Fabrication and evaluation of [Co(phen)2L]3+-modified DNA-MWCNT and SDS-MWCNT electrodes for electrochemical detection of 6-mercaptopurine

A multiple sweep voltammetry is effectively applied to the electrochemical assembly of polypyridyl cobalt(III) complexes [Co(phen)2(tatp)]3+ and [Co(phen)3]3+ (where phen = 1,10-phenanthroline and tatp = 1,4,8,9-tetra-aza-triphenylene) on a glassy carbon electrode modified with DNA or sodium dodecyl sulfate (SDS)-dispersed multi-walled carbon nanotubes (MWCNTs). The DNA-MWCNTs and SDS-MWCNTs are found to impact redox reactions of [Co(phen)2L]3+ (L = phen or tatp) adsorbed on the electrode surfaces. The anionic surfactant (SDS) facilitates the adsorption of [Co(phen)2L]3+ on the MWCNT surfaces via a fully-packed π–π stacking mode. An excess amount of DNA as the dispersant attached to the surface of MWCNTs interferes with the π–π stacking between MWCNTs and [Co(phen)2L]3+, representing a DNA-bridged binding mode. Moreover, the DNA-MWCNT or SDS-MWCNT modified electrodes are suitable for the detection of 6-mercaptopurine (6-MP) using [Co(phen)2(tatp)]3+ as voltammetric probes. The proposed sensor exhibits a high selectivity to 6-MP (detection limit = 0.05 μM) and a good linear response in the range from 0.2 μM to 0.2 mM.

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► Electrochemical assembly of [Co(phen)2L]3+ on MWCNT surfaces.
► SDS facilitates adsorption of [Co(phen)2L]3+ by fully-packed π–π stacking.
► Adsorption of [Co(phen)2L]3+ on DNA-MWCNT surfaces is via DNA-bridged binding mode.
► A 6-mercaptopurine sensor shows a good linear response between 0.2 μM and 0.2 mM.