Dongkyun Gil

A dual-target fluorescent chemosensor BQC (((E)-N-benzhydryl-2-(quinolin-2-ylmethylene)hydrazine-1-carbothioamide) was synthesized for detecting In³⁺ and ClO⁻. BQC displayed green and blue fluorescence responses to In³⁺ and ClO⁻ with low detection limits (0.83 µM for In³⁺ and 2.50 µM for ClO⁻), respectively. Importantly, BQC is the first fluorescent chemosensor capable of detecting In³⁺ and ClO⁻. The binding ratio between BQC and In³⁺ was determined to be a 2:1 through Job plot and ESI-MS analysis. BQC could be successfully utilized as a visible test kit to detect In³⁺. Meanwhile, BQC showed a selective turn-on response to ClO⁻ even in the presence of anions or reactive oxygen species. The sensing mechanisms of BQC for In³⁺ and ClO⁻ were demonstrated by ¹ H NMR titration, ESI-MS and theoretical calculations.

A dinitrophenol-based colorimetric chemosensor sequentially sensing Cu²⁺ and S²⁻, HDHT ((E)-2-(2-(2-hydroxy-3,5-dinitrobenzylidene)hydrazineyl)-N,N,N-trimethyl-2-oxoethan-1-aminium), was designed and synthesized. The HDHT selectively detected Cu²⁺ through a color change of yellow to colorless. The calculated detection limit of the HDHT for Cu²⁺ was 6.4 × 10⁻² μM. In the interference test, the HDHT was not considerably inhibited by various metal ions in its detection of Cu²⁺. The chelation ratio of the HDHT to Cu²⁺ was determined as 1:1 by using a Job plot and ESI-MS experiment. In addition, the HDHT–Cu²⁺ complex showed that its color selectively returned to yellow only in the presence of S²⁻. The detection limit of the HDHT–Cu²⁺ complex for S²⁻ was calculated to be 1.2 × 10⁻¹ μM. In the inhibition experiment for S²⁻, the HDHT–Cu²⁺ complex did not significantly interfere with other anions. In the real water-sample test, the detection performance of the HDHT for Cu²⁺ and S²⁻ was successfully examined. The detection features of HDHT for Cu²⁺ and the HDHT–Cu²⁺ for S²⁻ were suggested by the Job plot, UV–Vis, ESI-MS, FT-IR spectroscopy, and DFT calculations.

A practical hydrazine-carbothioamide-based fluorescent chemosensor TCC (N-(4-chlorophenyl)-2-(thiophene-2-carbonyl)hydrazine-1-carbothioamide) was applied for Zn²⁺ detection. TCC exhibited selective fluorescence emission for Zn²⁺ and did not show any interference with other metal ions. In particular, TCC was utilized for the detection of Zn²⁺ in paper strips, zebrafish and real water samples. TCC could detect Zn²⁺ down to 0.39 μM in the solution phase and 51.13 μM in zebrafish. The association ratio between TCC and Zn²⁺ was determined to be 2:1 by ESI-mass and Job plot. The sensing mechanism of TCC for Zn²⁺ was illustrated to be a chelation-enhanced fluorescence process through spectroscopic experiments and theoretical calculations.