Electrochemical behavior of APAP and AA mixtures
In therapeutic use, APAP is often found to be associated with AA and/or other pharmacologically and biologically active compounds [9]. The copresence of AA and APAP leads to diminished toxicity and intensified positive effects of APAP [10]. Therefore, the ability to selectively determine these species has been a major goal of electroanalysis research. We studied the electrochemical behaviors of APAP and AA in a mixture solution. Fig. 1C shows the CVs of a mixture solution of APAP and AA at the bare CCE and SWCNT/CCE. At the bare CCE, two broad and overlapped anodic peaks are obtained, and the peak potentials of APAP and AA are nearly indistinguishable (curve 1). Therefore, it is impossible to determine the individual concentration of each compound from the merged voltammetric peak on the surface of CCE. At the SWCNT/CCE, the voltammetric peaks of APAP and AA appear at 390 and 70 mV in phosphate buffer solution (pH 7.0) (curve 2). Larger separation of the peak potentials allows them to be simultaneously detected in mixtures.
The above obtained results demonstrate that SWCNTs not only accelerate the oxidation of APAP and AA because of much edge plane graphite and/or many defects but also dramatically enlarge the peak separation between APAP and AA. On the other hand, the remarkable peak current enhancement and the drop of oxidation overpotentials undoubtedly testify to the electrocatalytic properties of the SWCNT/CCE in the oxidation of these compounds. Indeed, the SWCNT/CCE composite electrode presents an interlinked highly mesoporous three-dimensional structure with a relatively higher electrochemically accessible surface area and easier charge transfer at the electrode/electrolyte interface [40]. Therefore, the SWCNT/CCE greatly improves the selectivity, and consequently the simultaneous determination, of APAP and AA on account of the unusual structure and properties of SWCNTs (i.e., subtle electronic properties). It should be noted that, the calculated electroactive surface area for the SWCNT/CCE via application of Fe(CN)63−/4− as an electroactive probe ions is 0.330 cm2, which is higher than 2 orders of bare CCE [26]. The significant increase in electroactive surface area suggests that the SWCNT/CCE is promising for electrocatalytic oxidation and electrochemical sensing.
Buffer component, pH, and scan rate effects on the oxidation of APAP and AA
The electrochemical responses of APAP and AA were studied in different media, namely phosphate buffer solution, sodium borate solution, and acetate buffer solution. The anodic peak potentials for these two species are well separated in the three media, but the maximal peak currents of APAP and AA were obtained in phosphate buffer solution. The peak currents of these compounds in phosphate buffer solution were approximately two to three times higher than those in acetate buffer solution and sodium borate solution.
Because a proton takes part in the electrode reaction process of APAP and AA, the effect of the pH value on the voltammetric behavior of APAP and AA at the SWCNT/CCE was carefully investigated in a wide pH range (2.0–10.0). Fig. 2A shows that the oxidative potentials of APAP and AA shifted negatively as the pH increased. The relationships between the potentials and pH were linear, and the regression equations were as follows:
Electrochemical behavior of APAP and AA mixtures
In therapeutic use, APAP is often found to be associated with AA and/or other pharmacologically and biologically active compounds [9]. The copresence of AA and APAP leads to diminished toxicity and intensified positive effects of APAP [10]. Therefore, the ability to selectively determine these species has been a major goal of electroanalysis research. We studied the electrochemical behaviors of APAP and AA in a mixture solution. Fig. 1C shows the CVs of a mixture solution of APAP and AA at the bare CCE and SWCNT/CCE. At the bare CCE, two broad and overlapped anodic peaks are obtained, and the peak potentials of APAP and AA are nearly indistinguishable (curve 1). Therefore, it is impossible to determine the individual concentration of each compound from the merged voltammetric peak on the surface of CCE. At the SWCNT/CCE, the voltammetric peaks of APAP and AA appear at 390 and 70 mV in phosphate buffer solution (pH 7.0) (curve 2). Larger separation of the peak potentials allows them to be simultaneously detected in mixtures.
The above obtained results demonstrate that SWCNTs not only accelerate the oxidation of APAP and AA because of much edge plane graphite and/or many defects but also dramatically enlarge the peak separation between APAP and AA. On the other hand, the remarkable peak current enhancement and the drop of oxidation overpotentials undoubtedly testify to the electrocatalytic properties of the SWCNT/CCE in the oxidation of these compounds. Indeed, the SWCNT/CCE composite electrode presents an interlinked highly mesoporous three-dimensional structure with a relatively higher electrochemically accessible surface area and easier charge transfer at the electrode/electrolyte interface [40]. Therefore, the SWCNT/CCE greatly improves the selectivity, and consequently the simultaneous determination, of APAP and AA on account of the unusual structure and properties of SWCNTs (i.e., subtle electronic properties). It should be noted that, the calculated electroactive surface area for the SWCNT/CCE via application of Fe(CN)63−/4− as an electroactive probe ions is 0.330 cm2, which is higher than 2 orders of bare CCE [26]. The significant increase in electroactive surface area suggests that the SWCNT/CCE is promising for electrocatalytic oxidation and electrochemical sensing.
Buffer component, pH, and scan rate effects on the oxidation of APAP and AA
The electrochemical responses of APAP and AA were studied in different media, namely phosphate buffer solution, sodium borate solution, and acetate buffer solution. The anodic peak potentials for these two species are well separated in the three media, but the maximal peak currents of APAP and AA were obtained in phosphate buffer solution. The peak currents of these compounds in phosphate buffer solution were approximately two to three times higher than those in acetate buffer solution and sodium borate solution.
Because a proton takes part in the electrode reaction process of APAP and AA, the effect of the pH value on the voltammetric behavior of APAP and AA at the SWCNT/CCE was carefully investigated in a wide pH range (2.0–10.0). Fig. 2A shows that the oxidative potentials of APAP and AA shifted negatively as the pH increased. The relationships between the potentials and pH were linear, and the regression equations were as follows:
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