Abstract

Modification of gold electrode by self-assembled trans-[Fe(cyclam)(NCS)2]+ complex ion to produce an electrochemical sensor for nitric oxide detection was investigated. Dopamine, serotonin and nitrite were examined as interferents. The synthesized complex was characterized by X-ray diffraction and by infrared spectroscopy. The modified electrode was characterized by cyclic voltammetry and by surface enhanced Raman spectroscopy, analytical curves were obtained by square wave voltammetry and Monte Carlo calculations were made to model the interaction of NO molecules with the unmodified and modified surfaces. The complex has distorted octahedron geometry with the thiocyanate groups bonded to the iron ion by the nitrogen atom and in the trans orientation. SERS spectrum and Monte Carlo calculations supported that the complex ion is adsorbed on Au surface from the Au-S bond. The electrochemical current for NO oxidation on the modified electrode was higher than that presented by the bare Au electrode and a good correlation was presented by the experimental analytical curve and the calculated Monte Carlo interaction energy versus amount NO molecules plot. The Monte Carlo calculations indicated that the higher current response for NO oxidation on the Au/trans-[Fe(cyclam)(NCS)2]+ surface was due to the stronger interaction of the NO molecules with complex adsorbed on the Au surface than the interaction of NO with the bare Au surface. The theoretical analyses also revealed that NO molecules cluster on Au surface. Dopamine, serotonin and nitrite were interferents for the detection of NO with dopamine and serotonin was less significant interferents than the nitrite. The proposed modified electrode presented good electrochemical stability, detection limit and quantification limit of 5.15×10−8molL−1 and 1.72×10−7, respectively, which were about one order of magnitude lesser than the corresponding values obtained for the bare Au electrode. The results indicated that the proposed electrode has potential to be applied as a sensor for NO detection.

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