A1 Journal article (refereed)
Thiourea Organocatalysts as Emerging Chiral Pollutants : En Route to Porphyrin-Based (Chir)Optical Sensing (2021)

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

JYU authors or editors

Publication details

All authors or editors: Konrad, Nele; Horetski, Matvey; Sihtmäe, Mariliis; Truong, Khai-Nghi; Osadchuk, Irina; Burankova, Tatsiana; Kielmann, Marc; Adamson, Jasper; Kahru, Anne; Rissanen, Kari; et al.

Journal or series: Chemosensors

eISSN: 2227-9040

Publication year: 2021

Publication date: 29/09/2021

Volume: 9

Issue number: 10

Article number: 278

Publisher: MDPI AG

Publication country: Switzerland

Publication language: English

DOI: https://doi.org/10.3390/chemosensors9100278

Publication open access: Openly available

Publication channel open access: Open Access channel

Publication is parallel published (JYX): https://jyx.jyu.fi/handle/123456789/78613

Abstract

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.

Keywords: organic compounds; sulphur compounds; catalysts; ecotoxicology; bacteria; monitoring; supramolecular chemistry

Free keywords: porphyrin; thiourea; chiral amine; organocatalyst; Takemoto’s catalyst; host–guest binding; chirality; supramolecular chemistry; circular dichroism; toxicity; chiral pollutants; Vibrio fischeri

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Ministry reporting: Yes

Reporting Year: 2021

JUFO rating: 1