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This work was developed within the scope of project i3N (LA/P/0037/2020. I.P. N. F. Santos thanks i3N for the BPD Grant BPD/UI96/5177/2020. S. O. Pereira thanks i3N for the BPD Grant BPD/UI96/5808/2017. The authors also thank Jonas Deuermeier for the XPS measurements. Publisher Copyright: © 2022 Elsevier Ltd 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)6]2+/3+ and [Fe(CN)6]4−/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. publishersversion published

Direct laser scribing (DLS) technology is applied to commercial polyimide (PI) coated optical fibers producing laser-induced graphene (LIG) coated optical fibers. The PI-coated optical fiber is first inscribed with off-center Bragg gratings via point-by-point method using a femtosecond laser system. Then, the off-center Bragg grating is irradiated with a CO2 laser and the PI coating is photothermally converted into LIG without affecting the grating. Scanning electron microscopy (SEM) and Raman spectroscopy prove the presence of the laser-induced graphene layer on the optical fiber, and Fourier transform infrared (FTIR) spectroscopy confirms that all the PI coating was converted into LIG. The resulting LIG-coated off-center Bragg grating (FBG) sensors respond to variations of the surrounding refractive index (RI) with a sensitivity of 38.08 ± 1.57 nm per RI units (RIU). In addition, after removal of the PI coating, obtaining a bare-FBG, the sensitivity decreases to 25.63 ± 0.66 nm RIU−1. Therefore, this strategy, here reported for the first time, paves the way to produce promising novel optical transducers aiming to develop bio- and chem-sensing devices.

Stress is a normal physiological and behavioral response to a stimulus that somehow disturbs the maintenance of homeostasis, leading to changes in cortisol levels. When stress is persistent and uncontrolled, it can severely affect several areas, such as human health and some marine biology sectors, including aquaculture production. Currently, the detection of cortisol is performed in laboratories using conventional techniques with several disadvantages, one of them being the long waiting time for a response. Therefore, it is essential the development of miniaturized analytical devices capable of monitoring in real-time, detecting and quantifying cortisol in point of care (POC). Special optical fiber structure, in this case, D-shape in silica optical fibers (SOF) and polymeric optical fibers (POF) coated with gold (Au) were used in this work for the development of immunosensors based on surface plasmon resonance (SPR) for cortisol (stress hormone) detection. In the laboratory, Au coated SOF (Au-SOF) and Au coated POF (Au-POF) were initially characterized at refractive index (RI) with eight glucose concentrations ranging from 1.333 to 1.386 RI units (RIU). The obtained sensitivities were, respectively, 1646.67 ± 91.66 nm/RIU, being lower than the simulated one with 2138.95 ± 142.65 nm/RIU, and 1566.81 ± 96.87 nm/RIU. Subsequently, the fibers were functionalized with anti-cortisol antibodies using cysteamine as the intermediate linker to allow the immobilization of the antibodies to the Au surface. After this procedure, both immunosensors were tested for cortisol concentrations ranging from 0.1 to 100 ng/ml to compare the performances, in which the Au-SOF and Au-POF immunosensors presented a total resonance wavelength shift of 3.22 and 2.10 nm, and sensitivities of 1.08 ± 0.21 nm/log(ng/mL) and 0.52 ± 0.03 nm/log(ng/mL), respectively. Different limits of detection (LODs) were calculated using different methods for each type of immunosensor. One method consisted in performing a Hill fitting to the results and another considering the response of the control interferents. For Au-SOF and Au-POF, the LODs attained through the first method were 0.12 and 0.13 ng/mL (considering the resonance wavelength shift), respectively, and 0.14 ng/mL considering the intensity variation of Au-POF. The second method enabled a LOD of 1.75 and 1.97 ng/mL for Au-SOF and Au-POF, respectively.

Antibiotic pollution of freshwaters and even food products has become an important concern worldwide. Hence, it is of utmost importance to develop cost-effective and reliable devices that can provide information on the presence of such contaminants to the general population. In the present work, zinc oxide (ZnO) nanotetrapods (NTP) produced via a high yield laser processing approach were used as transducers in a luminescent-based immunosensor to detect tetracycline (TC). These tetrapodal structures present needle-shaped branches with a high aspect ratio, exhibiting lengths from hundreds of nanometers to a few micrometers and an average thickness of tens of nanometers, providing a high surface area for bioreceptor immobilization and analyte reaction, which is quite desirable in a transducer material. Besides, these ZnO NTP display intense photoluminescence (PL) at room temperature, making such a signal rather promising for transduction. Indeed, the intensity of the ZnO PL signal was seen to correlate with the TC concentration. The PL quenching with increasing analyte concentration is explained considering the rise in the bending of the electronic bands of the semiconductor near its surface due to increased charge density at this region, induced by the interaction between the bioreceptor (anti-TC antibodies) and the TC molecules. As a larger depletion width (and potential barrier) is promoted near the surface, the excitonic recombination probability is reduced and, consequently, the PL intensity in the ultraviolet spectral region, allowing us to use this relationship as a sensing mechanism. This information enabled us to define a calibration curve for TC quantification in the 0.001 to 1 μg L–1 range, which is the range of interest of this antibiotic in freshwaters. A limit of detection (LOD) of ∼1.2 ng L–1 is reported, corresponding to one of the lowest LOD found in the literature for this antibiotic, indicating that the present ZnO NTP-based biosensors rival the current state-of-the-art ones. published

Zinc oxide (ZnO) nanostructures have been widely used in biosensor applications. However, little attention has been given to the interaction of ZnO structures with physiological buffer solutions. In the present work, it is shown that the use of buffers containing phosphate ions leads to the modification of the ZnO tetrapodal micro/nanostructures when immersed in such solutions for several hours, even at the physiological pH (7.4). ZnO samples designed to be used as transducers in biosensors were immersed in phosphate buffers for several durations at pH = 5.8 and pH = 7.4. Their detailed morphological, structural and optical characterization was carried out to demonstrate the effect of the ZnO interaction with the phosphate ions. The pH had an important role in the ZnO conversion into zinc phosphate, with lower pH promoting a more pronounced effect. After 72 h and at pH = 5.8, a significant amount of the ZnO structures were converted into crystalline zinc phosphate, while immersion during the same time at pH = 7.4 resulted predominantly in amorphous zinc phosphate particles mixed with the original ZnO tetrapods. Photoluminescence spectra show remarkable changes with prolonged immersion times, particularly when the luminescence of the sample was investigated at 14 K. These findings highlight the importance of a careful analysis of the sensing results when phosphate-based buffer solutions are in contact with the ZnO transducers, as the changes observed on the transduction signal during sensing experiments may also comprise a non-negligible contribution from a phosphate-induced transformation of ZnO, which can hamper an accurate assessment of the sensing behavior.

The inherent scalability, low production cost and mechanical flexibility of laser-induced graphene (LIG) combined with its high electrical conductivity, hierarchical porosity and large surface area are appealing characteristics for many applications. Still, other materials can be combined with LIG to provide added functionalities and enhanced performance. This work exploits the most adequate electrodeposition parameters to produce LIG/ZnO nanocomposites. Low-temperature pulsed electrodeposition allowed the conformal and controlled deposition of ZnO rods deep inside the LIG pores whilst maintaining its inherent porosity, which constitute fundamental advances regarding other methods for LIG/ZnO composite production. Compared to bare LIG, the composites more than doubled electrode capacitance up to 1.41 mF cm−2 in 1 M KCl, while maintaining long-term cycle stability, low ohmic losses and swift electron transfer. The composites also display a luminescence band peaked at the orange/red spectral region, with the main excitation maxima at ~ 3.33 eV matching the expected for the ZnO bandgap at room temperature. A pronounced sub-bandgap tail of states with an onset absorption near 3.07 eV indicates a high amount of defect states, namely surface-related defects. This work shows that these environmentally sustainable multifunctional nanocomposites are valid alternatives for supercapacitors, electrochemical/optical biosensors and photocatalytic/photoelectrochemical devices.

Carbon-based electrodes have demonstrated great promise as electrochemical transducers in the development of biosensors. More recently, laser-induced graphene (LIG), a graphene derivative, appears as a great candidate due to its superior electron transfer characteristics, high surface area and simplicity in its synthesis. The continuous interest in the development of cost-effective, more stable and reliable biosensors for glucose detection make them the most studied and explored within the academic and industry community. In this work, the electrochemistry of glucose oxidase (GOx) adsorbed on LIG electrodes is studied in detail. In addition to the well-known electroactivity of free flavin adenine dinucleotide (FAD), the cofactor of GOx, at the expected half-wave potential of −0.490 V vs. Ag/AgCl (1 M KCl), a new well-defined redox pair at 0.155 V is observed and shown to be related to LIG/GOx interaction. A systematic study was undertaken in order to understand the origin of this activity, including scan rate and pH dependence, along with glucose detection tests. Two protons and two electrons are involved in this reaction, which is shown to be sensitive to the concentration of glucose, restraining its origin to the electron transfer from FAD in the active site of GOx to the electrode via direct or mediated by quinone derivatives acting as mediators.

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.

In the present study, the pulsed laser ablation in water technique was used to produce chromium-doped ZnGa2O4 nanostructures from a sintered pellet target. The materials obtained mainly comprised the cubic spinel crystalline structure of ZnGa2O4 and the monoclinic β-Ga2O3 as a minority phase (3%). Intra-ionic Cr3+ red luminescence from the ions in the spinel structure was the dominant recombination process in the bulk target and nanostructures. Overlapping of the Cr-related emitting centers was identified and the samples exhibited persistent red luminescence, which is of interest for bioimaging. Moreover, the temperature-dependent luminescence demonstrated the versatility of the nanostructures obtained, which can be further explored as temperature sensors based on the low energy shift of the zero phonon line peak positions as the temperature increased.

Hypothesis 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. Methods 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. Findings 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.

New approaches for coupling Au NPs to the photoanode of dye sensitized solar cells (DSSCs) were proposed herein, aiming to improve the typical energy conversion efficiency of these cells. For this purpose, colloidal Au NPs with different particles sizes, ∼5 nm and ∼22 nm, were chemically synthesized and attached (i) directly to titanium dioxide (TiO2) or (ii) to TiO2 surface modified with siliceous shells enriched in dithiocarbamate moieties (SiO2/SiDTC). Photoanodes composed by films of TiO2 anatase, TiO2@Au NPs (∼5 nm and ∼22 nm), or TiO2 functionalized with SiO2/SiDTC, loaded with colloidal Au NPs, were made. DSSCs were set-up in a typical sandwich configuration, using the photoanode, a Pt counter electrode, and an iodide electrolyte solution (I−/I3−). In general, a relevant contribution in the plasmonic DSSC performance was evidenced by using Au NPs of ∼22 nm loaded in different amounts 23.9 wt%, 31.0 wt% and 44.0 wt%. Photoanodes composed by 23.9% of Au yielded an increment of 14.40% in photocurrent and of 11.21% in the overall power conversion efficiency (PCE), when compared to the conventional one. In turn, the new strategy used in the chemical modification of the conventional photoanodes with dithiocarbamate groups showed also a significant improvement of the DSSC parameters.

Carbon dots (CDs) have become one of the most investigated nanomaterials in the last few years, since they offer excellent prospects to be used in a wide range of technological applications. Nonetheless, the understanding of the photoluminescence (PL) processes remains unclear and solely based on spectroscopic measurements at room temperature, which hampered a full discussion on the nature of recombination mechanisms. Insights into the CDs’ PL and corresponding recombination models can be achieved from temperature, excitation energy and excitation density dependency studies. Thus, in this paper, CDs with a mean diameter of ∼3.0 nm were embedded in poly(methyl methacrylate) (PMMA) and studied by such optical techniques. The recombination of CDs/PMMA composites was found to be due to an overlap of emitting centres, both in the blue and green regions, with intensity and peak position strongly dependent on the excitation density. Moreover, this emission was found to be preferentially populated by two overlapped excitation bands. Temperature-dependent PL measurements corroborate the hypothesis of overlapped emitting optical centres (e.g. small molecules at the CDs’ surface), as no shift on peak position and no changes in spectral shape were observed, which allow to exclude the hypothesis of a conventional free excitonic transition and quantum confinement effects, as observed in typical nanosized semiconductors with dimensions lower than the exciton Bohr radius.

Hybrid diamond-graphite nanoplatelet (DGNP) thin films are produced and applied to label-free impedimetric biosensors for the first time, using avidin detection as a proof of concept. The DGNPs are synthesized by microwave plasma chemical vapor deposition through H2/CH4/N2 gas mixtures in a reproducible and rapid single-step process. The material building unit consists of an inner two-dimensional-like nanodiamond with preferential vertical alignment covered by and covalently bound to nanocrystalline graphite grains, exhibiting {111}diamond||{0002}graphite epitaxy. The DGNP films' morphostructural aspects are of interest for electrochemical transduction, in general, and for Faradaic impedimetric biosensors, in particular, combining enhanced surface area for biorecognition element loading and facile Faradaic charge transfer. Charge transfer rate constants in phosphate buffer saline/[Fe(CN)6]4- solution are shown to increase up to 5.6 × 10-3 cm s-1 upon N2 addition to DGNP synthesis. For the impedimetric detection of avidin, biotin molecules are covalently bound as avidin specific recognition elements on (3-aminopropyl)triethoxysilane-functionalized DGNP surfaces. Avidin quantification is attained within the 10-1000 μg mL-1 range following a logarithmic dependency. The limits of detection and of quantitation are 1.3 and 6.4 μg mL-1 (19 and 93 nM), respectively, and 2.3 and 13.8 μg mL-1 (33 and 200 nM) when considering the nonspecific response of the sensors.

Wide and ultrawide bandgap oxides, such as β-Ga2O3, ZnGa2O4 and Zn1-xGa2-2xGexO4, are of particular importance for a myriad of technological applications, including electronics, optoelectronics, and medical devices. In the case of the latter, the development of new, affordable and non-invasive methodologies for bioimaging and diagnosis is of crucial importance towards solutions that can improve health and wellbeing of the populations. For these purposes, red/near infrared emitters within the biological transparency window are required. Therefore, the here studied oxides were subjected to a controlled Cr-doping giving rise to intraionic emission in this region. In the case of the here studied oxide systems, we will investigate the intraionic luminescence properties of Cr3+, with particular emphasis on the persistent luminescence recorded in micro/nano particles of Cr-doped ZnGa2O4 and Zn1-xGa2-2xGexO4 synthesised by laser ablation in liquid media.

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.

Metal oxide semiconductors, and particularly zinc oxide (ZnO), are amongst the most investigated materials to be applied as transducer elements in biosensing devices due to properties as biochemical stability, biocompatibility and functionalisation simplicity. In the present work, ZnO nanotetrapods were produced by the laser-assisted flow deposition technique to be used as transducers in a photoluminescence (PL)-based immunosensor to detect the human chorionic gonadotropin (hCG) hormone. The produced nanostructures were analysed by electron microscopy, Raman and PL spectroscopies. The ZnO tetrapods exhibit an intense PL in both the ultraviolet and visible range, whose intensity changed after the direct immobilisation of the anti-hCG antibodies into the semiconductor’s surface. The changes in the PL intensity after the interaction of the immobilised antibodies with hCG were used as the transduction mechanism for the envisaged sensors. It was observed that when antibody-antigen interactions occur, charge rearrangement at the surface of the semiconductor leads to a reduction in overall intensity of the PL signal with increasing hCG concentration, allowing to establish a correlation between the PL output and the probed concentration. Therefore, such behaviour suggests the adequacy of the developed ZnO-based transducers to be incorporated into optical biosensors. Additionally, the possible interaction mechanisms between the ZnO surface and the immobilised molecules responsible for the changes in the PL spectra were discussed.

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&ndash, 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&ndash, shell nanostructures were prepared via REEP and click chemistry. Thus, following the REEP strategy, colloidal gold nanoparticles (Au NPs, d = 15 nm) were coated with a poly(ethylene glycol) methyl ether acrylate (PEGA) macroRAFT agent containing an azide (N3) group to afford N3&ndash, macroRAFT@Au NPs. Then, chain extension was carried out from the NPs surface via REEP, at 44 &deg, C under monomer-starved conditions, to yield N3&ndash, copolymer@Au NPs&ndash, core&ndash, shell type structures. Biotin was anchored to N3-copolymer@Au NPs via click chemistry using an alkynated biotin to yield biofunctionalized Au nanostructures. The response of the ensuing biotin&ndash, copolymer@Au NPs to avidin was followed by visible spectroscopy, and the copolymer&ndash, biotin&ndash, avidin interaction was further studied using the Langmuir&ndash, Blodgett technique. This research demonstrates that REEP is a promising strategy to prepare robust functional core&ndash, 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.

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.

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 synthesis of core-shell Au nanoparticles protected by an amphiphilic block copolymer is investigated by distinct reversible addition fragmentation chain transfer (RAFT) emulsion polymerization routes. The controlled polymerization of polymer shells onto Au nanoparticles is attempted by using the macroRAFT (MR) agent based on 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid synthesized via RAFT polymerization of poly(ethylene glycol) methyl ether acrylate and exploring several approaches, which include (i) post-modification; (ii) in situ synthesis and (iii) “grafting from” strategies. In the conditions investigated here all these strategies lead to Au polymer nanocomposites but morphological well-defined core-shell nanoparticles are only obtained by applying the “grafting from” strategy. In particular, conditions that promote chain extension from the MR agent adsorbed onto the Au nanoparticles are found necessary to obtain nanostructures with such morphological characteristics and that still show the localized surface plasmon resonance typical of colloidal Au nanoparticles.