Picomolar-sensitive impedimetric sensor for salivary calcium analysis at POC based on SAM of Schiff base–modified gold electrode

• Published in: Journal of solid state electrochemistry Vol. 24; no. 3; pp. 723 - 737
• Main Authors: Magar, Hend Samy, Abbas, Mohammed Nooredeen, Ali, Mounir Ben, Ahmed, Mona A.
• Format: Journal Article
• Language: English
• Published: Berlin/Heidelberg Springer Berlin Heidelberg 01.03.2020; Springer Nature B.V
• Subjects: Adhesion tests; Analytical Chemistry; Benzoic acid; Calcium compounds; Characterization and Evaluation of Materials; Chemical bonds; Chemistry; Chemistry and Materials Science; Circuits; Condensed Matter Physics; Contact angle; Diagnostic software; Diagnostic systems; Electric contacts; Electrochemical impedance spectroscopy; Electrochemistry; Electrodes; Energy Storage; Gold; Imines; Morphology; Original Paper; Physical Chemistry; Saliva; Selectivity; Self-assembled monolayers; Self-assembly; Sensors; Salivary calcium; POC; Impedimetric sensor; SAM of aminosalicylic acid; Modified gold electrode
• ISSN: 1432-8488; 1433-0768
• DOI: 10.1007/s10008-020-04500-w

Analysis of saliva is a potential diagnostic tool in the management of human diseases. Analysis of saliva in healthy individuals is vital to comparison in a diseased state. Salivary glandular secretion constantly bathes the teeth and oral mucosa. The presence of saliva is vital for healthy oral tissue. Positive correlation has been shown in salivary calcium and phosphate and oral health. We have developed a highly sensitive and selective impedimetric calcium sensor for its non-invasive determination in saliva. The sensor is based on 2-hydroxy-4-(2-oxo-1,2-diphenylethylidene)amino) benzoic acid ionophore; self-assembled monolayer (SAM) on gold electrode has been developed. The calcium sensor was constructed by SAM-Au formation of the compound developed by covalently attaching 4-aminothiophenol (ATP) to the ionophore molecule through amide bond formation between its amino group and the carboxylic group of the ionophore. Characterization of the SAM formation on the gold electrode was performed using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The modification of the gold electrode was confirmed by measuring the adhesion and surface morphology using contact angle (CA) measurements and SEM. EIS was used as the measuring technique; the sensor showed a linear analytical range (LR) of 5 × 10 −12 –1 × 10 −6  mol L −1 and a limit of detection (LOD) of 3.6 × 10 −12  mol L −1 calculated on the basis of 3σ/s and limit of quantification (LOQ) of 1.2 × 10 −11  mol L −1 . Moreover, the sensor was found to exhibit high selectivity for Ca 2+ selectivity over a variety of common interfering ions. The impedance behavior of the proposed calcium sensor has been modeled by an equivalent electrical circuit using a modified Randles model. The covalent immobilization of the ionophore into the modified gold electrode was manifested in its prolonged stability. The sensor was utilized for the determination of calcium concentration in real samples of human saliva; therefore, we believe it is suitable for point of care (POC). Graphical abstract