title: Nanomolar determination of 4-nitrophenol based on a poly(methylene blue)-modified glassy carbon electrode.
abstract: A poly(methylene blue)-modified glassy carbon electrode (PMB/GCE) was fabricated by electropolymerisation of methylene blue on a GCE and further utilized to investigate the electrochemical determination of 4-nitrophenol (4-NP) by cyclic voltammetry (CV), differential pulse voltammetry and chronocoulometry. The morphology of the PMB on GCE was examined using a scanning electron microscope (SEM). An oxidation peak of 4-NP at the PMB modified electrode was observed at 0.28 V, and in the case of bare GCE, no oxidation peak was observed, which indicates that PMB/GCE exhibits a remarkable effect on the electrochemical determination of 4-NP. Due to this remarkable effect of PMB/GCE, a sensitive and simple electrochemical method was proposed for the determination of 4-NP. The effect of the scan rate and pH was investigated to determine the optimum conditions at which the PMB/GCE exhibits a higher sensitivity with a lower detection limit. Moreover, kinetic parameters such as the electron transfer number, proton transfer number and standard heterogeneous rate constant were calculated. Under optimum conditions, the oxidation current of 4-NP is proportional to its concentration in the range of 15-250 nM with a correlation coefficient of 0.9963. The detection limit was found to be 90 nM (S/N = 3). The proposed method based on PMB/GCE is simple, easy and cost effective. To further confirm its possible application, the proposed method was successfully used for the determination of 4-NP in real water samples with recoveries ranging from 97% to 101.6%. The interference due to sodium, potassium, calcium, magnesium, copper, zinc, iron, sulphate, carbonate, chloride, nitrate and phosphate was found to be almost negligible.
authors.affiliation: Department of Inorganic Chemistry, University of Madras, Guindy Maraimalai Campus, Chennai-600025, India. vnnara@yahoo.co.in.
authors.forename: Krishnamoorthy
authors.initials: K
authors.lastname: Giribabu
authors.forename: Ranganathan
authors.initials: R
authors.lastname: Suresh
authors.forename: Ramadoss
authors.initials: R
authors.lastname: Manigandan
authors.forename: Settu
authors.initials: S
authors.lastname: Munusamy
authors.forename: Sivakumar Praveen
authors.initials: SP
authors.lastname: Kumar
authors.forename: Selvamani
authors.initials: S
authors.lastname: Muthamizh
authors.forename: Vengidusamy
authors.initials: V
authors.lastname: Narayanan
mesh_terms: D002244:Carbon / Q000737:chemistry*; D004566:Electrodes; D005898:Glass / Q000737:chemistry*; D008751:Methylene Blue / Q000737:chemistry*; D053758:Nanoparticles / Q000737:chemistry; D036103:Nanotechnology / Q000379:methods*; D009596:Nitrophenols / Q000032:analysis*
chemical_list: D009596:Nitrophenols; D002244:Carbon; D008751:Methylene Blue; C024836:4-nitrophenol