DNA Electrochemical Biosensors for In Situ Probing of Pharmaceutical Drug Oxidative DNA Damage

Abstract

Deoxyribonucleic acid (DNA) electrochemical biosensors are devices that incorporate immobilized DNA as a molecular recognition element on the electrode surface, and enable probing in situ the oxidative DNA damage. A wide range of DNA electrochemical biosensor analytical and biotechnological applications in pharmacology are foreseen, due to their ability to determine in situ and in real-time the DNA interaction mechanisms with pharmaceutical drugs, as well as with their degradation products, redox reaction products, and metabolites, and due to their capacity to achieve quantitative electroanalytical evaluation of the drugs, with high sensitivity, short time of analysis, and low cost. This review presents the design and applications of label-free DNA electrochemical biosensors that use DNA direct electrochemical oxidation to detect oxidative DNA damage. The DNA electrochemical biosensor development, from the viewpoint of electrochemical and atomic force microscopy (AFM) characterization, and the bottom-up immobilization of DNA nanostructures at the electrode surface, are described. Applications of DNA electrochemical biosensors that enable the label-free detection of DNA interactions with pharmaceutical compounds, such as acridine derivatives, alkaloids, alkylating agents, alkylphosphocholines, antibiotics, antimetabolites, kinase inhibitors, immunomodulatory agents, metal complexes, nucleoside analogs, and phenolic compounds, which can be used in drug analysis and drug discovery, and may lead to future screening systems, are reviewed.

Kinetics and Mechanism of Plasmon-Driven Dehalogenation Reaction of Brominated Purine Nucleobases on Ag and Au

“…47 Typically, the triphosphate backbone shifts the oxidation potential of nucleotides toward a more positive potential by almost 0.250 V compared with the bases. 46 Therefore, it is likely that the oxidation of Gua takes place around 0.3 V vs SHE, which indicates toward the consumption of an unstable Gua radical product in the hole reduction, which can undergo oxidation even at a lower Second, we propose that the Br − byproduct from the reaction can act as hole scavenger. This involves a favorable one-electron transfer reaction to the hole that occurs at a potential of 0.10 V vs SHE (−4.54 eV) 48 with respect to the Fermi energy of 0.36 V vs SHE (−4.80 eV).…”

“… 47 Typically, the triphosphate backbone shifts the oxidation potential of nucleotides toward a more positive potential by almost 0.250 V compared with the bases. 46 Therefore, it is likely that the oxidation of Gua takes place around 0.3 V vs SHE, which indicates toward the consumption of an unstable Gua radical product in the hole reduction, which can undergo oxidation even at a lower potential than 0.3 V vs SHE. This appears just above the Fermi energy of the AgNP centered around 0.36 V vs SHE (or, E (eV) = −4.80 eV, absolute electrochemical energy with respect to vacuum given by the relation: E (eV)= −(4.44 + E SHE ) eV 13 such that the electrons generated by the oxidation of the base or base radical would be consumed by the hot-holes without any energetic loss.…”

“…A first plausible hole reduction pathway proposed is the oxidation of the product nucleobase radical (eq ). The oxidation of the free nucleobases is very well studied in solid electrodes by electrochemical techniques. , On a silver electrode, the values for the oxidation of deoxyguanosine 5′-triphosphate (dGTP) start around 0.49 V vs SHE (Standard hydrogen electrode) . Typically, the triphosphate backbone shifts the oxidation potential of nucleotides toward a more positive potential by almost 0.250 V compared with the bases .…”

“…The oxidation of the free nucleobases is very well studied in solid electrodes by electrochemical techniques. , On a silver electrode, the values for the oxidation of deoxyguanosine 5′-triphosphate (dGTP) start around 0.49 V vs SHE (Standard hydrogen electrode) . Typically, the triphosphate backbone shifts the oxidation potential of nucleotides toward a more positive potential by almost 0.250 V compared with the bases . Therefore, it is likely that the oxidation of Gua takes place around 0.3 V vs SHE, which indicates toward the consumption of an unstable Gua radical product in the hole reduction, which can undergo oxidation even at a lower potential than 0.3 V vs SHE.…”

8-oxoguanine and 8-oxodeoxyguanosine Biomarkers of Oxidative DNA Damage: A Review on HPLC–ECD Determination

“…Therefore, an optimum applied potential of ~ +0.25 V was found to reduce overlapping peaks and resolve the 8-oxodG overestimation problem [ 52 ]. The HPLC–ECD detection of 8-oxoG has generally been less employed than 8-oxodG, although 8-oxoG presents a lower oxidation potential than 8-oxodG [ 53 , 54 , 55 , 56 ].…”