In Situ Derivatization of an Intrinsic Iron Impurity as a Surface-Confined Iron(II)tris(2,2'-bipyridine) Complex on MWCNT and Its Application to Selective Electrochemical Sensing of DNA's Purine Bases.

The derivatization of an intrinsic iron impurity in a carbon nanotube (CNT-*Fe, *Fe-intrinsic, and redox-active iron impurity) as a functional molecular system has been challenging to realize. There are certain limitations on the derivatization of such iron impurities such as low concentration and limited accessibility. Herein, we report an in situ electroassisted derivatization of an intrinsic and redox-active iron impurity in a multiwalled carbon nanotube (MWCNT-*Fe, *Fe, 2.1 wt %) as MWCNT-*Fe(bpy)3(2+), where Fe(bpy)3(2+) = iron(II)tris(2,2'-bipyridine) complex and bpy = 2,2'-bipyridine. The hybrid complex was prepared by the electrochemical treatment of a 2,2'-bipyridine ligand adsorbed {MWCNT-*Fe + Nafion} modified glassy carbon electrode in pH 7 phosphate buffer solution. This new MWCNT-*Fe(bpy)3(2+) hybrid electrode showed well-defined, stable redox at E1/2 = 830 mV with a peak-to-peak separation (ΔEp) of 72 mV in a neutral pH solution. This is quite different from an ex situ Nafion-Fe(bpy)3(2+) complex system that showed an unstable response at neutral pH. This in situ approach can allow the redox-active iron impurity in the CNTs to be quantified using the current signal of the Fe(bpy)3(2+) hybrid system. This MWCNT-*Fe(bpy)3(2+) hybrid modified electrode was further used as an electrochemical detector for selective and separation-less flow injection analysis of DNA's purine bases, adenine and guanine, without interference from pyrimidine bases, cytosine, and thymine at different oxidative detection potentials of 1 V (for adenine and guanine) and 0.7 V vs Ag/AgCl (for guanine) using the pH 7 phosphate buffer solution as a carrier system.