Thiourea Organocatalysts as Emerging Chiral Pollutants : En Route to Porphyrin-Based (Chir)Optical Sensing
Konrad, N., Horetski, M., Sihtmäe, M., Truong, K.-N., Osadchuk, I., Burankova, T., Kielmann, M., Adamson, J., Kahru, A., Rissanen, K., Senge, M. O., Borovkov, V., Aav, R., & Kananovich, D. (2021). Thiourea Organocatalysts as Emerging Chiral Pollutants : En Route to Porphyrin-Based (Chir)Optical Sensing. Chemosensors, 9(10), Article 278. https://doi.org/10.3390/chemosensors9100278
© 2021 by the authors. Licensee MDPI, Basel, Switzerland.
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. ...
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Additional information about fundingThis work was supported by the Estonian Research Council grant PUTJD749 (for I.O.) PRG399, (for N.K., R.A., V.B.), PSG400 (for J.A), PRG749 (for M.S.), European Regional Development Fund grants NAMUR+ 2014-2020.4.01.16-0123 (for M.S. and A.K) and TK134 (for A.K., J.A.) and the European Union’s H2020-FETOPEN grant 828779 (INITIO) (for N.K., K.-N.T., K.R., M.K., M.O.S., D.K., R.A., V.B.). M.H. is grateful to the Dora Plus program for financial support of his research stay at Tallinn University of Technology. ...
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