor was tested for different cortisol concentrations, ranging from 0.005 to 10 ng/mL. The reported biosensor presented a total wavelength shift of 15 nm for the testing range, putting in evidence a high sensitivity. Control tests for selectivity assessment were also performed. Concentrations as high as 10 ng/mL of cortisol, in a sensor functionalized with anti-hCG antibodies, only resulted in 1 nm variation of the resonance wavelength, 15 times lower than the one functionalized with the anti-cortisol antibodies, which indicates a high selectivity for the proposed approach. For this sensing approach the limit of detection (LOD) was determined to be 1 pg/mL. The proposed SPR based POF sensor has a low-cost interrogation method, high sensitivity and low LOD, straightforward signal processing and find important applications in different biological fields.
Colloidal gold nanoparticles (Au NPs) have been used in several biological applications, which include the exploitation of size- and shape-dependent Localized Surface Plasmon Resonance (LSPR) in ...biosensing devices. In order to obtain functional and stable Au NPs in a physiological medium, surface modification and functionalization are crucial steps in these endeavors. Reversible addition-fragmentation chain transfer (RAFT) polymerization meets this need offering the possibility of control over the composition and architecture of polymeric shells coating Au NPs. Furthermore, playing with a careful choice of monomers, RAFT polymerization allows the possibility to design a polymer shell with the desired functional groups aiming at Au based nanocomposites suitable for biorecognition and biotargeting. This review provides important aspects concerning the synthesis and optical properties of Au NPs as well as concepts of RAFT polymerization. Understanding these concepts is crucial to appreciate the chemical strategies available towards RAFT-polymer coated Au core-shell nanostructures, which are here reviewed. Finally, examples of applications in opto-biodetection devices are provided and the potential of responsive "smart" nanomaterials based on such structures can be applied to other biological applications.
Laser-induced graphene from paper (paper-LIG) was applied in non-enzymatic electrochemical sensing of uric acid (UA) in human urine. Paper-LIG was formed by CO2 laser modification of paper into a 3D ...graphene arrangement. Kinetic analysis of paper-LIG electrodes returned effective heterogeneous electron transfer standard rate constants of 1.4 × 10−3 cm s−1 and 7.8 × 10−4 cm s−1 for Ru(NH3)62+/3+ and Fe(CN)64−/3− redox probes, respectively. These electrodes were able to detect and quantify uric acid in PBS within the 10–300 μM range at pH between 5.6 and 7.4. At pH 7.4, a linear response (R2 = 0.999) from 10 to 250 μM was achieved, with a limit of detection of 3.97 μM and a sensitivity of 0.363 μA cm−2 μM−1. Paper-LIG electrodes denoted adequate selectivity in synthetic urine as well as in ascorbic acid (AA) and dopamine (DA)-containing electrolytes. Determination of urinary UA content in human samples returned a concentration of c.a. 1.8–1.9 mM, within the range for healthy individuals. Recoveries of samples spiked with 50 and 100 μM UA were 100.6% and 95.4%, respectively, with satisfactory reproducibility and stability. These cheap, lightweight, flexible, and eco-friendly paper-LIG biosensors for non-enzymatic quantification of UA in human urine pave the way to widespread application in the detection of other important biomarkers.
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•“Green” graphene electrodes by CO2 laser irradiation of paper (“paper-LIG”).•Uric acid (UA) quantification at clinically relevant concentrations and pH (5.6–7.4).•Limit of detection of 3.97 μM and a sensitivity of 0.363 μA cm−2 μM−1 (pH = 7.4).•Adequate selectivity in synthetic urine, as well as in ascorbic acid and dopamine-containing electrolytes.•Recoveries of 100.6% and 95.4% for human urine samples spiked with 50 and 100 μM UA.
In the last years, optical fiber sensors have proven to be a reliable and versatile biosensing tool. Optical fiber biosensors (OFBs) are analytical devices that use optical fibers as transducers, ...with the advantages of being easily coated and biofunctionalized, allowing the monitorization of all functionalization and detection in real-time, as well as being small in size and geometrically flexible, thus allowing device miniaturization and portability for point-of-care (POC) testing. Knowing the potential of such biosensing tools, this paper reviews the reported OFBs which are, at the moment, the most cost-effective. Different fiber configurations are highlighted, namely, end-face reflected, unclad, D- and U-shaped, tips, ball resonators, tapered, light-diffusing, and specialty fibers. Packaging techniques to enhance OFBs’ application in the medical field, namely for implementing in subcutaneous, percutaneous, and endoscopic operations as well as in wearable structures, are presented and discussed. Interrogation approaches of OFBs using smartphones’ hardware are a great way to obtain cost-effective sensing approaches. In this review paper, different architectures of such interrogation methods and their respective applications are presented. Finally, the application of OFBs in monitoring three crucial fields of human life and wellbeing are reported: detection of cancer biomarkers, detection of cardiovascular biomarkers, and environmental monitoring.
Measuring cortisol levels as a stress biomarker is essential in many medical conditions associated with a high risk of metabolic syndromes such as anxiety and cardiovascular diseases, among others. ...One technology that has a growing interest in recent years is fiber optic biosensors that enable ultrasensitive cortisol detection. Such interest is allied with progress being achieved in basic interrogation, accuracy improvements, and novel applications. The development of improved cortisol monitoring, with a simplified manufacturing process, high reproducibility, and low cost, are challenges that these sensing mechanisms still face, and for which solutions are still needed. In this paper, a comprehensive characterization of a D-shaped fiber optic immunosensor for cortisol detection based on surface plasmon resonance (SPR) enabled by gold coating is reported. Specifically, the sensor instrumentation and fabrication processes are discussed in detail, and a simulation with its complete mathematical formalism is also presented. Moreover, experimental cortisol detection tests were performed for a detection range of 0.01 to 100 ng/mL, attaining a logarithmic sensitivity of 0.65 ± 0.02 nm/log(ng/mL) with a limit of detection (LOD) of 1.46 ng/mL. Additionally, an investigation of signal processing is also discussed, with the main issues addressed in order to highlight the best way to extract the sensing information from the spectra measured with a D-shaped sensor.
Bioapplications of gold nanoparticles (Au NPs) have received significant attention due to their sensitive optical characteristics which depend on particle size and shape, state of aggregation and to ...surrounding (bio)chemical environment. In this review, we present an overview of several methods to synthesise stable colloidal Au NPs with focus on the use of the electrostatic assembly method of polyelectrolytes (PE) to functionalise Au NPs. This versatile method allows adjusting the thickness, chemical functions and the surface charge of the shells surrounding the Au NPs, thus the relevance of these features for the bioapplications of Au NPs involving surface-mediated processes is discussed. Moreover, because the PE used can be functionalised with organic fluorophores, drugs or antibodies yielding multifunctional nanocomposites useful for those applications, this review also provides an overview of the electrostatic assembly of functionalised PE onto Au NPs and their bioapplications.
The use of reversible addition-fragmentation chain transfer (RAFT)-assisted encapsulating emulsion polymerization (REEP) has been explored to prepare diverse types of colloidal stable core-shell ...nanostructures. A major field of application of such nanoparticles is in emergent nanomedicines, which require effective biofunctionalization strategies, in which their response to bioanalytes needs to be firstly assessed. Herein, functional core-shell nanostructures were prepared via REEP and click chemistry. Thus, following the REEP strategy, colloidal gold nanoparticles (Au NPs,
= 15 nm) were coated with a poly(ethylene glycol) methyl ether acrylate (PEGA) macroRAFT agent containing an azide (
) group to afford
-macroRAFT@Au NPs. Then, chain extension was carried out from the NPs surface via REEP, at 44 °C under monomer-starved conditions, to yield
-copolymer@Au NPs-core-shell type structures. Biotin was anchored to
-copolymer@Au NPs via click chemistry using an alkynated biotin to yield biofunctionalized Au nanostructures. The response of the ensuing biotin-copolymer@Au NPs to avidin was followed by visible spectroscopy, and the copolymer-biotin-avidin interaction was further studied using the Langmuir-Blodgett technique. This research demonstrates that REEP is a promising strategy to prepare robust functional core-shell plasmonic nanostructures for bioapplications. Although the presence of azide moieties requires the use of low polymerization temperature, the overall strategy allows the preparation of tailor-made plasmonic nanostructures for applications of biosensors based on responsive polymer shells, such as pH, temperature, and photoluminescence quenching. Moreover, the interaction of biotin with avidin proved to be time dependent.
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