Dual-functional molecularly imprinted doped carbon dot based on metal-organic frameworks for tetracycline adsorption and determination.

ABSTRACT

A carbon dot (CD) was prepared by using tryptophan as a single carbon source and demonstrated its good selective fluorescence quenching effect on tetracycline (TC). The modified metal-organic frameworks (MOF) NH2-MIL-101 was chosen as matrix, doped with CD, molecularly imprinted polymer (MIP) prepared with TC as the template, and finally CD-MOF-MIP complexes (CD@MIP) was synthesized. For comparison, MIP were also prepared without CD as well as non-imprinted polymers and their ability was tested, respectively. CD@MIP is a nanomaterial with bright fluorescence under the irradiation of ordinary UV equipment (λ = 360 nm), which has a fast and stable fluorescence quenching for TC and a good linear relationship for TC in the concentration range 0-400 µmol L-1. The quantum yield of CD@MIP was 12.75% and the 3σ limit of detection (LOD) for CD@MIP was 0.59 µmol L-1. The maximum adsorption capacity of CD@MIP reached 304.6 mg g-1 and the adsorption equilibrium was reached after about 75 min. The adsorption of CD@MIP to tetracycline spiked in milk samples reached 90.0 mg g-1 within 2 h, which was much higher than that of NIP (48.4 mg g-1) under the same conditions, as demonstrated by high performance liquid chromatography (HPLC). The results obtained showed that CD@MIP combined the high adsorption capacity of MOF, the specific adsorption of molecular imprinting and the fluorescence properties of CD, can determine and rapidly removeTC in the environment.