a b s t r a c tOxidized Single-Wall Carbon Nanohorns (o-SWCNHs) were used, for the first time, to assemble chemically modified Screen Printed Electrodes (SPEs) selective towards the electrochemical detection of Epinephrine (Ep), in the presence of Serotonine-5-HT (S-5HT), Dopamine (DA), Nor-Epineprhine (NorEp), Ascorbic Acid (AA), Acetaminophen (Ac) and Uric Acid (UA). The Ep neurotransmitter was detected by using Differential Pulse Voltammetry (DPV), in a wide linear range of concentration (2-2500 μM) with high sensitivity (55.77 A M À 1 cm À 2 ), very good reproducibility (RSD% ranging from 2 to 10 for different SPEs), short response time for each measurement (only 2 s) and low detection of limit (LOD ¼0.1 μM). o-SWCNHs resulted in higher analytical performances when compared with other nanomaterials used in literature for electrochemical sensors assembly.
Nanodispersions of pristine single-wall carbon nanohorns (i.e., p-SWCNHs) and oxidized-SWCNHs (i.e.; o-SWCNHs) were used to modify screen printed electrode (SPE). p-SWCNHs and o-SWCNHs were fully characterized by using several analytical techniques, as: HR-TEM (High Resolution-Transmission Electron Microscopy), FE-SEM/EDX (Field Emission-Scanning Electron Microscopy/Energy Dispersive X-ray Analysis), Raman spectroscopy, thermogravimetric analysis, differential thermal analysis (DTA), and the Brunauer-Emmett-Teller (BET) method. The chemically modified SPEs were also characterized with Cyclic Voltammetry (CV), using several different electro-active targets. In all cases, p-SWCNHs showed better performances than those obtained for o-SWCNHs as well as with respect to conventional Glassy Carbon (GC) electrodes, in terms of peak currents, significant shift at lower redox-potential ranges and enhanced heterogeneous apparent kinetic constants
Fullerene Black (FB) and Extracted Fullerene Black (EFB) were used in modified screen‐printed electrodes producing electrochemical transducers (FB‐SPEs and EFB‐SPEs). A complete electrochemical study was performed and the best results are obtained working with FB‐SPEs, especially in terms of: 1. improved electron‐transfer kinetic mechanisms and 2. sensitivity and selectivity toward Acetaminophen (Ac) and Guanine (G). These latter represent two important electro‐active targets to quantify in medicine field application, because: Ac is a preferred alternative (as analgesic‐antipyretic agent) to aspirin, particularly for patients who cannot tolerate aspirin; the oxidation signal of G is useful for the fabrication of emerging analytical tools, such as DNA chipsand user‐friendly diagnostic devices. Ac and G are quantify by using FB‐SPEs electrochemical devices, with an extended linearity (1–300 μM for Ac; 0.1–300 μM for G), an excellent sensitivity (2.82 μA μM−1 cm−2 in the case of Ac; and 0.183 μA μM−1 cm−2 in the case of G), a low detection limit (0.01 μM for Ac; 0.005 μM for G), a very good reproducibility (both: intra‐; inter‐electrodes reproducibility RSD % ranging from 0.3–0.5 for Ac; and 0.50–0.85 for G) and a very fast response time (6 s for Ac; 5 s in the case of G). In addition, high selectivity is obtained at FB‐SPEs, meaning that the FB‐SPEs electrochemical transducers are suitable to simultaneously quantify Ac and G in real samples, having several different (highly concentrated) interference.
Specific Pd‐based organometallic complex, in particular the [Pd(η1‐CH2CH=CH2)(PNP’)]BF4 was used for the assembly of chemically modified Screen Printed Electrodes (SPEs) and their electrochemical reactivity was also investigated. For this purpose potassium ferricyanide, hexaammineruthenium(III) chloride, sodium hexachloroiridate‐(III) hydrate, ascorbic acid (AA), uric acid (UA), acetaminophen (Ac), guanine (G) and adenine (A) were used to study the electron‐transfer processes, which occurred at modified SPEs, fabricated by using the [Pd(η1‐CH2CH=CH2)(PNP’)]BF4, applying the drop casting procedure. Interesting results were obtained in the case of the guanine (G) quantitative detection, especially in terms of a wide range of concentration (2.5–40 nM), an high sensitivity (of 49.0 A M−1 cm−2), a low detection limit (LOD=1.0 nM) and a fast response time (of t=2 s). The intra‐electrode reproducibility (RSD%) was <1 % for the same SPE used for each point of the calibration plot. The inter‐electrode reproducibility (RSD%), estimated by using different SPEs for each single point of the quantitative calibration graph, ranging from 5 to 10 %, better than that exhibited by other different chemical sensors, described in literature, and reported in this work for comparison. In addition, the high selectivity of the chemically modified sensors toward the oxidation of guanine, exhibited in presence of a mixture of G+A, in the same electrochemical bath solution, could be related to the different electro‐catalytic mechanisms, as demonstrated by the XPS study. This chemical sensor prototype could be very promising for bio‐medicine applications.
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