Tramadol sensing in non-invasive biological fluids using a voltammetric electronic tongue and an electrochemical sensor based on biomimetic recognition

Tramadol (TRA) is a weak opioid analgesic, prescribed to relieve mild to moderately severe pain. However, side effects of TRA overdoses, including vomiting, depression, tachycardia, convulsions, morbidity and mortality are often reported. In this study, an electrochemical sensor based on molecularly imprinted conductive polymer was firstly developed for the quantitative and non-invasive detection of TRA. Secondly, a voltammetric electronic tongue (VE-Tongue) combined with chemometric methods was used for the qualitative analysis. The MIP sensor was constructed by self-assembling a poly-aniline layer coated with silver nanoparticles (PANI-AgNPs) on a screen-printed gold electrode (Au-SPE). Then, 2-amino-thiophenol was polymerised in the presence of TRA. The electronic device exhibits, under optimal conditions, responses proportional to TRA concentrations (0.01-100 µg/mL) with detection and quantification limits of 9.42 µg/mL and 28.55 µg/mL, respectively. Moreover, its selectivity was proven by insignificant interferences of substances (paracetamol and citric acid). Spiked saliva and urine samples were used for the sensor practical application with a significant recovery above 90% and standard deviations below 4.5%. Besides, urine samples' analyses using VE-Tongue and pattern recognition methods show good discrimination, classification, and prediction results with scores above 95%. Correspondingly, both electro-analytical devices could be viable for monitoring drugs in biological matrices.