Design of a chemical sensor for the detection and determination of citric acid using indicator displacement assay method

Document Type : Original Article


Department of Chemistry, Yasouj University, Yasouj, Iran


In this study, a colorimetric sensor was introduced to determine citric acid by the indicator displacement assay(IDA) method. The sensor was made from the complex formation reaction between the Chromeazurol S and the gadolinium ions in aqueous solutions. At optimum pH(pH =7.00), Chromeazurol S (yellow) was reacted with gadolinium (III) in a 1: 1 ratio, and the Chromeazurol S-gadolinium color complex solution changed to purple. With the addition of citric acid to the designed sensor, citric acid replaces Chromeazurol S and reacts with gadolinium ion in a 1: 1 ratio. The reason for the displacement of the indicator by the analyte in combination with the gadolinium ion acceptor is that it has a larger citric acid-gadolinium complex formation constant (logKF = 6.86) than the Chromeazurol S-gadolinium formation constant (logKF = 5.67). The linear range of this measurement and detection limit of this sensor (S/N=3) were determined 2.27×10-6 to 112.90×10-6 M and 2.08×10-6, respectively. To determine the selectivity of the designed sensor, the effect of different anions such as pyrophosphate, salicylic acid, periodic acid, benzoic acid, and other compounds on the sensor response under similar conditions was investigated, and no significant color change was observed. It was indicating that the sensor has a high selectivity to measure this analyte. The efficiency of the method was evaluated by measuring citric acid in the orange juice sample by the standard addition method.


Main Subjects

This is an open access article under the CC-BY-SA 4.0 license.(

[1] Wisniak, J. (2009). Reseña de" Carl Wilhelm Scheele. Revista CENIC. Ciencias Químicas40(3), 165-173.
[3] Tang, S. C., & Yang, J. H. (2018). Dual effects of alpha-hydroxy acids on the skin. Molecules23(4), 863.
[4] Morganti, P. (1996). Alpha hydroxy acids in cosmetic dermatology. skin1, 10.
[5] Kornhauser, A., Coelho, S. G., & Hearing, V. J. (2012). Effects of cosmetic formulations containing hydroxyacids on sun-exposed skin: Current applications and future developments. Dermatology Research and Practice2012.
[6] Abdel-Salam, O. M. E., Youness, E. R., Mohammed, N. A., Youssef Morsy, S. M., Omara, E. A. & Sleem, A. A. (2014). Citric acid effects on brain and liver oxidative stress in lipopolysaccharide-treated mice. Journal of medicinal food.
[7] Brima, E. I. & Abbas, A. M. (2014).  Determination of citric acid in soft drinks, juice drinks and energy drinks using titration. Int. J. Chem. Stud1(6), 30-34.
[8] Penniston, K. L., Nakada, S. Y., Holmes, R. P., & Assimos, D. G. (2008). Quantitative assessment of citric acid in lemon juice, lime juice, and commercially-available fruit juice products.  Journal of Endourology22(3), 567-570.
[9] Jacobs, S. L., & Lee, N. D. (1964). Determination of citric acid in serum and urine using Br82. Journal of Nuclear Medicine5(4), 297-301.
[10] Saffran, M., Denstedt, O. F. (1948).  A rapid method for the determination of citric acid. Journal of Biological Chemistry175, 849-855.
[11] Hartford, C. G. (1962). Rapid Spectrophotometric Method for the Determination of Itaconic, Citric, Aconitic, and Fumaric Acids. Analytical Chemistry34(3), 426-428.
[12] Taraborelli, J. A., & Upton, R. P. (1975). Enzymatic determination of citrate in detergent products. Journal of the American Oil Chemists' Society52(7), 248-251.
[13] Mato, I., Huidobro, J. F., Cendo´n, Muniategui, V., Muniategui, S., Ferna´ndez-Muino, M. A. & Teresa Sancho, M. (1998).  Enzymatic determination of citric acid in honey by using polyvinylpolypyrrolidone clarification. Journal of agricultural and food chemistry46(1), 141-144.
[14] Guerrant, G. O., Lambert, M. A., & Moss, C. W. (1982). Analysis of short-chain acids from anaerobic bacteria by high-performance liquid chromatography. Journal of Clinical Microbiology16(2), 355-360.
[15] Weikle, K. (2012). Determination of citric acid in fruit juices using HPLC. Concordia college journal of analytical chemistry3, 57-62.
[16] Saccani, G., Gherardi, S., Trifiro, A., Soresi Bordini, C., Calza, M. & C. Freddi. (1995). Use of ion chromatography for the measurement of organic acids in fruit juices. Journal of Chromatography A706(1-2), 395-403.
[17] Chepurnoi, I. & Bolbat, K. (1996). Development of methods for gas chromatographic measurement of sugars and organic acids in the urine of patients with diabetes mellitus. Klinicheskaia laboratornaia diagnostika, (3), 48-50.
[18] Yedur, S., & Berglung, K. (1996). Use of fluorescence spectroscopy in concentration and supersaturation measurements in citric acid solutions. Applied spectroscopy50(7), 866-870.
[19] van Staden, J. F., Mashamba, M. G., & Stefan, R. I. (2002). Determination of the total acidity in soft drinks using potentiometric sequential injection titration. Talanta, 58(6), 1109-1114.
[20] Lahav, O., Shlafman, E., & Cochva, M. (2005). Determination of low citric acid concentrations in mixture of weak acid/bases. Water SA, 31(4), 497-502.
[21] Khajehsharifi, H., & Bordbar, M. M. (2015). A highly selective chemosensor for detection and determination of cyanide by using an indicator displacement assay and PC-ANN and its logic gate behavior. Sens. Actuators B Chem, 209, 1015-1022.
[22] Janowski, V., & Severin, K. (2011). Carbohydrate sensing with a metal-based indicator displacement assay. Chem. Commun, 47(30), 8521-8523.
[23] Tavallali, H., Deilamy-Rad, G., & Mosallanejad, N. (2018). Development of a New Colorimetric Chemosensor for Selective Determination of Urinary and Vegetable Oxalate Concentration Through an Indicator Displacement Assay (IDA) in Aqueous Media.  Food Technol. Biotechnol, 56(3), 329.
[24] Khajehsharifi, H., & Sheini, A. (2014). A selective naked-eye detection and determination of cysteine using an indicator-displacement assay in urine sample. Sens. Actuators B: Chem, 199, 457-462.
[25] Sasaki, Y., Zhang, Z. & Minami, T. (2019). A saccharide chemosensor array developed based on an indicator displacement assay using a combination of commercially available reagents. Front. Chem, 7, 49.
[26] Wu, D., Sedgwick, A. C., Gunnlaugsson, T., Akkaya, E. U., Yoon, J., & James,T. D. (2017). Fluorescent chemosensors: the past, present and future. Chem. Soc. Rev, 46(23), 7105-7123.
[28] Sangal, S. P. (1967). Metal chelates of lanthanoids in aqueous solution and their analytical applications. J. Prakt. Chem, 36(3‐4), 126-137.
[29] Salnikov, Y. I., Devyatov, F. V., Zhuravleva, N. E., & Golodnitskaya, D. V. (1984). Complex-formation of nickel (II) and cobalt (II) with citric-acid. Zhur. Neorg. Khim, 29(9), 2273-2276.
[30] Zabiszak, M., Nowak, M., Taras-Goslinska, K., Kaczmarek, M. T., Hnatejko, Z., & Jastrzab, R. (2018). Carboxyl groups of citric acid in the process of complex formation with bivalent and trivalent metal ions in biological systems. J. Inorg. Biochem, 182, 37-47