Sensitive fluorescent detection and micromechanism of Mn-doped CuS probe for oxytetracycline hydrochloride

The novel CuMnS nanoflower fluorescent probe based on Mn-doped CuS was developed to achieve the fluorescence detection of oxytetracycline hydrochloride (OTC), the fluorescent sensor has good selectivity and stability. The doping of Mn significantly increased the fluorescence intensity of CuS, which was above 10 times that of CuS. When the predominant species of OTC molecule was zwitterionic OTC^+/-at the solution pH of about 5.00, the fluorescence quenching efficiency of CuMnS by OTC reached the highest. Through fluorescence lifetime and UV absorption, the sensing mechanism between CuMnS and OTC was found to be static quenching. Moreover, Multiwfn wavefunction analysis program based on density function theory (DFT) calculation was applied to compare the interactions between different OTC species and CuMnS at different pH, to reveal the micromechanism of fluorescence quenching of CuMnS by OTC from the views of atoms. The molecular surface quantitative analysis and basin analysis of different OTC species demonstrated that the N atom and O atoms of tricarbonylamide moiety of zwitterionic OTC^+/- can provide lone pair electrons to form a non-fluorescent ground state complex with CuMnS. Meanwhile, the electrostatic attraction of OTC^+/- with negatively charged CuMnS was also beneficial to the interaction, resulting in the effective fluorescence quenching of CuMnS. This work offers a convenient method for sensitively detecting OTC and broadens the application of CuMnS in the field of fluorescence detection.