Rapid determination of uracil in biological fluids at mercury thin film electrode for early detection of potential 5-fluorouracil toxicity due to dihydropyrimidine dehydrogenase deficiency.

Determination of plasma uracil was reported as a method for evaluation of Dihydropyrimidine dehydrogenase (DPD) activity that is highly demanded to ensure the safe administration of 5-fluorouracil (5-FU)-based therapies to cancer patients. This work reports the development of a simple electroanalytical method based on adsorptive stripping square wave voltammetry (AdSWV) at mercury film-coated glassy carbon electrode (MF/GCE) for the highly sensitive determination of uracil in biological fluids that can be used for diagnosis of decreased DPD activity. Due to the formation of the HgII-Uracil complex at the electrode surface, the accuracy of the measurement was not affected by the complicated matrices in biological fluids including human serum, plasma, and urine. The high sensitivity of the developed method results in a low limit of detection (≈1.3 nM) in human plasma samples, falling below the practical cut-off level of 15 ng mL-1 (≈0.14 µM). This threshold concentration is crucial for predicting 5-FU toxicity, as reported in buffer, and ≤1.15% in biological samples), and accuracy (recovery percentage close to 100%).

Enhancing the substrate selectivity of enzyme mimetics in biosensing and bioassay: Novel approaches.

A substantial development in nanoscale materials possessing catalytic activities comparable with natural enzymes has been accomplished. Their advantages were owing to the excellent sturdiness in an extreme environment, possibilities of their large-scale production resulting in higher profitability, and easy manipulation for modification. Despite these advantages, the main challenge for artificial enzyme mimetics is the lack of substrate selectivity where natural enzymes flourish. This review addresses this vital problem by introducing substrate selectivity strategies to three classes of artificial enzymes: molecularly imprinted polymers, nanozymes (NZs), and DNAzymes. These rationally designed strategies enhance the substrate selectivity and are discussed and exemplified throughout the review. Various functional mechanisms associated with applying enzyme mimetics in biosensing and bioassays are also given. Eventually, future directives toward enhancing the substrate selectivity of biomimetics and related challenges are discussed and evaluated based on their efficiency and convenience in biosensing and bioassays.

2D graphene-based advanced nanoarchitectonics for electrochemical biosensors: Applications in cancer biomarker detection.

Low-cost, rapid, and easy-to-use biosensors for various cancer biomarkers are of utmost importance in detecting cancer biomarkers for early-stage metastasis control and efficient diagnosis. The molecular complexity of cancer biomarkers is overwhelming, thus, the repeatability and reproducibility of measurements by biosensors are critical factors. Electrochemical biosensors are attractive alternatives in cancer diagnosis due to their low cost, simple operation, and promising analytical figures of merit. Recently graphene-derived nanostructures have been used extensively for the fabrication of electrochemical biosensors because of their unique physicochemical properties, including the high electrical conductivity, adsorption capacity, low cost and ease of mass production, presence of oxygen-containing functional groups that facilitate the bioreceptor immobilization, increased flexibility and mechanical strength, low cellular toxicity. Indeed, these properties make them advantageous compared to other alternatives. However, some drawbacks must be overcome to extend their use, such as poor and uncontrollable deposition on the substrate due to the low dispersity of some graphene materials and irreproducibility of the results because of the differences in various batches of the produced graphene materials. This review has documented the most recently developed strategies for electrochemical sensor fabrication. It differs in the categorization method compared to published works to draw greater attention to the wide opportunities of graphene nanomaterials for biological applications. Limitations and future scopes are discussed to advance the integration of novel technologies such as artificial intelligence, the internet of medical things, and triboelectric nanogenerators to eventually increase efficacy and efficiency.

Correction: Sýs et al. Bis(2,2'-bipyridil)Copper(II) Chloride Complex: Tyrosinase Biomimetic Catalyst or Redox Mediator? Materials 2021, 14, 113.

In the original publication [...].

In Situ Investigation of the Cytotoxic and Interfacial Characteristics of Titanium When Galvanically Coupled with Magnesium Using Scanning Electrochemical Microscopy.

Recently, the cytotoxic properties of galvanically coupled Ti-Mg particles have been shown in different cells. This cytotoxic effect has been attributed mainly to Mg due to its tendency to undergo activation when coupled with Ti, forming a galvanic cell consisting of an anode (Mg) and a cathode (Ti). However, the role of the Ti cathode has been ignored in explaining the cytotoxic effect of Ti-Mg particles due to its high resistance to corrosion. In this work, the role of titanium (Ti) in the cytotoxic mechanism of galvanically coupled Ti-Mg particles was examined. A model galvanic cell (MGC) was prepared to simulate the Mg-Ti particles. The electrochemical reactivity of the Ti sample and the pH change in it due to galvanic coupling with Mg were investigated using scanning electrochemical microscopy (SECM). It was observed that the Ti surface changed from passive to electrochemically active when coupled with Mg. Furthermore, after only 15 min of galvanic coupling with Mg, the pH in the electrolyte volume adjacent to the Ti surface increased to an alkaline pH value. The effects of the galvanic coupling of Ti and Mg, as well as those of the alkaline pH environment, on the viability of Hs27 fibroblast cells were investigated. It was shown that the viability of Hs27 cells significantly diminished when Mg and Ti were galvanically coupled compared to when the two metals were electrically disconnected. Thus, although Ti usually exhibited high corrosion resistance when exposed to physiological environments, an electrochemically active surface was observed when galvanically coupled with Mg, and this surface may participate in electron transfer reactions with chemical species in the neighboring environment; this participation resulted in the increased pH values above its surface and enhanced generation of reactive oxygen species. These features contributed to the development of cytotoxic effects by galvanically coupled Ti-Mg particles.

A Novel Biocompatible Titanium-Gadolinium Quantum Dot as a Bacterial Detecting Agent with High Antibacterial Activity.

: In this study, the titanium-gadolinium quantum dots (TGQDs) were novel, first of its type to be synthesized, and fully characterized to date. Multiple physical characterization includes scanning electron microscopy (SEM), scanning electrochemical microscope (SCEM), x-ray fluorescence, spectrophotometry, and dynamic light scattering were carried out. The obtained results confirmed appropriate size and shape distributions in addition to processing optical features with high quantum yield. The synthesized TGQD was used as a fluorescent dye for bacterial detection and imaging by fluorescent microscopy and spectrophotometry, where TGQD stained only bacterial cells, but not human cells. The significant antibacterial activities of the TGQDs were found against a highly pathogenic bacterium (Staphylococcus aureus) and its antibiotic resistant strains (vancomycin and methicillin resistant Staphylococcus aureus) using growth curve analysis and determination of minimum inhibitory concentration (MIC) analysis. Live/dead cell imaging assay using phase-contrast microscope was performed for further confirmation of the antibacterial activity. Cell wall disruption and release of cell content was observed to be the prime mode of action with the reduction of cellular oxygen demand (OD).

Bis(2,2'-bipyridil)Copper(II) Chloride Complex: Tyrosinase Biomimetic Catalyst or Redox Mediator?

In this article, construction of amperometric sensor(s) based on screen-printed carbon electrodes covered by thin layers of two types of carbon nanomaterials serving as amplifiers, and containing [Cu(bipy)2Cl]Cl∙5H2O complex is reported. Their performance and biomimetic activity towards two selected neurotransmitters (dopamine and serotonin) was studied mainly using flow injection analysis (FIA). The important parameters of FIA such as working potential, flow rate, and pH were optimized. The mechanism of the catalytic activity is explained and experimentally confirmed. It reveals that presence of hydrogen peroxide plays a crucial role which leads to answer the title question: can presented complex really be considered as a tyrosinase biomimetic catalyst or only as a redox mediator?