The Relationship between NMR Chemical Shifts of Thermally Polarized and Hyperpolarized 89Y Complexes and Their Solution Structures

• Published in: Chemistry : a European journal Vol. 22; no. 46; pp. 16657 - 16667
• Main Authors: Xing, Yixun, Jindal, Ashish K., Regueiro-Figueroa, Martín, Le Fur, Mariane, Kervarec, Nelly, Zhao, Piyu, Kovacs, Zoltan, Valencia, Laura, Pérez-Lourido, Paulo, Tripier, Raphaël, Esteban-Gómez, David, Platas-Iglesias, Carlos, Sherry, A. Dean
• Format: Journal Article
• Language: English
• Published: WEINHEIM Blackwell Publishing Ltd 07.11.2016; Wiley; Wiley Subscription Services, Inc
• Subjects: Chemistry; Chemistry, Multidisciplinary; Coordination compounds; Correlation; density functional calculations; Design; Empirical equations; hyperpolarization; Imaging; Ligands; magnetic resonance imaging; Mathematical analysis; NMR; NMR spectroscopy; Nuclear magnetic resonance; Nuclei; Physical Sciences; Polarization; Science & Technology; Sensitivity; Sensors; Signal to noise ratio; Spectroscopic analysis; Spectroscopy; Technology; Yttrium; magnetic resonance imaging; CRYSTAL-STRUCTURES; LANTHANIDE(III) COMPLEXES; DOTA COMPLEXES; COORDINATION EQUILIBRIA; density functional calculations; yttrium; FAST WATER EXCHANGE; MAGNETIC-RESONANCE; YTTRIUM COMPLEXES; hyperpolarization; BASIS-SETS; NMR spectroscopy; MRI CONTRAST AGENTS; NUCLEAR-POLARIZATION
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201602901

Recently developed dynamic nuclear polarization (DNP) technology offers the potential of increasing the NMR sensitivity of even rare nuclei for biological imaging applications. Hyperpolarized 89Y is an ideal candidate because of its narrow NMR linewidth, favorable spin quantum number (I=1/2 ), and long longitudinal relaxation times (T1). Strong NMR signals were detected in hyperpolarized 89Y samples of a variety of yttrium complexes. A dataset of 89Y NMR data composed of 23 complexes with polyaminocarboxylate ligands was obtained using hyperpolarized 89Y measurements or 1H,89Y‐HMQC spectroscopy. These data were used to derive an empirical equation that describes the correlation between the 89Y chemical shift and the chemical structure of the complexes. This empirical correlation serves as a guide for the design of 89Y sensors. Relativistic (DKH2) DFT calculations were found to predict the experimental 89Y chemical shifts to a rather good accuracy. Into the side pocket! The 89Y NMR chemical shifts measured for a wide range of Y3+ complexes can be estimated from a set of empirical contributions associated to the different types of donor atoms coordinated to the metal ion. This correlation will serve as a guide for the design of magnetic resonance imaging sensors based on hyperpolarized 89Y.