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The redox reaction of 5-fluorouracil (FU) at a hanging mercury drop electrode (HMDE) is studied by means of square-wave voltammetry (SWV). It is demonstrated that the redox reaction proceeds according to the scheme:− , which involves both chemisorption of FU on the electrode surface and creation of a sparingly soluble compound with the electrode material. The overall response exhibits properties of a surface process in which both the reactant and the product of the redox reaction are immobilized on the electrode surface. The square-wave voltammetric response of FU possesses features typical of surface confined processes such as 'split SW peaks' and a 'quasi-reversible maximum'. The proposed electrode mechanism is studied theoretically. The numerically calculated response under conditions of SWV is in qualitative agreement with the experimental data. Comparing the theoretical and the experimental data, the kinetic parameters of the redox reaction investigated are estimated. The standard rate constant appears to be within the interval 545 k s /s − 1 5 108, the adsorption constant is K =10 cm − 1 , and the transfer coefficient is h =0.549 0.01. The effect of the Cu(II) ions on the adsorptive SWV response of FU is discussed from an analytical point of view. It is demonstrated that SWV is a particularly appealing technique, which enables determination of FU at an ultra-trace concentration level. A linear calibration plot was established at 10 − 11 mol l − 1 concentration level with a correlation coefficient of R 2 = 0.992. The detection limit is 7.7× 10 − 12 mol l − 1 . The reproducibility of the results in terms of the relative standard deviation ranges from 0.9 to 3.2%.
The redox reaction of 5-fluorouracil (FU) at a hanging mercury drop electrode (HMDE) is studied by means of square-wave voltammetry (SWV). It is demonstrated that the redox reaction proceeds according to the scheme:− , which involves both chemisorption of FU on the electrode surface and creation of a sparingly soluble compound with the electrode material. The overall response exhibits properties of a surface process in which both the reactant and the product of the redox reaction are immobilized on the electrode surface. The square-wave voltammetric response of FU possesses features typical of surface confined processes such as 'split SW peaks' and a 'quasi-reversible maximum'. The proposed electrode mechanism is studied theoretically. The numerically calculated response under conditions of SWV is in qualitative agreement with the experimental data. Comparing the theoretical and the experimental data, the kinetic parameters of the redox reaction investigated are estimated. The standard rate constant appears to be within the interval 545 k s /s − 1 5 108, the adsorption constant is K =10 cm − 1 , and the transfer coefficient is h =0.549 0.01. The effect of the Cu(II) ions on the adsorptive SWV response of FU is discussed from an analytical point of view. It is demonstrated that SWV is a particularly appealing technique, which enables determination of FU at an ultra-trace concentration level. A linear calibration plot was established at 10 − 11 mol l − 1 concentration level with a correlation coefficient of R 2 = 0.992. The detection limit is 7.7× 10 − 12 mol l − 1 . The reproducibility of the results in terms of the relative standard deviation ranges from 0.9 to 3.2%.
The sections in this article are Introduction History Nucleic Acid Samples Electrochemical Behavior of NA Components Adsorption/Desorption Behavior Mercury Electrodes Solid Electrodes Reduction and Oxidation Microanalysis of Nucleic Acid Components by Stripping Techniques Principles Reactions of Pyrimidine and Purine Bases with the Electrode Mercury Unusual Bases and Nucleosides Sparingly Soluble Compounds of Nucleic Acid Components with Copper Adsorption/Desorption Behavior of NAs Mercury Dropping Electrode Adsorption of Double‐stranded (Native) DNA Adsorption of Single‐stranded (Denatured) DNA Adsorption Kinetics at Mercury Dropping and Hanging Electrodes Electrochemical Impedance Spectroscopy ( EIS ) Other Techniques Adsorption of NAs on Other Electrodes DNA Adsorption to Charged Lipid Membranes Reduction and Oxidation of NAs on Different Electrodes Mercury Electrodes Reduction of Adenine and Cytosine Residues Anodic Signal of Guanine Residues Carbon Electrodes Other Solid Electrodes Analysis of NAs by Different Electrochemical Techniques Relations Between Structures and Electrochemical Responses of DNA DNA Structure on Electrode Surfaces Dependence of the ds DNA Signals at the HMDE on Potential Scanning Direction Opening of the DNA Double Helix Around −1.2 V (Region U ) Opening of ds DNA at Acid p Hs in a Wider Potential Range T Interactions of NAs with Small Molecules Reversible (Noncovalent) Interactions Inorganic Cations and Simple Metal Complexes Organic Metal Chelates Other Noncovalent DNA Binders Covalent Interactions Electroactive Markers of NAs Other Nucleic Acid Modifications DNA Conductivity Application of Electrodes in DNA Conductivity Studies Analytical Applications Sensors for DNA Hybridization Immobilization of DNA on the Electrode Detection of the Hybridization Event Redox Indicators Covalently Bound to DNA Indicator‐free Detection Systems. Intrinsic Electroactivity of DNA Changes in Interfacial Properties and DNA Conductivity Blocking and Interfacing the Transducer Electrocatalytic Reactions Detection of Point Mutations Sensors for DNA Damage Detection of DNA Strand Breaks Damage to DNA Bases Detection of Damaging Agents Specifically Interacting with DNA DNA Cleavage Controlled by Electrochemical Reactions Other Determinations Determination of ss DNA in an Excess of ds DNA Determination of RNA Traces in DNA Solutions Determination of Proteins Conclusion Addendum Acknowledgment
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