A Ratiometric Electrochemical Sensor Based on Mixed-Valence ZIF-90/Cu-Mn Framework for Highly Sensitive and Reliable Detection of L-Tryptophan in Milk
摘要
L-Tryptophan (L-Trp), an amino acid with both neutral and aromatic properties, plays a critical role in organismal growth and development. Given that the human body is incapable of synthesizing L-Trp and has to acquire it from outside sources, it is of vital importance to precisely monitor the L-Trp level in food. In this study, a ratiometric electrochemical sensing was developed based on a mixed-valence ZIF-90/Cu-Mn framework for detection of L-Trp. By doping ZIF-90 with Cu and Mn via solvothermal method, the Cu(I)/Cu(II) and Mn(II)/Mn(III) redox couples were formed within ZIF-90 framework, which endowed originally non-responsive ZIF-90 with an amplified electrochemical signal and excellent electrocatalytic reactivity toward the oxidation of Trp. Using the signal from the ZIF-90/Cu-Mn as a reference and the oxidized L-Trp signal as the detection signal, the ratio of these two signals enables more accurate detection of L-Trp, thereby enhancing the accuracy of sensor. As a result, this ratiometric sensor exhibits a wider linear range of 0 – 1000 μM, a lower detection limit of 1.67 μM (S/N = 3), excellent selectivity, repeatability, and stability. Furthermore, the ratiometric sensor was effectively employed to quantify the levels of Trp in milk, demonstrating considerable promise for practical applications, especially in the domains of food safety and quality assurance.