Electrocatalytic oxidation of pyrrole on a quasi-reversible silver nanodumbbell particle surface for supramolecular porphyrin production.

Photoactive supramolecular porphyrin assemblies are attractive molecules for light-harvesting applications. This is due to their relatively non-toxicity, biological activities and charge and energy exchange characteristics. However, the extreme cost associated with their synthesis and requirements for toxic organic solvents during purification pose a challenge to the sustainability characteristics of their applications. This work presents the first report on the sustainable synthesis, spectroscopic and photophysical characterizations of a near-infrared (NIR) absorbing Ca(II)-meso-tetrakis (4-hydroxyphenyl)porphyrin using an electrolyzed pyrrole solution. The latter was obtained by cycling the pyrrole solution across the silver nanodumbbell particle surface at room temperature. The electrolyzed solution condensed readily with acidified p-hydroxybenzaldehyde, producing the targeted purple porphyrin. The non-electrolyzed pyrrole solution formed a green substance with significantly different optical properties. Remarkable differences were observed in the voltammograms of the silver nanodumbbell particles and those of the conventional gold electrode during the pyrrole cycling, suggesting different routes of porphyrin formation. The rationale behind these formations and the associated mechanisms were extensively discussed. Metalation with aqueous Ca2+ ion caused a Stokes shift of 38.75 eV. The current study shows the advantage of the electrochemical method towards obtaining sustainable light-harvesting porphyrin at room temperature without the need for high-energy-dependent conventional processes.

Functionalities of electrochemical fluoroquinolone sensors and biosensors.

Fluoroquinolones (FQs) are a class of broad-spectrum antimicrobial agents that are used to treat variety of infectious diseases. This class of antibiotics was being used for patients exhibiting early symptoms of a human respiratory disease known as the COVID-19 virus. As a result, this outbreak causes an increase in drug-resistant strains and environmental pollution, both of which pose serious threats to biota and human health. Thus, to ensure public health and prevent antimicrobial resistance, it is crucial to develop effective detection methods for FQs determination in water bodies even at trace levels. Due to their characteristics like specificity, selectivity, sensitivity, and low detection limits, electrochemical biosensors are promising future platforms for quick and on-site monitoring of FQs residues in a variety of samples when compared to conventional detection techniques. Despite their excellent properties, biosensor stability continues to be a problem even today. However, the integration of nanomaterials (NMs) could improve biocompatibility, stability, sensitivity, and speed of response in biosensors. This review concentrated on recent developments and contemporary methods in FQs biosensors. Furthermore, a variety of modification materials on the electrode surface are discussed. We also pay more attention to the practical applications of electrochemical biosensors for FQs detection. In addition, the existing challenges, outlook, and promising future perspectives in this field have been proposed. We hope that this review can serve as a bedrock for future researchers and provide new ideas for the development of electrochemical biosensors for antibiotics detection in the future.

Bode Phase Angle Signaling of a TB Disease Biomarker.

Tuberculosis (TB) is a worldwide burden whose total control and eradication remains a challenge due to factors including false positive/negative diagnoses associated with the poor sensitivity of the current diagnostics in immune-compromised and post-vaccinated individuals. As these factors complicate both diagnosis and treatment, the early diagnosis of TB is of pivotal importance towards reaching the universal vision of a TB-free world. Here, an aptasensor for signaling an interferon gamma (IFN-γ) TB biomarker at low levels is reported. The aptasensor was assembled through gold-thiol interactions between poly(3,4-propylenedioxythiophene), gold nanoparticles, and a thiol-modified DNA aptamer specific to IFN-γ. The aptasensor sensitively detected IFN-γ in spiked pleural fluid samples with a detection limit of 0.09 pg/mL within a linear range from 0.2 pg/mL to 1.2 pg/mL. The good performance of the reported aptasensor indicates that it holds the potential for application in the early diagnosis of, in addition to TB, various diseases associated with IFN-γ release in clinical samples.

Recent Advances in Applications of Oxidases and Peroxidases Polymer-Based Enzyme Biocatalysts in Sensing and Wastewater Treatment: A Review.

Oxidase and peroxidase enzymes have attracted attention in various biotechnological industries due to their ease of synthesis, wide range of applications, and operation under mild conditions. Their applicability, however, is limited by their poor stability in harsher conditions and their non-reusability. As a result, several approaches such as enzyme engineering, medium engineering, and enzyme immobilization have been used to improve the enzyme properties. Several materials have been used as supports for these enzymes to increase their stability and reusability. This review focusses on the immobilization of oxidase and peroxidase enzymes on metal and metal oxide nanoparticle-polymer composite supports and the different methods used to achieve the immobilization. The application of the enzyme-metal/metal oxide-polymer biocatalysts in biosensing of hydrogen peroxide, glucose, pesticides, and herbicides as well as blood components such as cholesterol, urea, dopamine, and xanthine have been extensively reviewed. The application of the biocatalysts in wastewater treatment through degradation of dyes, pesticides, and other organic compounds has also been discussed.

Quantum Dot-Sensitised Estrogen Receptor-α-Based Biosensor for 17ß-Estradiol.

17ß-estradiol (E2) is an important natural female hormone that is also classified as an estrogenic endocrine-disrupting compound (e-EDC). It is, however, known to cause more damaging health effects compared to other e-EDCs. Environmental water systems are commonly contaminated with E2 that originates from domestic effluents. The determination of the level of E2 is thus very crucial in both wastewater treatment and in the aspect of environmental pollution management. In this work, an inherent and strong affinity of the estrogen receptor-α (ER-α) for E2 was used as a basis for the development of a biosensor that was highly selective towards E2 determination. A gold disk electrode (AuE) was functionalised with a 3-mercaptopropionic acid-capped tin selenide (SnSe-3MPA) quantum dot to produce a SnSe-3MPA/AuE electroactive sensor platform. The ER-α-based biosensor (ER-α/SnSe-3MPA/AuE) for E2 was produced by the amide chemistry of carboxyl functional groups of SnSe-3MPA quantum dots and the primary amines of ER-α. The ER-α/SnSe-3MPA/AuE receptor-based biosensor exhibited a formal potential (E0') value of 217 ± 12 mV, assigned as the redox potential for monitoring the E2 response using square-wave voltammetry (SWV). The response parameters of the receptor-based biosensor for E2 include a dynamic linear range (DLR) value of 1.0-8.0 nM (R2 = 0.99), a limit of detection (LOD) value of 1.69 nM (S/N = 3), and a sensitivity of 0.04 µA/nM. The biosensor exhibited high selectivity for E2 and good recoveries for E2 determination in milk samples.

Enhanced visible light driven photoelectrochemical degradation of tetracycline hydrochloride using a BiOI photoanode modified with MnO2 films.

Removal of pharmaceuticals in wastewater has been the focus of many research due to the recalcitrant nature and hazardous effects of these compounds. The photoelectrochemical degradation process has proven to be suitable to harness solar energy for the mineralization of organic compounds in wastewater. Herein, we report the application of BiOI/MnO2 heterostructured anode for the photoelectrochemical degradation of tetracycline hydrochloride in aqueous solution. The photoanode was prepared through electrodeposition technique and fully characterized through microscopic, spectroscopic and electrochemical techniques. The results showed that formation of p-n heterojunction between BiOI and MnO2 in the photoanode led to improved charge separation which was evident in improved optical and photoelectrochemical properties. The FTO-BiOI/MnO2 electrode attained a photocurrent density of 0.104 mA cm-2 with applied potential of 1.0 V (vs Ag/AgCl) which was almost double that of pristine BiOI suggesting efficient charge separation. The heterostructured photoanode achieved 94% removal of tetracycline hydrochloride after 120 min through the PEC degradation process with 61% mineralization efficiency. The electrode showed good reusability and stability with 92% PEC removal after eight cycles. Hence, the FTO-BiOI/MnO2 has a great potential as anode for PEC wastewater treatments.

Advances in polymer-based detection of environmental ibuprofen in wastewater.

Globally, ibuprofen is the third most consumed drug and its presence in the environment is a concern because little is known about its adverse effects on humans and aquatic life. Environmentalists have made monitoring and the detection of ibuprofen in biological and environmental matrices a priority. For the detection and monitoring of ibuprofen, sensors and biosensors have provided rapid analysis time, sensitivity, high-throughput screening, and real-time analysis. Researchers are increasingly seeking eco-friendly technology, and this has led to an interest in developing biodegradable, bioavailable, and non-toxic sensors, or biosensors. The integration of polymers into sensor systems has proven to significantly improve sensitivity, selectivity, and stability and minimize sample preparation using bioavailable and biodegradable polymers. This review provides a general overview of perspectives and trends of polymer-based sensors and biosensors for the detection of ibuprofen compared to non-polymer-based sensors.

Recent advances in the detection of interferon-gamma as a TB biomarker.

Tuberculosis (TB) is one of the main infectious diseases worldwide and accounts for many deaths. It is caused by Mycobacterium tuberculosis usually affecting the lungs of patients. Early diagnosis and treatment are essential to control the TB epidemic. Interferon-gamma (IFN-γ) is a cytokine that plays a part in the body's immune response when fighting infection. Current conventional antibody-based TB sensing techniques which are commonly used include enzyme-linked immunosorbent assay (ELISA) and interferon-gamma release assays (IGRAs). However, these methods have major drawbacks, such as being time-consuming, low sensitivity, and inability to distinguish between the different stages of the TB disease. Several electrochemical biosensor systems have been reported for the detection of interferon-gamma with high sensitivity and selectivity. Microfluidic techniques coupled with multiplex analysis in regular format and as lab-on-chip platforms have also been reported for the detection of IFN-γ. This article is a review of the techniques for detection of interferon-gamma as a TB disease biomarker. The objective is to provide a concise assessment of the available IFN-γ detection techniques (including conventional assays, biosensors, microfluidics, and multiplex analysis) and their ability to distinguish the different stages of the TB disease.

A review on water treatment technologies for the management of oxoanions: prospects and challenges.

Oxoanions are a class of contaminants that are easily released into the aquatic systems either through natural or anthropogenic activities. Depending on their oxidation states, they are highly mobile, resulting in the contamination of underground water. Above the permissible level in groundwater, they pose as threats to mammals when the contaminated water is consumed. Some of the health challenges caused are cancer, neurological, cardiac, gastrointestinal, and skin disorders. Several treatment technologies have been adopted over the years for the management of these oxoanions present in the aquatic systems. However interesting these treatment technologies might be, they also have their limitations such as cost-effectiveness, the complexity of the process, and generation of secondary pollutants. This work focused on some of the water treatment technologies applied for the removal of oxoanions. Some of the advantages and disadvantages of these treatment technologies are also highlighted. Amongst all the treatment technologies, adsorption is the most applied method for the removal of oxoanions. However, photocatalysis has a higher prospect since it is non-selective and secondary pollutants are not generated after the treatment process. Also, photocatalysis can simultaneously reduce and oxidise oxoanions as well as organic pollutants respectively.

Recent advances in degradation of pharmaceuticals using Bi2WO6 mediated photocatalysis - A comprehensive review.

The pollution of water bodies by residual pharmaceuticals is a major problem globally. Bismuth tungstate mediated photocatalysis has been effective in the removal of these organics from water. Bismuth tungstate (Bi2WO6) has proven to be an excellent visible light active photocatalyst because of its non-toxicity, low band gap energy and ease of preparation. It has been widely applied for the removal of a wide array of organic pollutants, particularly dyes, from wastewater. However, recently, much attention has been channelled to its application for the degradation of pharmaceuticals. In this present review, the recent trends in the applications of Bi2WO6 based photocatalysts for the removal of pharmaceuticals in wastewater are comprehensively discussed. The fabrication of Bi2WO6 based photocatalysts with enhanced photocatalytic performances through morphology control, doping and formation of heterojunctions are highlighted. Much discussion centres on the mechanisms and possible degradation pathways of antibiotic pharmaceuticals in wastewater. Finally, areas needing more attention and investigation on the use of Bi2WO6 based photocatalysts for removal of pharmaceuticals from wastewater especially towards real-life applications are presented for future research directions.

Graphitic Carbon Nitride: A Highly Electroactive Nanomaterial for Environmental and Clinical Sensing.

Graphitic carbon nitride (g-C3N4) is a two-dimensional conjugated polymer that has attracted the interest of researchers and industrial communities owing to its outstanding analytical merits such as low-cost synthesis, high stability, unique electronic properties, catalytic ability, high quantum yield, nontoxicity, metal-free, low bandgap energy, and electron-rich properties. Notably, graphitic carbon nitride (g-C3N4) is the most stable allotrope of carbon nitrides. It has been explored in various analytical fields due to its excellent biocompatibility properties, including ease of surface functionalization and hydrogen-bonding. Graphitic carbon nitride (g-C3N4) acts as a nanomediator and serves as an immobilization layer to detect various biomolecules. Numerous reports have been presented in the literature on applying graphitic carbon nitride (g-C3N4) for the construction of electrochemical sensors and biosensors. Different electrochemical techniques such as cyclic voltammetry, electrochemiluminescence, electrochemical impedance spectroscopy, square wave anodic stripping voltammetry, and amperometry techniques have been extensively used for the detection of biologic molecules and heavy metals, with high sensitivity and good selectivity. For this reason, the leading drive of this review is to stress the importance of employing graphitic carbon nitride (g-C3N4) for the fabrication of electrochemical sensors and biosensors.

Core-Shell Palladium Telluride Quantum Dot-Hemethiolate Cytochrome Based Biosensor for Detecting Indinavir Drug.

Indinavir is a first-generation HIV protease inhibitor anti-retroviral (ARV) drug. Due to interindividual differences in the rate of indinavir metabolism, clinicians and pharmacologists have expressed urgent need for sensor devices that will enable real time determination of appropriate dosage. In this study, an indinavir biosensor was developed by the functionalization of a cysteamine-modified gold (Cyst|Au) electrode with biocompatible core-shell 3-mercaptopropionic acid (3-MPA)-capped palladium telluride quantum dot (PdTeQD) and the heme-thiolate cytochrome P450-3A4 (CYP3A4) enzyme. The PdTeQD was capped with 3-mercaptopropionic acid (3-MPA) to improve its reactivity, biocompatibility and thermal stability. Small angle X-ray scattering (SAXS) studies revealed that the 3-MPA-PdTeQD particles formed core-shells with diameters of 4.7 nm. Fourier transformed infrared spectroscopy (FTIR) experiments confirmed the formation of 3-MPA-PdTeQD by the presence of specific COOH and CH2 FTIR signature bands. Ultraviolet-visible (UV-Vis) spectrophotometric analysis of the quantum dot, exhibited a broad characteristic band at ~320 nm, corresponding to a band gap energy (Eg) value of 3.87 eV, indicating that the QD is a semiconducting material. Cyclic voltammetry (CV) responses of the biosensor (i.e., CYP3A4|3-MPA-PdTeQD|Cyst|Au) indicated that 0.26 V was the suitable potential for measuring indinavir metabolism. The biosensor has a sensitivity, dynamic linear range (DLR) and limit of detection (LOD) values of 0.0218 µA/nM, 0.0004-0.01 nM (i.e., 3×10-7 -7×10-6 mg L-1) and 0.023×10-7 mg L-1, respectively, for indinavir. The LOD value was lower than the maximum plasma concentration (Cmax) value (0.13-8.6 mg L-1) of indinavir which is normally measure 8 h after intake. The low DLR value makes the biosensor suitable for application at point-of-care, where indinavir concentration is expected to be in ng L-1 level in physiological samples within a few minutes of the drug administration.

Dendritic copolymer electrode for second harmonic alternating current voltammetric signalling of pyrene in oil-polluted wastewater.

A sensitive dendritic star copolymer-based sensor for pyrene (PY), was developed by in situ electrosynthesis of generation 3 poly(propylene thiophenoimine)-co-poly(3-hexylthiophene) (G3PPT-co-P3HT) on a gold disk electrode (Au). The electrochemical reactivity and the signal transduction properties of the Au|G3PPT-co-P3HT co-polymer electrode were studied by second harmonic alternating current voltammetry (SHACV) and alternating current voltammetry (ACV), respectively. SHACV analysis confirmed the occurrence of Faradaic electrode process (with a standard rate constant, k0 value of 3.36 cm s-1), possibly originating from the surface-confined thiophene groups of the co-polymer electrode. The ACV responses of the Au|G3PPT-co-P3HT electrode to pyrene gave a linear range (LR) of 2.73-26.86 nM and a limit of detection (LOD) of 1.34 nM PY. The low LOD value suggests that the PY sensor has promise for monitoring compliance to the World Health Organization (WHO) approved limit for polyaromatic hydrocarbons (PAHs) in wastewater, which is 3.93 nM. The sensor was used to determine PY levels in oil-polluted wastewater samples, which were found to contain 4.93-23.49 nM PY, depending on how far into the sea the samples were collected. The high recovery rate obtained for the oil-polluted seawater samples, indicate that ACV signalling protocol makes the Au|G3PPT-co-P3HT electrode very suitable for application in samples that have complex matrices.