Fluorescent Polyurea-Carbon Dots: Preparation, Characterization and Use as Sensor for Doxycycline Detection

Abstract

Fluorescent polyurea-carbon dots (PU-CD) were successfully achieved through a co-pyrolysis technique, combining polyurea (PU) with carboxyl-containing carbon dots (PCD) at a temperature of 220 °C. The PU was fabricated via a simple precipitation polymerization process using toluene diisocyanate in a water/acetone binary solvent system. PCD was generated by thermal treatment of poly(ethylene glycol) (PEG) at the same elevated temperature. To elucidate the structural characteristics of PU-CD, as well as its precursor components PU and PCD, a comprehensive suite of analytical techniques was employed, including transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR), dynamic light scattering (DLS) and X-ray photoelectron spectroscopy (XPS). These analyses confirmed the formation of amide bonds resulting from the reaction between the terminal amines of PU and the carboxyl groups of PCD. An in-depth comparison of the fluorescence properties of PU-CD revealed marked enhancements in fluorescence intensity when contrasted with PU, PEG, and the individual PCD. The research explored the impact of various factors such as concentration, pH in aqueous solutions, and solvent type on the fluorescence emission of these materials, providing valuable insights into their emission mechanisms. It was particularly noteworthy that both PCD and PU-CD exhibited a confined-domain crosslink-enhanced emission effect. Utilizing the aqueous dispersion of PU-CD as a fluorescent probe, the detection of doxycycline (DOX), a long-acting, broad-spectrum, semi-synthetic tetracycline antibiotic, was achieved with a detection limit of 2.9×10⁻⁷ mol/L. This study introduces a simple, green, and cost-effective fluorescent probe for the detection of DOX, which has significant potential for application in the realms of analytical chemistry and food safety monitoring in the future.