Motivated by the possibility of exploiting species containing high spin quantum number nuclei (referred to as quadrupole nuclei) as novel contrast agents for Magnetic Resonance Imaging, based on Quadrupole Relaxation Enhancement (QRE) effects, 1H spin-lattice relaxation has been investigated for tris(2-methoxyphenyl)bismuthane and tris(2,6-dimethoxyphenyl)bismuthane in powder. The relaxation experiment has been performed in the magnetic field range of 0.5 T to 3 T (the upper limit corresponds to the field used in many medical scanners). A very rich QRE pattern (several frequency specific 1H spin-lattice relaxation rate maxima) has been observed for both compounds. Complementary Nuclear Quadrupole Resonance experiments have been performed in order to determine the quadrupole parameters (quadrupole coupling constant and asymmetry parameters) for 209Bi. Knowing the parameters, the QRE pattern has been explained on the basis of a quantum-mechanical picture of the system including single and double-quantum coherences for the participating nuclei (1H and 209Bi). In this way the quantum-mechanical origin of the spin transitions leading to the QRE effects has been explained.
Nuclear Quadrupole Resonance (NQR) experiments were performed for deuterated and non-deuterated triphenylbismuth (BiPh3) to inquire into 209Bi relaxation mechanisms. The studies are motivated by the idea of exploiting Quadrupole Relaxation Enhancement (QRE) as a novel contrast mechanism for Magnetic Resonance Imaging. From this perspective relaxation features of nuclei possessing quadrupole moment (quadrupole nuclei) are of primary importance for the contrast effect. Spin-spin relaxation rates associated with the NQR lines were described in terms of the Redfield relaxation theory assuming that the relaxation is caused by fluctuations of the electric field gradient tensor at the position of the quadrupole nucleus that are described by an exponential correlation function. The description referred to as a model-free approach is an analogy of the description used for paramagnetic contrast agents. It was demonstrated that for the deuterated compound this approach captures the essential features of 209Bi relaxation, but it should not be applied for non-deuterated compounds as dipolar interactions between neighbouring protons and the quadrupole nucleus considerably contribute to the relaxation of the last one. Thus, the relaxation scenario for species containing quadrupole nuclei is fundamentally different than for paramagnetic contrast agents and this fact has to be taken into account when predicting contrast effects based on QRE.
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