Development of a nanozyme-based electrochemical catalyst for real-time biomarker sensing of superoxide and nitric oxide anions released from living cells and exogenous donors.

Developing quantitative biosensors of superoxide (O2•-) and nitric oxide (NO) anion is crucial for pathological research. As of today, the main challenge for electrochemical detection is to develop high-selectivity nano-mimetic materials to replace natural enzymes. In this study, the dendritic-like morphological structure of silver organic framework (Ag-MOF) was successfully synthesized via a solvothermal strategy. Owing to the introduction of polymeric composites results in improved electrical conductivity and catalytic activity, which promotes mass transfer and leads to faster electron efficiency. For monitoring the electrochemical signals of O2•- and NO, the Ag-MOF electrode substrate was produced by drop-coating, and composites were designed by cyclic voltammetric potential cycles. The designed electrode substrates demonstrate high sensitivity, wide linear concentrations of 1 nM-1000 µM and 1 nM-850 µM, and low detection limits of 0.27 nM and 0.34 nM (S/N = 3) against O2•- and NO. Aside from that, the sensor successfully monitored the cellular release of O2•-, and NO from HepG2 and RAW 264.7 living cells and has the potential to monitor exogenous NO release from donors of Diethylamine (DEA)-NONOate and sodium nitroprusside (SNP). Additionally, the developed system was applied to the analysis of O2•- and NO in real biological fluid samples, and the results were good satisfactory (94.10-99.57 ± 1.23%). The designed system provides a novel approach to obtaining a good electrochemical biosensor platform that is highly selective, stable, and flexible. Finally, the proposed method provides a quantitative way to follow the dynamic changes in O2•- and NO in biological systems.

Self-Immolative Electrochemical Redox Substrates: Emerging Artificial Receptors in Sensing and Biosensing.

The development of artificial receptors has great significance in measurement science and technology. The need for a robust version of natural receptors is getting increased attention because the cost of natural receptors is still high along with storage difficulties. Aptamers, imprinted polymers, and nanozymes are some of the matured artificial receptors in analytical chemistry. Recently, a new direction has been discovered by organic chemists, who can synthesize robust, activity-based, self-immolative organic molecules that have artificial receptor properties for the targeted analytes. Specifically designed trigger moieties implant selectivity and sensitivity. These latent electrochemical redox substrates are highly stable, mass-producible, inexpensive, and eco-friendly. Combining redox substrates with the merits of electrochemical techniques is a good opportunity to establish a new direction in artificial receptors. This Review provides an overview of electrochemical redox substrate design, anatomy, benefits, and biosensing potential. A proper understanding of molecular design can lead to the development of a library of novel self-immolative redox molecules that would have huge implications for measurement science and technology.

Development of an activity-based ratiometric electrochemical probe of the tumor biomarker γ-glutamyl transpeptidase: Rapid and convenient sensing in whole blood, urine and live-cell samples.

γ-Glutamyl transpeptidase (GGT) is a key biomarker for cancer diagnosis and post-treatment surveillance. Currently available methods for sensing GGT show high potential, but face certain challenges including an inability to be used to directly sense analytes in turbid biofluid samples such as whole blood without tedious sample pretreatment. To overcome this issue, activity-based electrochemical probes (GTLP and GTLPOH) were herein developed for a convenient and specific direct targeting of GGT activity in turbid biosamples. Both probes were designed to have GGT catalyze the hydrolysis of the gamma-glutamyl amide moiety of the probe, and result in a self-immolative reaction and concomitant ejection of the masked amino ferrocene reporter. The GTLPOH probe, delivered distinctive key results including high sensitivity, high affinity, a wide detection range of 2-100 U/L, and low LOD of 0.38 U/L against GGT. This probe delivered a precise target for sensing GGT and was free of interference from other electroactive biological species. Furthermore, the GTLPOH probe was employed to monitor and quantify the activity of GGT on the surfaces of tumor cells. The designed sensing method was also validated by the direct quantitative measurement of GGT activity in whole blood and urine samples, and the results were found to be consistent with those of the standard fluorometric assay kit. Thus, GTLPOH is of great significance for its promise as a point-of-care tool for early-stage cancer diagnosis as well as a new drug screening method.

Biomass derived nitrogen functionalized carbon nanodots for nanomolar determination of levofloxacin in pharmaceutical and water samples.

Binder-free and efficient electrochemical sensing of levofloxacin (LF) was successfully developed based on the nitrogen-doped carbon nanodots (NCNDs). The NCNDs were synthesized by hydrothermal carbonation (180°C for 12 h), and the heteroatom was embedded in aqueous solution of ammonia (NH3). Spectral and microscopic characteristization techniques were used to analyze the topological, crystallinity, and chemical binding behavior of synthesized biomass functional material. HR-TEM image revealed a uniform spherical dot (2.96 nm), and superior quantum yield efficiency (0.42 Φ). The NCNDs was drop coated on a glassy carbon electrode (GCE) and electrochemical sensing of LF was performed by cyclic voltammetry (CV), differential pulse voltammetry (DPV), and amperometric i-t curve in phosphate-buffered saline (PBS; pH = 7.0). The NCNDs modified electrode showed a sharp oxidation peak at +0.95 V (vs. Ag/AgCl) with a four-fold higher current response than the bare GC electrode. The NCNDs/GCE surface not only increases the current response, but has lower detection potential, and facilitates electron transfer reaction. Under optimized working parameters, the NCNDs/GCE showed wide linear concentrations range from 200 nM to 2.8 mM and a low detection limit (LOD) of 48.26 nM (S/N = 3). The electrode modified with NCNDs has high electrochemical sensing stability (RSD = 1.284 ± 0.05% over 5 days), and superior reproducibility (RSD = 1.682 ± 0.06% (n = 3)). Finally, the NCNDs modified GC electrode was successfully applied to quantify the concentration of LF in drug and river water samples with acceptable recovery percentages of 96.60-99.20% and 97.20-99.00% (n=3), respectively.