Rational design of efficient nanosensor for glyphosate and temperature out of terbium complexes with 1,3-diketone calix[4]arenes
| Autor: | Andrey M. Kuznetsov, Dmitry V. Lapaev, Rustem Zairov, V. V. Syakaev, Yulia H. Budnikova, Irek R. Nizameev, Asiya R. Mustafina, Svetlana N. Sudakova, Gulnaz Sh. Gimazetdinova, Alexey N. Masliy, Oleg G. Sinyashin, Alexey P. Dovzhenko, Sergey N. Podyachev |
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| Rok vydání: | 2022 |
| Předmět: |
Diketone
Chemistry Ligand Metals and Alloys Rational design chemistry.chemical_element Terbium Condensed Matter Physics Surfaces Coatings and Films Electronic Optical and Magnetic Materials Colloid Polymer chemistry Materials Chemistry Proton NMR Electrical and Electronic Engineering Luminescence Instrumentation Stoichiometry |
| Zdroj: | Sensors and Actuators B: Chemical. 350:130845 |
| ISSN: | 0925-4005 |
| Popis: | The temperature and substrate dependent luminescence of terbium complexes with calix[4]arene derivatives makes them promising building blocks of nanosensors. Thus, calix[4]arene 1,3-diketones in 1,3-alternate and cone isomeric forms bearing buthyl, dodecyl, nonyl and bromine substituents are introduced as ligands forming luminescent Tb3+ complexes in basified DMF solutions. The structure variation of the ligands allows to highlight buthyl-substituted derivative of calix[4]arene 1,3-diketone in 1,3-alternate isomeric form as the optimal structure. The detailed studies of the complex stoichiometry by means of UV-Vis and H1 NMR diffusion spectroscopy methods reveal 2:2 stoichiometry as the main for the calix[4]arene 1,3-diketones in 1,3-alternate isomeric form. The predominance of 2:2 over 1:1 and 1:2 (Tb:L) complex stoichiometries for the buthyl-substituted ligand was confirmed by comparison of the quantum chemically calculated thermochemical parameters of their complex formation. However, the 2:2 complex formation is either restricted for their dodecyl-substituted derivative or interferes with the 1:2 stoichiometry for the bromo-substituted counterpart. The conversion of the Tb3+ complexes from the DMF solutions to the PSS-stabilized colloids through the solvent-exchange procedure reveals the unfavorable effect of the nonyl- and dodecyl-substituted ligands on aggregation behavior of the colloids. Thus, 2:2 terbium complex with buthyl-substituted ligand in 1,3-alternate isomeric form is the optimal basis for production of the luminescent PSS-colloids with high colloid stability. The Tb3+- luminescence of the colloids exhibit the enhanced sensitivity to both environmental pollutant glyphosate with LOD = 1.97 nM and temperature changes within the physiological temperature range with SI = −4.67 K-% at 323 K. |
| Databáze: | OpenAIRE |
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