Ratiometric electrochemical detection of kojic acid based on glassy carbon modified MXene nanocomposite.

The significance of developing a selective and sensitive sensor for quality control purposes is underscored by the prevalent use of kojic acid (KA) in cosmetics, pharmaceuticals, and food items. KA's utility stems from its ability to inhibit tyrosinase activity. However, the instability of KA and its potential adverse effects have created a pressing need for accurate and sensitive sensors capable of analyzing real samples. This research introduces an electrochemical ratiometric sensor designed to accurately detect KA in actual cosmetic and food samples. The ratiometric sensor offers distinct advantages such as enhanced selectivity, reproducibility, and sensitivity. It achieves this by leveraging the ratio between two output signals, thereby producing reliable and undistorted results. The sensor is constructed by modifying a Glassy Carbon Electrode (GCE) with a nanocomposite consisting of Ti3C2 MXene, Prussian blue, and gold nanoparticles. The incorporation of MXene and gold nanoparticles heightens sensitivity and reduces impedance. Meanwhile, the Prussian blue signal diminishes proportionally with increasing KA concentration, forming the basis for the ratiometric sensing mechanism. The outcomes of the study reveal a broad linear range (1-600 µM), a low detection limit (1 µM), and strong selectivity for KA. These findings suggest the sensor's potential efficacy in quality control across cosmetics, pharmaceuticals, and food products.

Recent Trends in Metal Nanoparticles Decorated 2D Materials for Electrochemical Biomarker Detection.

Technological advancements in the healthcare sector have pushed for improved sensors and devices for disease diagnosis and treatment. Recently, with the discovery of numerous biomarkers for various specific physiological conditions, early disease screening has become a possibility. Biomarkers are the body's early warning systems, which are indicators of a biological state that provides a standardized and precise way of evaluating the progression of disease or infection. Owing to the extremely low concentrations of various biomarkers in bodily fluids, signal amplification strategies have become crucial for the detection of biomarkers. Metal nanoparticles are commonly applied on 2D platforms to anchor antibodies and enhance the signals for electrochemical biomarker detection. In this context, this review will discuss the recent trends and advances in metal nanoparticle decorated 2D materials for electrochemical biomarker detection. The prospects, advantages, and limitations of this strategy also will be discussed in the concluding section of this review.

Conformationally Flexible Dimeric-Serotonin-Based Sensitive and Selective Electrochemical Biosensing Strategy for Serotonin Recognition.

A novel electrochemical sensor was constructed based on an enzyme-mediated physiological reaction between neurotransmitter serotonin per-oxidation to reconstruct dual-molecule 4,4'-dimeric-serotonin self-assembled derivative, and the potential biomedical application of the multi-functional nano-platform was explored. Serotonin accelerated the catalytic activity to form a dual molecule at the C4 position and created phenolic radical-radical coupling intermediates in a peroxidase reaction system. Here, 4,4' dimeric-serotonin possessed the capability to recognize intermolecular interactions between amine groups. The excellent quenching effects on top of the gold surface electrode system archive logically inexpensive and straightforward analytical demands. In biochemical sensing analysis, the serotonin dimerization concept demonstrated a robust, low-cost, and highly sensitive immunosensor, presenting the potential of quantifying serotonin at point-of-care (POC) testing. The high-specificity serotonin electrochemical sensor had a limit of detection (LOD) of 0.9 nM in phosphate buffer and 1.4 nM in human serum samples and a linear range of 10 to 400 with a sensitivity of 2.0 × 10-2 nM. The bivalent 4,4'-dimer-serotonin interaction strategy provides a promising platform for serotonin biosensing with high specificity, sensitivity, selectivity, stability, and reproducibility. The self-assembling gold surface electrochemical system presents a new analytical method for explicitly detecting tiny neurotransmitter-responsive serotonin neuromolecules.

Advances of MXenes; Perspectives on Biomedical Research.

The last decade witnessed the emergence of a new family of 2D transition metal carbides and nitrides named MXenes, which quickly gained momentum due to their exceptional electrical, mechanical, optical, and tunable functionalities. These outstanding properties also rendered them attractive materials for biomedical and biosensing applications, including drug delivery systems, antimicrobial applications, tissue engineering, sensor probes, auxiliary agents for photothermal therapy and hyperthermia applications, etc. The hydrophilic nature of MXenes with rich surface functional groups is advantageous for biomedical applications over hydrophobic nanoparticles that may require complicated surface modifications. As an emerging 2D material with numerous phases and endless possible combinations with other 2D materials, 1D materials, nanoparticles, macromolecules, polymers, etc., MXenes opened a vast terra incognita for diverse biomedical applications. Recently, MXene research picked up the pace and resulted in a flood of literature reports with significant advancements in the biomedical field. In this context, this review will discuss the recent advancements, design principles, and working mechanisms of some interesting MXene-based biomedical applications. It also includes major progress, as well as key challenges of various types of MXenes and functional MXenes in conjugation with drug molecules, metallic nanoparticles, polymeric substrates, and other macromolecules. Finally, the future possibilities and challenges of this magnificent material are discussed in detail.

Recombinant Histidine-Tagged Nano-protein-based Highly Sensitive Electro-Sensing Device for Salivary Cortisol.

We have developed a powerful biosensing strategy for immobilizing histidine-tagged (His-Tag)-oriented recombinant nano-protein immobilization on a chemically modified glassy carbon electrode (GCE) surfaces via (S)-N-(5-amino-1-carboxypentyl)iminodiacetic acid (ANTA) acting as a chelating Ni2+ centered interaction. Here, we introduce a label-free electro-sensor to quantify cortisol levels in saliva samples for point-of-care testing (POCT). The high specificity of the chemically modified GCE was established by genetically bio-engineered metal-binding sites on the selected recombinant apoferritin (R-AFTN) nano-protein to impart functionality to its surface and by coating the carbon surface with the self-assembled monolayers of 4-aminobenzoic acid (4-ABA) attached to ANTA groups complexed with Ni2+ transition metal ions. Despite the variety of conventional assays available to monitor cortisol levels, they require bulky exterior outfits, which hinders use in the healthcare systems. Therefore, we performed a rapid, easy-to-implement, and low-cost quantitative electro-sensor to enable the real-time detection of cortisol levels in saliva samples. As a result, the cortisol electro-sensor fabricated with high specificity utilizing a GCE could measure cortisol levels with a detection limit of 0.95 ng/ml and sensitivity of 7.91 µA/(ng/mL), which is a practical approach in human saliva. Thus, protein nanoprobe-based cortisol biosensing showed high sensitivity and selectivity for the direct electro-sensing of cortisol for POCT.

Concurrent and Selective Determination of Dopamine and Serotonin with Flexible WS2 /Graphene/Polyimide Electrode Using Cold Plasma.

Makers of point-of-care devices and wearable diagnostics prefer flexible electrodes over conventional electrodes. In this study, a flexible electrode platform is introduced with a WS2 /graphene heterostructure on polyimide (WGP) for the concurrent and selective determination of dopamine and serotonin. The WGP is fabricated directly via plasma-enhanced chemical vapor deposition (PECVD) at 150 °C on a flexible polyimide substrate. Owing to the limitations of existing fabrication methods from physical transfer or hydrothermal methods, many studies are not conducted despite excellent graphene-based heterostructures. The PECVD synthesis method can provide an innovative WS2 /graphene heterostructure of uniform quality and sufficient size (4 in.). This unique heterostructure affords excellent electrical conductivity in graphene and numerous electrochemically active sites in WS2 . A large number of uniform qualities of WGP electrodes show reproducible and highly sensitive electrochemical results. The synergistic effect enabled well-separated voltammetric signals for dopamine and serotonin with a potential gap of 188 mV. Moreover, the practical application of the flexible sensor is successfully evaluated by using artificial cerebrospinal fluid.

'Laccase-like' properties of coral-like silver citrate micro-structures for the degradation and determination of phenolic pollutants and adrenaline.

Laccases are multicopper containing oxidase enzymes that are highly important in environmental remediation and biotechnology. To date, complex Copper containing materials have been reported as laccase mimic, and the possibility of a non-Cu laccase mimic remained unknown. In this work, we report an exceptionally simple functional laccase mimic based on coral-like silver citrate (AgCit) microstructures. The AgCit was synthesized by a simple precipitation method and was found to possess excellent laccase-like activity capable of oxidizing phenolic substrates and the endocrine hormone adrenaline. Compared to the natural laccase enzyme, our reported laccase-mimic has a higher υmax and lower Km value using adrenaline as a substrate. In addition, the AgCit laccase mimic was observed to be stable at extreme pH, higher temperature, and suitable for long-term storage at room temperature. The laccase-like properties of the AgCit nanozyme were successfully applied for the quantification and degradation of various phenolic pollutants and the adrenaline hormone.

A MoS2@Ti3C2Tx MXene hybrid-based electrochemical aptasensor (MEA) for sensitive and rapid detection of Thyroxine.

In the present study, a MoS2@Ti3C2Tx MXene hybrid-based electrochemical aptasensor (MEA) was introduced for sensitive and rapid quantification of Thyroxine (T4). T4 is a crucial hormone and plays a key role in various body functions. Therefore, there is high demand for an accurate, sensitive, and rapid method for the detection of T4. To construct the aptasensor, a nano-hybrid (NH) consisting of Ti3C2Tx MXene and MoS2 nanosheets (NS) was synthesized, and applied to a carbon electrode surface, followed by the electroplating of gold nanostructures (GN). The smart combination of Ti3C2Tx MXene and MoS2NS enhanced the physiochemical properties of the electrode surface, as well as provided a building block to form 3D GN. The 3D architecture of the GN offered a unique substrate to capture numerous T4 aptamer molecules, which consequently amplified the signal by nearly 6-fold. The MEA quantified thyroxine with a limit of detection (LOD) of 0.39 pg/mL over a dynamic range ((7.8 × 10-1) to (7.8 × 106)) pg/mL within 10 min. Moreover, the MEA successfully detected T4 in human serum samples. Lastly, the results obtained from the aptasensor were compared with those from the ELISA standard method. The comparative analysis showed good agreement between the two methods.

Ultrasensitive Materials for Electrochemical Biosensor Labels.

Since the fabrication of the first electrochemical biosensor by Leland C. Clark in 1956, various labeled and label-free sensors have been reported for the detection of biomolecules. Labels such as nanoparticles, enzymes, Quantum dots, redox-active molecules, low dimensional carbon materials, etc. have been employed for the detection of biomolecules. Because of the absence of cross-reaction and highly selective detection, labeled biosensors are advantageous and preferred over label-free biosensors. The biosensors with labels depend mainly on optical, magnetic, electrical, and mechanical principles. Labels combined with electrochemical techniques resulted in the selective and sensitive determination of biomolecules. The present review focuses on categorizing the advancement and advantages of different labeling methods applied simultaneously with the electrochemical techniques in the past few decades.

Gold nanoparticle/MXene for multiple and sensitive detection of oncomiRs based on synergetic signal amplification.

Multiple and sensitive detection of oncomiRs for accurate cancer diagnostics is still a challenge. Here, a synergetic amplification strategy was introduced by combining a MXene-based electrochemical signal amplification and a duplex-specific nuclease (DSN)-based amplification system for rapid, attomolar and concurrent quantification of multiple microRNAs on a single platform in total plasma. Synthesized MXene-Ti3C2Tx modified with 5 nm gold nanoparticles (AuNPs) was casted on a dual screen-printed gold electrode to host vast numbers of DNA probes identically co-immobilized on dedicated electrodes. Interestingly, presence of MXene provided biofouling resistance and enhanced the electrochemical signals by almost 4 folds of magnitude, attributed to its specious surface area and remarkable charge mobility. The 5 nm AuNPs were perfectly distributed within the whole flaky architect of the MXene to give rise to the electrochemical performance of MXene and provide the thiol-Au bonding feature. This synergetic strategy reduced the DSN-based biosensors' assay time to 80 min, provided multiplexability, antifouling activity, substantial sensitivity and specificity (single mutation recognition). The limit of detection of the proposed biosensor for microRNA-21 and microRNA-141 was respectively 204 aM and 138 aM with a wide linear range from 500 aM to 50 nM. As a proof of concept, this newly-developed strategy was coupled with a 96-well adaptive sensing device to successfully profile three cancer plasma samples based on their altered oncomiR abundances.

ß-Hydroxybutyrate dehydrogenase decorated MXene nanosheets for the amperometric determination of ß-hydroxybutyrate.

MXene nanosheets of type Ti3C2Tx were modified with ß-hydroxybutyrate dehydrogenase and then used as a biosensor for amperometric sensing of ß-hydroxybutyrate. The MXene and the nanocomposite were characterized by X-ray photoelectron spectroscopy, field-emission scanning electron microscopy, X-ray diffraction, and Fourier transform infrared spectroscopy. The MXene has a layered structure and proved to be an excellent immobilization matrix providing good compatibility with the enzyme ß-hydroxybutyrate dehydrogenase. The MXene-based biosensor, best operated at a potential of - 0.35 V (vs. Ag/AgCl), displays a wide linear range (0.36 to 17.9 mM), a sensitivity of 0.480 µA mM-1 cm-2, and a low detection limit (45 µM). The biosensor was successfully applied to the determination of ß-hydroxybutyrate in (spiked) real serum samples. Graphical abstract Schematic representation of the synthesis and decoration of Mxene 2D sheets with ß-hydroxybutyrate dehydrogenase for the amperometric determination of ß-hydroxybutyric acid.

Dual enzyme-like properties of silver nanoparticles decorated Ag2WO4 nanorods and its application for H2O2 and glucose sensing.

The facile one-pot hydrothermal synthesis of silver nanoparticles decorated silver tungstate nanorods (Ag@Ag2WO4 NRs) and their catalytic activities similar to those of natural enzymes catalase and peroxidase were reported. The Ag@Ag2WO4 NRs could catalyze the decomposition reaction of H2O2 into water and oxygen besides catalyzing the reduction of H2O2 into water in the presence of peroxidase substrates. Spectrophotometric and electrochemical methods were used to investigate the pH-dependent dual enzyme mimics exhibited by Ag@Ag2WO4 NRs. The Ag@Ag2WO4 NRs showed a lower Km value when compared to the natural horseradish peroxidase enzyme showing the stronger affinity for hydrogen peroxide and TMB. The peroxidase-like property of the synthesized Ag@Ag2WO4 NRs was exploited to develop a H2O2 sensor with a broad linear range and low detection limit. Thus, a wide linear range of 45.4 µM- 2.38 mM and a low detection limit of 5.4 µM was obtained by spectrophotometry while a wide linear range of 62.34 µM- 2.4 mM and a low detection limit of 6.25 µM was obtained by amperometry for H2O2. Further, the detection method was extended for the detection of glucose with a wide linear range of 27.7 µM- 0.33 mM and a low detection limit of 2.6 µM.

Relay-race RNA/barcode gold nanoflower hybrid for wide and sensitive detection of microRNA in total patient serum.

Development of a very sensitive biosensor is accompanied with an inevitable shrinkage in the linear detection range. Here, we developed an electrochemical biosensor with a novel methodology to detect microRNA-21 (miR21) at an ultralow level and broad linear detection range. A three-way junction RNA structure was designed harboring (i) a methylene blue (MB)-modified hairpin structure at its one leg to function as the sensing moiety and (ii) the other two legs to be further hybridized with barcode gold nanoparticles (MB/barG) as the signal amplifiers. Addition of target miR21 resulted in opening the hairpin moiety and subsequent hybridization with DNA-modified gold nanoflower/platinum electrode (GNF@Pt) to form the MB-3 sensor. Inspired by the relay-race run, to extend the dynamic detection range and increase the sensitivity of the biosensor, MB/barG was added to form the second detection modality (MBG-3). The combined sensor required very low sample volume (4 µL) and could identify 135 aM or 324 molecules of miR21 with the ability to operate within a wide linear range from 1 µM down to 500 aM. The fabricated GNF@Pt showed a remarkable conductivity compared with the gold nanoparticle-modified electrode. Addition of MB/barG boosted the electrochemical signal of the MB by almost 230 times. Moreover, a new protocol was introduced by the authors to increase the efficiency of microRNA extraction from the total serum. Possessing a sound selectivity and specificity towards single base-pair mutations, the developed biosensor could profile cancer development stages of two patient serums.