Electroanalytical study of sulfa drugs at diamond electrodes and their determination by

HPLC with amperometric detection

Electroanalytical study of sulfa drugs at diamond

electrodes and their determination by HPLC with
amperometric detection
Tata N. Rao, B. V. Sarada, D. A. Tryk and A. Fujishima ,

Department of Applied Chemistry, School of Engineering, University of Tokyo, 7-3-1

Hongo, Bunkyo-ku, Tokyo 113-8656, Japan

Received 5 March 2000;

revised 2 June 2000;
accepted 4 June 2000.
Available online 18 December 2000.

Abstract

Conductive boron-doped diamond thin film electrodes were examined for the
electroanalysis of three sulfa drugs, sulfadiazine, sulfamerazine and sulfamethazine.
Cyclic voltammetry, flow injection analysis and liquid chromatography with
electrochemical detection were used to study the oxidation reactions. At diamond
electrodes, highly reproducible and well-defined cyclic voltammograms were obtained
for all three drugs with a signal to background (S/B) ratio of a factor of ten greater than
that obtained at two types of freshly polished glassy carbon (GC) electrodes. Diamond
exhibited a highly reproducible amperometric response, with a peak variation of 5%,
even at a concentration of 100 nM. A detection limit of 50 nM and a linear dynamic
range of three orders of magnitude were obtained. No fouling of the electrode was
observed within the experimental period of several hours. A rapid stabilization of the
background current is achieved, within 10 min after the application of the operating
potential under flow conditions, unlike the case of GC electrodes, which requires more
than 30 min for reasonable stabilization. We have demonstrated the application of the
diamond electrode for the simple and sensitive amperometric detection of the sulfa drugs
in a standard mixture after their separation with reverse-phase HPLC to produce
chromatograms with a flat baseline and high reproducibility, even at concentrations as
low as 100 nM.

Author Keywords: Diamond electrodes; Sulfa drug analysis; Amperometric detection

Article Outline

1. Introduction
2. Experimental
3. Results and discussion
3.1. Voltammetric studies
3.2. Flow injection analysis
3.3. Liquid chromatography with electrochemical detection
4. Conclusions
Acknowledgements
References

Fig. 1. Cyclic voltammograms for 50 μM sulfadiazine in 0.1 M

phosphate buffer (pH 7.1) at (a) diamond electrode (area, 0.12 cm2) and (b) GC
electrode (area, 0.07 cm2). The sweep rate was 100 mV s−1. Background voltammograms
are also shown in the figure.

Fig. 2. Plot of voltammetric peak potential (Ep) vs. pH for sulfadiazine.

Fig. 3. Hydrodynamic voltammograms for 100 μM concentrations of

sulfadiazine, sulfamerazine and sulfamethazine in 0.1 M phosphate
buffer (pH 7.1). The injection volume was 20 μl, and the flow rate was
1 ml min−1.

Fig. 4. FIA-ED results for (a) 100 μM and (b) 100 nM concentrations of
sulfadiazine at an applied potential of 1 V vs. Ag AgCl. Other conditions
were the same as for Fig. 3.

Fig. 5. Background current vs. time profiles for diamond and glassy carbon electrodes at
1 V under flow conditions. The mobile phase was 85% 0.1 M phosphate buffer (pH
7.1)+15% methanol (v/v).

Fig. 6. Chromatograms of a standard mixture containing 100 nM concentrations of (1)

sulfadiazine, (2) sulfamerazine and (3) sulfamethazine at diamond and GC electrodes.
The mobile phase was 85% 0.1 M phosphate buffer (pH 7.1)+15% methanol (v/v). The
injection volume was 20 μl, and the flow rate was 1 ml min−1.

Corresponding author. Tel.: +81-3-5841-7245; fax: +81-3-38126227; email: akira-

fu@fchem.chem.t.u-tokyo.ac.jp