Longitudinal and transverse 1 H nuclear magnetic resonance relaxivities of Ln(III)-DOTA complexes (with Ln = Gd, Tb, Dy, Er; DOTA = 1,4,7,10-tetraazacyclododecane-N,N ′ ,N ′′ ,N ′′′ -tetraacetic acid) and Mn(II) aqueous solutions were measured in a wide range of frequencies, 10 kHz to 700 MHz. The experimental data were interpreted by means of models derived from the Solomon-Bloembergen-Morgan theory. The data analysis was performed assuming the orbital angular momentum L = 0 for Gd-DOTA and the aqua ion [Mn(H 2 O) 6 ] 2+ and L ≠ 0 for Dy-, Tb-, and Er-DOTA. A refined estimation of the zero-field-splitting barrier Δ and of the modulation correlation time τv was obtained for [Mn(H 2 O) 6 ] 2+ by extending the fitting of nuclear magnetic relaxation dispersion profiles to the low-field regime. The Gd-DOTA fitting parameters resulted in good agreement with the literature, and the fit of transverse relaxivity data confirmed the negligibility of the scalar interaction in the nuclear relaxation mechanism. Larger transverse relaxivities of Dy-DOTA and Tb-DOTA (∼10 mM −1 s −1 ) with respect to Er-DOTA (∼1 mM −1 s −1 ) were observed at 16 T. Such higher values are suggested to be due to a shorter residence time τm that is possibly linked to the fluctuations of the hyperfine interaction and the different shape of the magnetic anisotropy. The possible employment of Dy-DOTA, Tb-DOTA, and Er-DOTA as negative magnetic resonance imaging contrast agents for high-field applications was envisaged by collecting spin-echo images at 7 T. Particularly in Dy-and Tb-derivatives, the transverse relaxivity at 16 T is of the order of the Gd-one at 1.5 T.
Proton resonance frequency shift (PRFS) is currently the gold standard method for magnetic resonance thermometry. However, the linearity between the temperature‐dependent phase accumulation and the static magnetic field B0 confines its use to rather high‐field scanners. Applications such as thermal therapies could naturally benefit from lower field MRI settings through leveraging increased accessibility, a lower physical and economical footprint, and further consideration of the technical challenges associated with the integration of heating systems into conventional clinical scanners. T1‐based thermometry has been proposed as an alternative to the gold standard; however, because of longer acquisition times, it has found clinical use solely with adipose tissue where PRFS fails. At low field, the enhanced T1 dispersion, combined with reduced relaxation times, make T1 mapping an appealing candidate. Here, an interleaved Look‐Locker–based T1 mapping sequence was proposed for temperature quantification at 0.1 T. A variable averaging scheme was introduced, to maximize the signal‐to‐noise ratio throughout T1 recovery. In calibrated samples, an average T1 accuracy of 85% ± 4% was achieved in 10 min, compared with the 77% ± 7% obtained using a standard averaging scheme. Temperature maps between 29.0 and 41.7°C were eventually reconstructed, with a precision of 3.0 ± 1.1°C and an accuracy of 1.5 ± 1.0°C. Accounting for longer thermal treatments and less strict temperature constraints, applications such as MR‐guided mild hyperthermia treatments at low field could be envisioned.
We investigated the effect of different organic coatings on the 1H-NMR relaxation properties of ultra-small iron-oxide-based magnetic nanoparticles. The first set of nanoparticles, with a magnetic core diameter ds1 = 4.4 ± 0.7 nm, was coated with polyacrylic acid (PAA) and dimercaptosuccinic acid (DMSA), while the second set, ds2 = 8.9 ± 0.9 nm, was coated with aminopropylphosphonic acid (APPA) and DMSA. At fixed core diameters but different coatings, magnetization measurements revealed a similar behavior as a function of temperature and field. On the other hand, the 1H-NMR longitudinal r1 nuclear relaxivity in the frequency range ν = 10 kHz ÷ 300 MHz displayed, for the smallest particles (diameter ds1), an intensity and a frequency behavior dependent on the kind of coating, thus indicating different electronic spin dynamics. Conversely, no differences were found in the r1 relaxivity of the biggest particles (ds2) when the coating was changed. It is concluded that, when the surface to volume ratio, i.e., the surface to bulk spins ratio, increases (smallest nanoparticles), the spin dynamics change significantly, possibly due to the contribution of surface spin dynamics/topology.
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 pKa 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.
Thanks to the enhanced T1 dispersion and its linear dependence on temperature over the typical hyperthermia range, T1 mapping represents a serious candidate for temperature mapping at low magnetic fields. Nonetheless, T1 acquisitions are typically long and sensitivity if further reduced at low field regimes. Here we propose a Look-Locker-based temperature mapping sequence that takes advantage of the inherently higher signal gathered using a bSSFP approach. Temperatures spanning from 25 to 50°C could be mapped in doped-water samples with a temporal resolution of 20s/slice and with a precision of 2.6±1.9°C.
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