Coating influence on inner shell water exchange: An underinvestigated major contributor to SPIONs relaxation properties.

Superparamagnetic iron oxide nanoparticles (SPIONs) are heavily studied as potential MRI contrast enhancing agents. Every year, novel coatings are reported which yield large increases in relaxivity compared to similar particles. However, the reason for the increased performance is not always well understood mechanistically. In this review, we attempt to relate these advances back to fundamental models of relaxivity, developed for chelated metal ions, primarily gadolinium. We focus most closely on the three-shell model which considers the relaxation of surface-bound, entrained, and bulk water molecules as three distinct contributions to total relaxation. Because SPIONs are larger, more complex, and entrain significantly more water than gadolinium-based contrast agents, we consider how to adapt the application of classical models to SPIONs in a predictive manner. By carefully considering models and previous results, a qualitative model of entrained water interactions emerges, based primarily on the contributions of core size, coating thickness, density, and hydrophilicity.

Bright Asymmetric Shielding Strategy-Based NIR-II Probes for Angiography and Localized Photothermal Therapy.

Fluorescent probes with fluorescence emission in the NIR-II window have been widely studied due to increased imaging depth. However, the currently reported NIR-II fluorescent probes present some disadvantages, such as complicated synthesis routes and low fluorescence quantum yields (QYs). The shielding strategy has been used in the development of NIR-II probes to improve their QYs. So far, this strategy has only been used for the symmetric NIR-II probes, especially those based on the benzo[1,2-c:4,5-c']bis([1,2,5]thiadiazole) (BBTD) skeleton. This work reports the synthesis of a series of asymmetric NIR-II probes based on shielding strategies accompanied by simple synthetic routes, high synthetic yields (above 90%), high QYs, and large Stoke shifts. Furthermore, the use of d-α-tocopheryl polyethylene glycol succinate (TPGS) as a surfactant for an NIR-II fluorescence probe (NT-4) improved its water solubility. In vivo studies showed that TPGS-NT-4 NPs with a high QY (3.46%) achieve high-resolution angiography and efficient local photothermal therapy, while displaying good biocompatibility. Hence, we combined angiography and local photothermal therapy to improve the tumor uptake of nanophotothermal agents while reducing their damage to normal tissues.