Paramagnetic Relaxation of Long‐Lived Coherences in Solution NMR

Long‐lived coherences (LLCs) are known to have lifetimes much longer than transverse magnetization or single quantum coherences (SQCs). The effect of paramagnetic ions on the relaxation of LLCs is not known. This is particularly important, as LLCs have potential applications in various fields like analytical NMR, in vivo NMR and MR imaging methods. We study here the behaviour of LLCs in the presence of paramagnetic relaxation agents. The stepwise increase in the concentration of the metal ion is followed by measuring various relaxation rates. The effect of paramagnetic ions is analysed in terms of the external random field’s contribution to the relaxation of two coupled protons in 2,3,6‐trichlorobenzaldehyde. The LLCs relax faster than ordinary SQCs in the presence of paramagnetic ions of varying character. This is explained on the basis of an increase in the contribution of the external random field to relaxation due to a paramagnetic relaxation mechanism. Comparison is also made with ordinary Zeeman relaxation rates like R₁, R₂, R_1ρ and also with rate of relaxation of long‐lived states R_LLS which are known to be less sensitive to paramagnetically induced relaxation. Also, the extent of correlation of random fields at two proton sites is studied and is found to be strongly correlated with each other. The obtained correlation constant is found to be independent of the nature of added paramagnetic impurities.     

Nanosized T1 MRI Contrast Agent Based on a Polyamidoamine as Multidentate Gd Ligand

A linear polyamidoamine (PAA) named BAC-EDDS, containing metal chelating repeat units composed of two tert-amines and four carboxylic groups, has been prepared by the aza-Michael polyaddition of ethylendiaminodisuccinic (EDDS) with 2,2-bis(acrylamido)acetic acid (BAC). It was characterized by size exclusion chromatography (SEC), FTIR, UV–Vis and NMR spectroscopies. The pK_a values of the ionizable groups of the repeat unit were estimated by potentiometric titration, using a purposely synthesized molecular ligand (Agly-EDDS) mimicking the structure of the BAC-EDDS repeat unit. Dynamic light scattering (DLS) and ζ-potential analyses revealed the propensity of BAC-EDDS to form stable nanoaggregates with a diameter of approximately 150 nm at pH 5 and a net negative charge at physiological pH, in line with an isoelectric point <2. BAC-EDDS stably chelated Gd (III) ions with a molar ratio of 0.5:1 Gd (III)/repeat unit. The stability constant of the molecular model Gd-Agly-EDDS (log K = 17.43) was determined as well, by simulating the potentiometric titration through the use of Hyperquad software. In order to comprehend the efficiency of Gd-BAC-EDDS in contrasting magnetic resonance images, the nuclear longitudinal (r₁) and transverse (r₂) relaxivities as a function of the externally applied static magnetic field were investigated and compared to the ones of commercial contrast agents. Furthermore, a model derived from the Solomon–Bloembergen–Morgan theory for the field dependence of the NMR relaxivity curves was applied and allowed us to evaluate the rotational correlation time of the complex (τ = 0.66 ns). This relatively high value is due to the dimensions of Gd-BAC-EDDS, and the associated rotational motion causes a peak in the longitudinal relaxivity at ca. 75 MHz, which is close to the frequencies used in clinics. The good performances of Gd-BAC-EDDS as a contrast agent were also confirmed through in vitro magnetic resonance imaging experiments with a 0.2 T magnetic field.     

Ultrasmall iron oxide nanoparticles: Magnetic and NMR relaxometric properties

Ultrasmall iron oxide (USPIO) nanoparticles, with diameter mostly less than 3 nm dispersed in an organic carrier fluid were synthesized by polyol route. The evolution of ZFC-FC magnetization curves with temperature, as well as the shift of the ac susceptibility peaks upon changing the frequency, reveal that the nanoparticles in the fluid are non-interacting and superparamagnetic with the blocking temperature T_B ∼10 K. The Mössbauer spectra analysis proposed the core/shell structure of the nanoparticles consisting of stoichiometric γ-Fe₂O₃ core and non-stoichiometric shell. The nanoparticle surface layer has a great influence on their properties which is principally manifested in significant reduction of the magnetization and in a large increase in magnetic anisotropy. Magnetic moments do not saturate in fields up to 5 T, even at the lowest measured temperature, T = 5 K. The average magnetic particle diameter is changed from 1.3 to 1.8 nm with increasing magnetic field from 0 to 5 T which is noticeably smaller than the particle sizes measured by TEM. The estimated effective magnetic anisotropy constant value, K_eff = 2 × 10⁵ J/m³, is two orders of magnitude higher than in the bulk maghemite. Measurements of the longitudinal and transverse NMR relaxivity parameters on water diluted nanoparticle dispersions at 1.5 T gave the values r₁ = 0.028 mmol⁻¹ s⁻¹, r₂ = 0.050 mmol⁻¹ s⁻¹ and their ratio r₂/r₁ = 1.8. Continuous increase of the T₁-weighted MRI signal intensity with increasing Fe concentration in the nanoparticle dispersions was observed which makes this ferrofluid to behave as a positive T₁ contrast agent.