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Keywords = IHOAM model

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16 pages, 3048 KB  
Article
Electrochemical Characterization of Modified Glassy Carbon Electrodes for Non-Enzymatic Glucose Sensors
by Julia Maria Mazurków, Anna Kusior and Marta Radecka
Sensors 2021, 21(23), 7928; https://doi.org/10.3390/s21237928 - 27 Nov 2021
Cited by 11 | Viewed by 5576
Abstract
The diversity of materials proposed for non-enzymatic glucose detection and the lack of standardized protocols for assessing sensor performance have caused considerable confusion in the field. Therefore, methods for pre-evaluation of working electrodes, which will enable their conscious design, are currently intensively sought. [...] Read more.
The diversity of materials proposed for non-enzymatic glucose detection and the lack of standardized protocols for assessing sensor performance have caused considerable confusion in the field. Therefore, methods for pre-evaluation of working electrodes, which will enable their conscious design, are currently intensively sought. Our approach involved comprehensive morphologic and structural characterization of copper sulfides as well as drop-casted suspensions based on three different polymers—cationic chitosan, anionic Nafion, and nonionic polyvinylpyrrolidone (PVP). For this purpose, scanning electron microscopy (SEM), X-ray diffraction (XRD), and Raman spectroscopy were applied. Subsequently, comparative studies of electrochemical properties of bare glassy carbon electrode (GCE), polymer- and copper sulfides/polymer-modified GCEs were performed using electrochemical impedance spectroscopy (EIS) and voltammetry. The results from EIS provided an explanation for the enhanced analytical performance of Cu-PVP/GCE over chitosan- and Nafion-based electrodes. Moreover, it was found that the pH of the electrolyte significantly affects the electrocatalytic behavior of copper sulfides, indicating the importance of OHads in the detection mechanism. Additionally, diffusion was denoted as a limiting step in the irreversible electrooxidation process that occurs in the proposed system. Full article
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17 pages, 4767 KB  
Article
Insightful Analysis of Phenomena Arising at the Metal|Polymer Interphase of Au-Ti Based Non-Enzymatic Glucose Sensitive Electrodes Covered by Nafion
by Adrian Olejnik, Jakub Karczewski, Anna Dołęga, Katarzyna Siuzdak and Katarzyna Grochowska
Coatings 2020, 10(9), 810; https://doi.org/10.3390/coatings10090810 - 21 Aug 2020
Cited by 11 | Viewed by 3418
Abstract
This paper focuses on the examination of glucose oxidation processes at an electrode material composed of gold nanoparticles embedded in a titanium template. Three different conditions were investigated: the chloride content in the electrolyte, its ionic conductivity and the presence of a Nafion [...] Read more.
This paper focuses on the examination of glucose oxidation processes at an electrode material composed of gold nanoparticles embedded in a titanium template. Three different conditions were investigated: the chloride content in the electrolyte, its ionic conductivity and the presence of a Nafion coating. The impact of the provided environment on the oxidation reaction was evaluated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Two models, namely: chemisorption and incipient hydrous oxide/adatom mediator (IHOAM), were applied to explain the complex voltammetric responses of the electrodes exposed to solutions of varied glucose concentrations. Three different phenomena were observed for the studied cases. The first is related to the transition between the dominant mechanism of glucose oxidation from the IHOAM model to the chemisorption model. This happens only in an electrolyte containing chlorides after exceeding a certain amount of glucose. The second effect exhibits a bottleneck nature resulting from the presence of Nafion on the electrode’s surface. In this case, mass transport through the semi-permeable polymer is hampered, due to the blocking of channels and physical internal cross-linking. This leads to a preconcentration of glucose inside the pores resulting in an increase in both the material sensitivity and the linear range of the calibration curve. Lastly, the third effect is manifested in a low concentration of the supporting electrolyte. It is based on the fact that mass transport of hydroxyl ions is governed not only by diffusion, but also by migration. These three effects have a tremendous impact on the glucose oxidation mechanism and reveal its very complex nature. Full article
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