Carbon Nanodots with Solvatochromic Photoluminescence for the Electrochemical Determination of Estrogenic Steroids

Herein, we utilized carbon nanodots (R-CNDs) for the electrochemical detection of estrogens in tap and natural water samples and simulated effluents from Swedish waste water treatment plants (WWTPs). R-CNDs were prepared from 2aminophenol by solvothermal synthesis and used as a modifier for chitosan-based selective membranes. The data obtained from atomic force microscopy and transmission electron microscopy suggest a spherical morphology of the R-CNDs with lateral size in the range of 3-8 nm and the height of 1-8 nm. In contrast to most other known carbon nanodots, R-CNDs are soluble in various organic solvents, including apolar, and less soluble in water. Small nanodots (3 nm) are more hydrophilic than large ones (6-8 nm) and can be separated from the bulk suspension of R-CNDs in heptane by their extraction into a water/ethanol mixture. Suspensions of large R-CNDs in apolar solvents exhibit green photoluminescence, while small R-CNDs in polar solvents have orange. This phenomenon was attributed to a solvatochromic rather than to a quantum effect. The R-CNDs were embedded on a chitosan-modified pencil electrode and the electrode was applied for voltammetric determination of four abandoned estrogens: estrone, estradiol, estriol, and ethynyl estradiol. The sensor demonstrates a group-selective response to the estrogens with a detection limit of 17.0 nmol L-1. It can be applied to determine the estrogens in the range of 0.05-4.6 mu mol L-1 in the presence of typical interfering bioactive compounds, such as paracetamol, uric acid, progesterone, sulfamethoxazole, trimethoprim, ibuprofen, and caffeine. The developed sensors show repeatability and reproducibility values of 1.8-3.4% and 4.3%, respectively. The efficiency was proved by application for tap and lake water samples, where the recovery range was found to be 93-100%. The low cost, stability, and high sensitivity and selectivity of fabricated sensors make R-CNDs a perspective modifier for electrochemical sensors for the detection of estrogen microquantities in variable water samples.