Bacterial nanocellulose as a simple and tailorable platform for controlled drug release.

In this study we present a proof of concept of a simple and straightforward approach for the development of a Bacterial Nanocellulose drug delivery system (BNC-DDS), envisioning the local delivery of immunomodulatory drugs to prevent foreign body reaction (FBR). Inspired by the self-adhesion behavior of BNC upon drying, we proposed a BNC laminate entrapping commercial crystalline drugs (dexamethasone-DEX and GW2580) in a sandwich system. The stability of the bilayer BNC-DDS was evidenced by the high interfacial energy of the bilayer films, 150 ± 11 and 88 ± 7 J/m2 respectively for 2 mm- and 10-mm thick films, corresponding to an increase of 7.5 and 4.4-fold comparatively to commercial tissue adhesives. In vitro release experiments unveiled the tunability of the bilayer BNC-DDS by showing extended drug release when thicker BNC membranes were used (from 16 to 47 days and from 35 to 132 days, for the bilayer-BNC entrapping DEX and GW2580, respectively). Mathematical modeling of the release data pointed to a diffusion-driven mechanism with non-fickian behavior. Overall, the results have demonstrated the potential of this simple approach for developing BNC-drug depots for localized and sustained release of therapeutic agents over adjustable timeframes.

Fast, Efficient Tailoring Growth of Nanocrystalline Diamond Films by Fine-Tuning of Gas-Phase Composition Using Microwave Plasma Chemical Vapor Deposition.

Nanocrystalline diamond (NCD) films are attractive for many applications due to their smooth surfaces while holding the properties of diamond. However, their growth rate is generally low using common Ar/CH4 with or without H2 chemistry and strongly dependent on the overall growth conditions using microwave plasma chemical vapor deposition (MPCVD). In this work, incorporating a small amount of N2 and O2 additives into CH4/H2 chemistry offered a much higher growth rate of NCD films, which is promising for some applications. Several novel series of experiments were designed and conducted to tailor the growth features of NCD films by fine-tuning of the gas-phase compositions with different amounts of nitrogen and oxygen addition into CH4/H2 gas mixtures. The influence of growth parameters, such as the absolute amount and their relative ratios of O2 and N2 additives; substrate temperature, which was adjusted by two ways and inferred by simulation; and microwave power on NCD formation, was investigated. Short and long deposition runs were carried out to study surface structural evolution with time under identical growth conditions. The morphology, crystalline and optical quality, orientation, and texture of the NCD samples were characterized and analyzed. A variety of NCD films of high average growth rates ranging from 2.1 µm/h up to 6.7 µm/h were successfully achieved by slightly adjusting the O2/CH4 amounts from 6.25% to 18.75%, while that of N2 was kept constant. The results clearly show that the beneficial use of fine-tuning of gas-phase compositions offers a simple and effective way to tailor the growth characteristics and physical properties of NCD films for optimizing the growth conditions to envisage some specific applications.

Biodegradation of e-waste microplastics by Penicillium brevicompactum.

Electronic and electric waste (e-waste) management strategies often fall short in dealing with the plastic constituents of printed circuit boards (PCB). Some plastic materials from PCB, such as epoxy resins, may release contaminants, but neither potential environmental impact has been assessed nor mitigation strategies have been put forward. This study assessed the biodegradation of microplastics (1-2 mm in size) from PCB by the fungus Penicillium brevicompactum over 28 days, thus contributing to the discussion of mitigation strategies for decreasing the environmental impact of such plastics in the environment. The capacity of P. brevicompactum to induce microplastic fragmentation and degradation has been determined by the increased the number of smaller-sized particles and microplastic mass reduction (up to 75 % within 14 days), respectively. The occurrence of chain scission and oxidation of microplastics exposed to P. brevicompactum when compared with the control conditions (which occurred only after 28 days of exposure) can be observed. Furthermore, Attenuated Total Reflectance-Fourier Transform Infrared (ATR-FTIR) spectroscopy performed in dried biomass put in evidence an increase in the absorption intensities in regions that could be attributed to functional groups associated with carbohydrates. The results underline the potential role of the genus Penicillium, particularly P. brevicompactum, in the biodegradation of microplastics from PCB, thus providing the basis for further exploration of its potential for e-waste bioremediation and research on the underlying mechanisms for sustainable approaches to mitigate e-waste pollution.

Detection of NT-proBNP Using Optical Fiber Back-Reflection Plasmonic Biosensors.

Heart failure (HF) is a clinical entity included in cardiovascular diseases affecting millions of people worldwide, being a leading cause of hospitalization of older adults, and therefore imposing a substantial economic burden on healthcare systems. HF is characterized by dyspnea, fatigue, and edema associated with elevated blood levels of natriuretic peptides, such as N Terminal pro-B-type Natriuretic Peptide (NT-proBNP), for which there is a high demand for point of care testing (POCT) devices. Optical fiber (OF) biosensors offer a promising solution, capable of real-time detection, quantification, and monitoring of NT-proBNP concentrations in serum, saliva, or urine. In this study, immunosensors based on plasmonic uncladded OF tips were developed using OF with different core diameters (200 and 600 µm). The tips were characterized to bulk refractive index (RI), anddetection tests were conducted with NT-proBNP concentrations varying from 0.01 to 100 ng/mL. The 200 µm sensors showed an average total variation of 3.6 ± 2.5 mRIU, an average sensitivity of 50.5 mRIU/ng·mL-1, and a limit of detection (LOD) of 0.15 ng/mL, while the 600 µm sensors had a response of 6.1 ± 4.2 mRIU, a sensitivity of 102.8 mRIU/ng·mL-1, and an LOD of 0.11 ng/mL. Control tests were performed using interferents such as uric acid, glucose, and creatinine. The results show the potential of these sensors for their use in biological fluids.

Microplastics in Internal Tissues of Companion Animals from Urban Environments.

Companion animals living in urban areas are exposed to environmental contaminants, which may include microplastics. A preliminary study was conducted by collecting postmortem samples from the internal tissue (lungs, ileum, liver, kidney, and blood clots) of 25 dogs (Canis familiaris) and 24 cats (Felis catus) living in an urban environment in Porto metropolitan area, Portugal. Suspected microplastics were found in 80 samples from 35 animals (18 cats and 17 dogs), often occurring in more than one tissue of the same animal (71.4%), primarily under small sizes (50.3% as 1-10 µm). Micro-Raman spectroscopy confirmed a fraction of particles as common polymer types (e.g., polyethylene terephthalate). However, the number of particles was very low. This study highlights the possibilities of the internalization and distribution of microplastics in the internal tissues of terrestrial vertebrates.

Label-free plasmonic immunosensor for cortisol detection in a D-shaped optical fiber.

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.

Relevance of the Spectral Analysis Method of Tilted Fiber Bragg Grating-Based Biosensors: A Case-Study for Heart Failure Monitoring.

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.

A Review on the Applications of Graphene in Mechanical Transduction.

A pressing need to develop low-cost, environmentally friendly, and sensitive sensors has arisen with the advent of the always-connected paradigm of the internet-of-things (IoT). In particular, mechanical sensors have been widely studied in recent years for applications ranging from health monitoring, through mechanical biosignals, to structure integrity analysis. On the other hand, innovative ways to implement mechanical actuation have also been the focus of intense research in an attempt to close the circle of human-machine interaction, and move toward applications in flexible electronics. Due to its potential scalability, disposability, and outstanding properties, graphene has been thoroughly studied in the field of mechanical transduction. The applications of graphene in mechanical transduction are reviewed here. An overview of sensor and actuator applications is provided, covering different transduction mechanisms such as piezoresistivity, capacitive sensing, optically interrogated displacement, piezoelectricity, triboelectricity, electrostatic actuation, chemomechanical and thermomechanical actuation, as well as thermoacoustic emission. A critical review of the main approaches is presented within the scope of a wider discussion on the future of this so-called wonder material in the field of mechanical transduction.

Immunosensing Based on Optical Fiber Technology: Recent Advances.

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.

Electrochemical Response of Glucose Oxidase Adsorbed on Laser-Induced Graphene.

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.

Preparation of biological samples for microplastic identification by Nile Red.

Many methods have been used to isolate and identify microplastics from biological matrices. In biological samples, Nile Red can stain undigested residues, such as fats, soaps, and gels formed during organic matter removal, hindering the identification of fluorescent microplastics (≥2 µm). Thus, adjustments on sample preparation (e.g., fat removal) are required for the accurate identification of Nile Red stained microplastics. Multiples tests allowed to identify that digestion with 10% KOH at 60 °C for 24 h, followed by treatments with boiling water, acetone, and staining, produced good results in fourteen biological samples, including vertebrates and invertebrates. Digestion efficiencies were 94-100%, except for feces, which were 87%. Recovery rates of spiked microplastics were 97-100%, and few effects were observed in the infrared spectra and carbonyl index of seven polymers, with only the occasional yellowing suggesting surface changes. Filtration rates were improved by reducing the amount of sample. Small fluorescent microplastics could be identified in all samples under the microscope. Overall, the proposed method was efficient in removing natural organic matter from biological samples for Nile Red staining, requiring minimal sample handling, improving sample throughput, and allowing quantification of fluorescent microplastics in biological samples.

Selection of microplastics by Nile Red staining increases environmental sample throughput by micro-Raman spectroscopy.

Nile Red staining enables visual identification and quantification of fluorescent particles as a proxy to microplastics at low cost and high throughput, including those of small sizes (≥2 µm), when preceded by proper natural organic matter removal, but providing no chemical characterization. On the other hand, micro-spectroscopy methods allow chemical characterization of particles based on their spectra, essential for polymer identification, but are costly and time-consuming. This work addresses the combination of both Nile Red staining with micro-Raman spectroscopy for the identification of microplastics. Besides being useful for quantification, Nile Red staining can be advantageously used as an objective criterion for pre-selection of particles for micro-Raman spectroscopy, producing little interference. The use of the 442 nm laser in micro-Raman spectroscopy induces Nile Red luminescence thus allowing to target the specific suspected microplastics when using an orange filter, reducing the number of particles subjected to identification and improving sample throughput. Staining dyes could also be used for mapping suspected microplastics before targeted analysis by micro-Raman spectroscopy. Thus, coupling Nile Red with micro-Raman spectroscopy can be useful to improve time efficiency while using this equipment.

Laser-Induced Graphene from Paper for Mechanical Sensing.

The ability to synthesize laser-induced graphene (LIG) on cellulosic materials such as paper opens the door to a wide range of potential applications, from consumer electronics to biomonitoring. In this work, strain and bending sensors fabricated by irradiation of regular filter paper with a CO2 laser are presented. A systematic study of the influence of the different process parameters on the conversion of cellulose fibers into LIG is undertaken, by analyzing the resulting morphology, structure, conductivity, and surface chemistry. The obtained material is characterized by porous electrically conductive weblike structures with sheet resistances reaching as low as 32 Ω sq-1. The functionality of both strain (gauge factor of ≈42) and bending sensors is demonstrated for different sensing configurations, emphasizing the versatility and potential of this material for low-cost, sustainable, and environmentally friendly mechanical sensing.

Cortisol AuPd plasmonic unclad POF biosensor.

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.

Identification of microplastics in white wines capped with polyethylene stoppers using micro-Raman spectroscopy.

Beverages, often packaged in plastic, can be a source of microplastics in the human diet. In this study, an improved method for detection of microplastics in white wines capped with synthetic stoppers is explored. Visual quantification in the stereomicroscope or using Nile Red were excluded due to the small size of particles. Quantification in the optical microscope identified up to 5,857 particles.L-1 but lacked chemical characterization. Finally, micro-Raman spectroscopy was used for the first time in complex beverages in the identification of microplastics particles in white wines, allowing identification of at least one synthetic particle for each bottle, except in two cases. Improvements included reduction in volume filtered, selection of aluminum oxide filters, selection of blue laser and lack of H2O2 treatment. Using this method, identification of all particles present in small representative areas of the filter by micro-Raman spectroscopy will allow proper quantification of microplastics in complex beverage matrices.

Physical Structure and Electrochemical Response of Diamond-Graphite Nanoplatelets: From CVD Synthesis to Label-Free Biosensors.

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.

Molecularly-imprinted chloramphenicol sensor with laser-induced graphene electrodes.

Graphene has emerged as a novel material with enhanced electrical and structural properties that can be used for a multitude of applications from super-capacitors to biosensors. In this context, an ultra-sensitive biosensor was developed using a low-cost, simple and mask-free method based on laser-induced graphene technique for electrodes patterning. The graphene was produced on a polyimide substrate, showing a porous multi-layer structure with a resistivity of 102.4 ±â€¯7.3 Ω/square. The biosensor was designed as a 3-electrode system. Auxiliary and working electrodes were made of graphene by laser patterning and the reference electrode was handmade by casting a silver ink. A molecularly-imprinted polymer (MIP) was produced at the working electrode by direct electropolymerization of eriochrome black T (EBT). As proof-of-concept, the MIP film was tailored for chloramphenicol (CAP), a common contaminant in aquaculture. The resulting device was evaluated by cyclic voltammetry and electrochemical impedance spectroscopy readings against a redox standard probe. The limit of detection (LOD) was 0.62 nM and the linear response ranged from 1 nM to 10 mM. These analytical features were better than those produced by assembling the same biorecognition element on commercial graphene- and carbon-based screen-printed electrodes. Overall, the simplicity and quickness of the laser-induced graphene technique, along with the better analytical features obtained with the graphene-based electrodes, shows the potential to become a commercial approach for on-site sensing.

ZnO decorated laser-induced graphene produced by direct laser scribing.

A scalable laser scribing approach to produce zinc oxide (ZnO) decorated laser-induced graphene (LIG) in a unique laser-processing step was developed by irradiating a polyimide sheet covered with a Zn/ZnO precursor with a CO2 laser (10.6 µm) under ambient conditions. The laser scribing parameters revealed a strong impact on the surface morphology of the formed LIG, on ZnO microparticles' formation and distribution, as well as on the physical properties of the fashioned composites. The ZnO microparticles were seen to be randomly distributed along the LIG surface, with the amount and dimensions depending on the used laser processing conditions. Besides the synthesis conditions, the use of different precursors also resulted in distinct ZnO growth's yields and morphologies. Raman spectroscopy revealed the existence of both wurtzite-ZnO and sp2 carbon in the majority of the produced samples. Broad emission bands in the visible range and the typical ZnO near band edge (NBE) emission were detected by photoluminescence studies. The spectral shape of the luminescence signal was seen to be extremely sensitive to the employed processing parameters and precursors, highlighting their influence on the composites' optical defect distribution. The sample produced from the ZnO-based precursor evidenced the highest luminescence signal, with a dominant NBE recombination. Electrochemical measurements pointed to the existence of charge transfer processes between LIG and the ZnO particles.

Effect of N2 and H2 plasma treatments on band edge emission of ZnO microrods.

ZnO microrods were grown by laser assisted flow deposition technique in order to study their luminescence behaviour in the near band edge spectral region. Transmission electron microscopy analysis put in evidence the high crystallinity degree and microrod's compositional homogeneity. Photoluminescence revealed a dominant 3.31 eV emission. The correlation between this emission and the presence of surface states was investigated by performing plasma treatments with hydrogen and nitrogen. The significant modifications in photoluminescence spectra after the plasma treatments suggest a connexion between the 3.31 eV luminescence and the surface related electronic levels.