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

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

Journal

Inorganica Chimica Acta
ISSN: 1873-3255 , E-ISSN: 0020-1693

Output data

Year: 2019, Volume: 486, Pages: 340-344 Pages count : 5 DOI: 10.1016/j.ica.2018.10.044

Authors

Babailov Sergey P. ^1,2 , Zapolotsky Eugeny N. ¹ , Kruppa Alexander I. ³ , Stabnikov Pavel A. ¹ , Godovikov Ivan A. ⁴ , Bocharov Eduard V. ^5,6 , Fomin Eduard S. ⁷

Affiliations

1	A.V. Nikolaev Institute of Inorganic Chemistry, The Siberian Branch of the Russian Academy of Sciences, Av. Lavrentyev 3, Novosibirsk 630090, Russian Federation
2	National Research Tomsk Polytechnic University, Lenin Avenue 30, Tomsk 634050, Russian Federation
3	Voevodsky Institute of Chemical Kinetics and Combustion, Siberian Branch of the Russian Academy of Sciences, Insitutskaya 3, 630090 Novosibirsk, Russian Federation
4	A.N. Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences, Vavilova str. 28, Moscow 119334, Russian Federation
5	National Research Centre “Kurchatov Institute”, Akad. Kurchatova pl. 1, Moscow 123182, Russian Federation
6	Shemyakin-Ovchinnikov Institute of Bioorganic Chemistry RAS, Miklukho-Maklaya ul. 16/10, Moscow 117997, Russian Federation
7	Department of High Performance Computing in Bioinformatics, Institute of Cytology and Genetics of the Siberian Branch of the Russian Academy of Sciences, Av.Lavrentyev 10, 630090 Novosibirsk, Russian Federation

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.

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

Published print:

Sep 18, 2018

Web of science:	WOS:000454151300042
Scopus:	2-s2.0-85055906991
OpenAlex:	W2897545803

DB	Citing
Scopus	18
OpenAlex	19
Web of science	18