Thiourea organocatalysts as emerging chiral pollutants: En route to porphyrin-based (chir)optical sensing
Item Type:Journal Article
Citation:Konrad, N. and Horetski, M. and Sihtmäe, M. and Truong, K.-N. and Osadchuk, I. and Burankova, T. and Kielmann, M. and Adamson, J. and Kahru, A. and Rissanen, K. and Senge, M.O. and Borovkov, V. and Aav, R. and Kananovich, D., Thiourea organocatalysts as emerging chiral pollutants: En route to porphyrin-based (chir)optical sensing, Chemosensors, 2021, 9, 10
Konrad-2021-Thiourea-organocatalysts-as-emergin(1).pdf (PDF) 2.793Mb
Environmental pollution with chiral organic compounds is an emerging problem requiring innovative sensing methods. Amino-functionalized thioureas, such as 2-(dimethylamino)cyclohexyl-(3,5-bis(trifluoromethyl)phenyl)thiourea (Takemoto’s catalyst), are widely used organocatalysts with virtually unknown environmental safety data. Ecotoxicity studies based on the Vibrio fischeri luminescence inhibition test reveal significant toxicity of Takemoto’s catalyst (EC50 = 7.9 mg/L) and its NH2-substituted analog (EC50 = 7.2–7.4 mg/L). The observed toxic effect was pronounced by the influence of the trifluoromethyl moiety. En route to the porphyrin-based chemosensing of Takemoto-type thioureas, their supramolecular binding to a series of zinc porphyrins was studied with UV-Vis and circular dichroism (CD) spectroscopy, computational analysis and single crystal X-ray diffraction. The association constant values generally increased with the increasing electron-withdrawing properties of the porphyrins and electron-donating ability of the thioureas, a result of the predominant Zn⋯N cation–dipole (Lewis acid–base) interaction. The binding event induced a CD signal in the Soret band region of the porphyrin hosts—a crucial property for chirality sensing of Takemoto-type thioureas.
Author: Senge, Mathias
Type of material:Journal Article
Availability:Full text available
Keywords:chiral organic compounds, Amino-functionalized thioureas, Vibrio fischer iluminescence inhibition test, Vibrio fischeri, Chiral pollutants, Toxicity, Circular dichroism, Supramolecular chemistry, Chirality, Host–guest binding, Takemoto’s catalyst, Organocatalyst, Chiral amine, Thiourea, Porphyrin
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