Label-Free Ultrasensitive and Environment-Friendly Immunosensor Based on a Silica Optical Fiber for the Determination of Ciprofloxacin in Wastewater Samples

Emerging contaminants, including pharmaceutical compounds, are receiving research attention as a result of their widespread presence in effluents and wastewater treatment plants (WWTPs). The antibiotic ciprofloxacin (CIP) is extensively employed to treat infections in animal and human medicine. Both CIP and its metabolites are common contaminants found in WWTPs. In this study, a label-free ultrasensitive U-bent optical fiber-based immunosensor for the determination of CIP in wastewater samples was developed using the properties of the conducting polymer polyaniline (PANI). The anti-CIP immunoglobulin G (IgG) was deposited on a silica optical fiber surface previously functionalized with PANI. Scanning electron microscopy and micro-Raman spectroscopy were used to investigate the surface of the immunosensor. The analysis of CIP in wastewater was performed without the use of an organic solvent or sample preparation steps, with only the sample dilution in saline buffer (pH = 7.4). The linear range for CIP was from 0.01 to 10,000 ng L-1. The detection limit was 3.30 x 10(-3) ng L-1 and the quantification limit was 0.01 ng L-1. The immunosensor provided a high average recovery of 91% after spiking wastewater samples with CIP at a concentration of 9,100 ng L-1. The method was applied in triplicate to wastewater samples from Quebec (Canada), obtaining concentrations of 549 and 267 ng L-1. A comparison with a reference method showed no significant difference (t-test at 95% confidence). The new technique developed is selective, allowing a quantitative analysis of CIP in wastewater.