Hydration number: crucial role in nuclear magnetic relaxivity of Gd(III) chelate-based nanoparticles

Rustem Zairov; Gulshat Khakimullina; Sergey Podyachev; Irek Nizameev; Georgy Safiullin; Rustem Amirov; Alberto Vomiero; Asiya Mustafina

doi:10.1038/s41598-017-14409-6

Hydration number: crucial role in nuclear magnetic relaxivity of Gd(III) chelate-based nanoparticles

Sci Rep. 2017 Oct 25;7(1):14010. doi: 10.1038/s41598-017-14409-6.

Authors

Rustem Zairov¹, Gulshat Khakimullina², Sergey Podyachev³, Irek Nizameev⁴, Georgy Safiullin⁵, Rustem Amirov², Alberto Vomiero⁶, Asiya Mustafina³

Affiliations

¹ A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center of Russian Academy of Sciences, Arbuzov str., 8, 420088, Kazan, Russia. rustem02@yandex.ru.
² Kazan (Volga region) Federal university, Kremlyovskaya str., 18, 420008, Kazan, Russia.
³ A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center of Russian Academy of Sciences, Arbuzov str., 8, 420088, Kazan, Russia.
⁴ Kazan National Research Technical University, K. Marx str., 10, 420211, Kazan, Russia.
⁵ Zavoisky Physical -Technical Institute of Kazan Scientific Center of Russian Academy of Sciences, Sibirsky tract, 10/7, 420029, Kazan, Russia.
⁶ Division of Materials Science, Department of Engineering Sciences and Mathematics, Luleå University of Technology, SE-971 87, Luleå, Sweden.

Abstract

Today, nanostructure-based contrast agents (CA) are emerging in the field of magnetic resonance imaging (MRI). Their sensitivity is reported as greatly improved in comparison to commercially used chelate-based ones. The present work is aimed at revealing the factors governing the efficiency of longitudinal magnetic relaxivity (r₁) in aqueous colloids of core-shell Gd(III)-based nanoparticles. We report for the first time on hydration number (q) of gadolinium(III) as a substantial factor in controlling r₁ values of polyelectrolyte-stabilized nanoparticles built from water insoluble complexes of Gd(III). The use of specific complex structure enables to reveal the impact of the inner-sphere hydration number on both r₁ values for the Gd(III)-based nanoparticles and the photophysical properties of their luminescent Tb(III) and Eu(III) counterparts. The low hydration of TTA-based Gd(III) complexes (q ≈ 1) agrees well with the poor relaxivity values (r₁ = 2.82 mM^-1s^-1 and r₂ = 3.95 mM^-1s^-1), while these values tend to increase substantially (r₁ = 12.41 mM^-1s^-1, r₂ = 14.36 mM^-1s^-1) for aqueous Gd(III)-based colloids, when macrocyclic 1,3-diketonate is applied as the ligand (q ≈ 3). The regularities obtained in this work are fundamental in understanding the efficiency of MRI probes in the fast growing field of nanoparticulate contrast agents.

Publication types

Research Support, Non-U.S. Gov't