RESUMO
An ensemble of nanosystems can be considered to improve magnetic resonance imaging (MRI) transverse relaxivity. Herein, an interacting superparamagnetic competing structure of an isotropic-anisotropic trimagnetic hybrid nanosystem, γ-Fe2O3@δ-MnO2@NiFe2O4, is considered for MRI relaxivity exploration. The interacting superparamagnetic system reveals fascinating dynamic magnetic behavior, where flower-shaped two-dimensional flakes are decorated over nanoparticles. The hybrid nanosystem exhibits modulated shape anisotropy with spin blocking and energy barrier broadening, which help in achieving faster MR transverse relaxivity. The hierarchical architecture ensemble of the trimagnetic landscape shows effective MR transverse relaxivity with a transverse (r2)/longitudinal (r1) relaxivity of 61.5 and potential cell viability. The competing trimagnetic system with regulated activation energy is found to be the underlying reason for such signal enhancement in MRI contrast efficiency. Hence, this study displays a novel pathway correlating MR transverse relaxivity with dynamic magnetic behavior and competing landscape of hierarchical trimagnetic ensembles.
RESUMO
The potential application of magnetic nanosystems as magnetic resonance imaging (MRI) contrast agents has been thoroughly investigated. This work seeks to attain robust MRI-contrast efficiency by designing an interacting landscape of a bimagnetic ensemble of zinc ferrite nanorods and maghemite nanoparticles, γ-Fe2O3@ZnFe2O4. Because of competing spin clusters and structural anisotropy triggered by isotropic γ-Fe2O3 and anisotropic ZnFe2O4, γ-Fe2O3@ZnFe2O4 undergoes the evolution of cluster spin-glass state as evident from the critical slowing down law. Such interacting γ-Fe2O3@ZnFe2O4 with spin flipping of 1.2 × 10-8 s and energy barrier of 8.2 × 10-14 erg reflects enhanced MRI-contrast signal. Additionally, γ-Fe2O3@ZnFe2O4 is cell-viable to noncancerous HEK 293 cell-line and shows no pro-tumorigenic activity as observed in MDA-MB-231, an extremely aggressive triple-negative breast cancer cell line. As a result, γ-Fe2O3@ZnFe2O4 is a feasible option for an MRI-contrast agent having longitudinal relaxivity, r1, of 0.46 s-1mM-1 and transverse relaxivity, r2, of 15.94 s-1mM-1, together with r2/r1 of 34.65 at 1.41 T up to a modest metal concentration of 0.1 mM. Hence, this study addresses an interacting isotropic/anisotropic framework with faster water proton decay in MR-relaxivity resulting in phantom signal amplification.
RESUMO
Y. Gossuin et al. in their Comment on "Structure-Correlated Magnetic Resonance Transverse Relaxivity Enhancement in Superparamagnetic Ensembles with Complex Anisotropy Landscape" [ Langmuir 2023, DOI: 10.1021/acs.langmuir.2c03428] put forward certain concerns about the proposed relaxation dependency hypothesis described in our work [ Langmuir 2022, 38 (36), 11087-11098.]. In this reply to their comment, we would like to express the justification of our considered hypothesis in the complex geometry of nanosystems in order to overcome the raised concerns of MR-relaxivity dependency on such complex landscape of anisotropy.
RESUMO
The aim of the work is to explore structure-relaxivity relationship by observing transverse relaxivity enhancement in magnetic resonance imaging (MRI) of differently organized superparamagnetic complex ensembles of zinc ferrite isotropic/anisotropic nanosystems. We observe that superparamagnetic systems show a correlation of MRI-transverse relaxivity, r2/r1, with spatial arrangement of nanoparticles, as well as magnetic easy axes and thermal-energy-dependent anisotropy energy landscape. The presence of highly random/partially aligned easy axes with enhanced anisotropy constant leads to modulation in transverse relaxation. As a result, we achieve highest contrast efficiency in compact ensemble of isotropic nanoparticles and hollow core ensemble. Indeed, core-shell ensemble with combined effect of aligned and randomly oriented easy magnetic axes shows a reduction in MRI contrast efficiency. However, we address a hypothesis for transverse contrast efficiency where we depict the correlation among MRI-transverse contrast efficiency with structural complexity of ensembles, differently arranged primary nanoparticles/magnetic easy axes, anisotropy constant, and collective magnetic behavior. In consequence, we simplify the limitation of quantum mechanical outer-sphere diffusion model of magnetic resonance relaxivity by neglecting the contribution of magnetization and introducing an anisotropy constant contribution with complex structure landscape of easy axes.