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 2-aminophenol 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 μmol 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.