Two types of conformational dynamics and thermo-sensor properties of praseodymium-DOTA by 1H/13C NMR

Sergey P. Babailov, Eugeny N. Zapolotsky, Alexander I. Kruppa, Pavel A. Stabnikov, Ivan A. Godovikov, Eduard V. Bocharov, Eduard S. Fomin

    Research output: Contribution to journalArticle

    Abstract

    In aqueous medium, [Pr(H2O)(DOTA)] (I) undergo a intramolecular interconversion between two conformers (here DOTA = 1, 4, 7, 10-tetraaza-1, 4, 7, 10-tetrakis (carboxymethyl)cyclododecan; n = 0, 1, 2). Two types of molecular dynamic processes were found {enantiomerization and interconversion of the square-anti-prismatic (SAP) to twisted-square-anti-prismatic conformers (TSAP)}. The free energies of activation of the SAP to TSAP interconversion (for I complex) are found to be 50 ± 3 and 54 ± 4 kJ mol−1 (according to 1H and 13C NMR respectively). And, the activation free energy of enantiomerization is ΔG 298 = 65 ± 2 kJ mol−1. It was evaluated that the activation energy of enantiomerization in [Gd(H2O) (DOTA)] (II) is 64 ± 2 kJ mol−1 (by analysis of the dependence of the free activation energy on the ionic radius of other lanthanide ions). The experimental paramagnetic LIS values of I are well fitted by linear dependence on 1/T. It was found that I may be used as NMR thermometric sensors for controlling the local temperature in aqueous medium.

    Original languageEnglish
    Pages (from-to)340-344
    Number of pages5
    JournalInorganica Chimica Acta
    Volume486
    DOIs
    Publication statusPublished - 24 Feb 2019

    Fingerprint

    Praseodymium
    praseodymium
    Free energy
    Activation energy
    Chemical activation
    free energy
    Nuclear magnetic resonance
    activation
    activation energy
    Lanthanoid Series Elements
    nuclear magnetic resonance
    sensors
    Sensors
    Rare earth elements
    Molecular dynamics
    Ions
    molecular dynamics
    radii
    ions
    Temperature

    Keywords

    • Conformation dynamics
    • DOTA
    • Free energy of activation
    • Lanthanide complexes
    • Lanthanide-induced shifts in NMR spectra
    • Molecular magnet
    • NMR/MRI temperature sensor

    ASJC Scopus subject areas

    • Physical and Theoretical Chemistry
    • Inorganic Chemistry
    • Materials Chemistry

    Cite this

    Babailov, S. P., Zapolotsky, E. N., Kruppa, A. I., Stabnikov, P. A., Godovikov, I. A., Bocharov, E. V., & Fomin, E. S. (2019). Two types of conformational dynamics and thermo-sensor properties of praseodymium-DOTA by 1H/13C NMR. Inorganica Chimica Acta, 486, 340-344. https://doi.org/10.1016/j.ica.2018.10.044

    Two types of conformational dynamics and thermo-sensor properties of praseodymium-DOTA by 1H/13C NMR. / Babailov, Sergey P.; Zapolotsky, Eugeny N.; Kruppa, Alexander I.; Stabnikov, Pavel A.; Godovikov, Ivan A.; Bocharov, Eduard V.; Fomin, Eduard S.

    In: Inorganica Chimica Acta, Vol. 486, 24.02.2019, p. 340-344.

    Research output: Contribution to journalArticle

    Babailov, SP, Zapolotsky, EN, Kruppa, AI, Stabnikov, PA, Godovikov, IA, Bocharov, EV & Fomin, ES 2019, 'Two types of conformational dynamics and thermo-sensor properties of praseodymium-DOTA by 1H/13C NMR', Inorganica Chimica Acta, vol. 486, pp. 340-344. https://doi.org/10.1016/j.ica.2018.10.044
    Babailov SP, Zapolotsky EN, Kruppa AI, Stabnikov PA, Godovikov IA, Bocharov EV et al. Two types of conformational dynamics and thermo-sensor properties of praseodymium-DOTA by 1H/13C NMR. Inorganica Chimica Acta. 2019 Feb 24;486:340-344. https://doi.org/10.1016/j.ica.2018.10.044
    Babailov, Sergey P. ; Zapolotsky, Eugeny N. ; Kruppa, Alexander I. ; Stabnikov, Pavel A. ; Godovikov, Ivan A. ; Bocharov, Eduard V. ; Fomin, Eduard S. / Two types of conformational dynamics and thermo-sensor properties of praseodymium-DOTA by 1H/13C NMR. In: Inorganica Chimica Acta. 2019 ; Vol. 486. pp. 340-344.
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    AU - Kruppa, Alexander I.

    AU - Stabnikov, Pavel A.

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