Label-free fluorescent discrimination and detection of epinephrine and dopamine based on bioinspired in situ copolymers and excitation wavelength switch

A simple and label-free fluorescence turn-on method is proposed for the discrimination and detection of epinephrine (Ep) and dopamine (DA) via polyethyleneimine (PEI)-initiated in situ copolymerization and excitation wavelength switch. The PEI solution in the presence of Ep, DA and the mixture of Ep and DA are denoted as P Ep-PEI , P DA-PEI and M Ep+DA , respectively. In this study, PEI aqueous solution medium initiates the auto-oxidization of Ep and DA and the bioinspired copolymerization. These resultant copolymers emit yellow-green fluorescence color with a fluorescence emission maximum at 515 nm. Interestingly, these fluorescent copolymers exhibit distinct different excitation spectra, although Ep and DA are structurally very similar. P DA-PEI exhibits only one excitation peak at 385 nm, and P Ep-PEI shows dual-excitation mode with two significant excitation peaks at 328 nm and 405 nm, respectively. M Ep+DA also shows dual-excitation mode with two excitation peaks at 330 nm and 395 nm, respectively. Thus, individual Ep, DA, and their mixture can be discriminated based on the different excitation spectral shapes and peak locations of P Ep-PEI , P DA-PEI and M Ep+DA . Furthermore, the quantitative analysis of Ep and DA in mixture can also be achieved by switching excitation wavelength between 330 and 395 nm and monitoring the fluorescence emission intensity of M Ep+DA at 515 nm. The fluorescence intensity of M Ep+DA only related to the concentration of Ep when excited at 330 nm. Moreover, the concentration of DA can also be calculated by subtracting the fluorescence intensity of P Ep-PEI from the total fluorescence intensity when excited at 395 nm. The resultant method has been used to simultaneously detect Ep and DA in human urine samples. The proposed fluorescence system is facile, eco-friendly, low-cost, and time-saving, and also provides a new and simple path for discriminating analogues.