Determination of methotrexate and folic acid by ion chromatography with electrochemical detection on a functionalized multi-wall carbon nanotube modified electrode

A simple and sensitive method was developed for simultaneous determination of methotrexate (MTX) and folic acid (FA) by ion chromatography with electrochemical detection (IC-ECD). Quaternary amine functionalized multi-wall carbon nanotubes (q-MWNTs) modified glassy carbon electrode (GCE) was used as an amperometric sensor to determine MTX and FA. The electrochemical behaviors of MTX and FA at the q-MWNTs/GCE were studied by cyclic voltammetry (CV). Results indicated that this modified electrode exhibited electrocatalytic oxidation toward MTX and FA with high sensitivity, stability and long life. Good separation of MTX and FA was demonstrated by IC on an anion-exchange column with phosphate buffer solution (PBS) as eluent. Under the optimal conditions, the linear ranges were from 0.01 to 20 mg/L for both MTX and FA with correlation coefficients r ≥ 0.9994. The obtained detection limits (LODs) for MTX and FA were 0.2 and 0.4 μg/L (S/N = 3), respectively. The method has been successfully applied to the determination of MTX and FA in plasma and urine of patients of rheumatoid arthritis.