6533b82afe1ef96bd128b79e
RESEARCH PRODUCT
Thiourea Organocatalysts as Emerging Chiral Pollutants: En Route to Porphyrin-Based (Chir)Optical Sensing
Kari RissanenAnne KahruMathias O. SengeDzmitry G. KananovichJasper AdamsonMariliis SihtmäeKhai-nghi TruongMarc KielmannIrina OsadchukRiina AavTatsiana BurankovaNele KonradVictor V. BorovkovMatvey Horetskisubject
Circular dichroismSupramolecular chemistrychiralitymonitorointiEnvironmental pollutionchiral amineVibrio fischeriQD415-436010402 general chemistryBiochemistry01 natural sciencesMedicinal chemistrysupramolecular chemistrybakteeritAnalytical Chemistry<i>Vibrio</i> <i>fischeri</i>chemistry.chemical_compoundkatalyytitrikkiyhdisteetsupramolekulaarinen kemiaMoiety[CHIM]Chemical Sciences[CHIM.COOR]Chemical Sciences/Coordination chemistryPhysical and Theoretical Chemistrythioureaorgaaniset yhdisteetchiral pollutantsTrifluoromethyl010405 organic chemistrytoxicityhost–guest bindingPorphyrin0104 chemical sciencesTakemoto’s catalystcircular dichroismekotoksikologiachemistryThiourea13. Climate action[SDV.TOX.ECO]Life Sciences [q-bio]/Toxicology/Ecotoxicology[SDE.BE]Environmental Sciences/Biodiversity and EcologyChirality (chemistry)porphyrinorganocatalystdescription
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.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2021-10-01 |