Hydrophilic colloids (PSS-[Ln2(TCAi)2] and PSS-[LnCAi], where i = 1, 2, or 3 and Ln = Gd or Tb) were prepared by precipitation of Gd(III) or Tb(III) complexes with tetrathiacalix[4]arenes (TCAi)… Click to show full abstract
Hydrophilic colloids (PSS-[Ln2(TCAi)2] and PSS-[LnCAi], where i = 1, 2, or 3 and Ln = Gd or Tb) were prepared by precipitation of Gd(III) or Tb(III) complexes with tetrathiacalix[4]arenes (TCAi) and calix[4]arenes bearing two 1,3-diketone groups (CAi) from dimethylformamide to an aqueous solution of poly(sodium 4-styrenesulfonate) (PSS). Dynamic light scattering and transmission electron microscopy demonstrated the formation of nanoparticles coated by the polymer. Luminescence decay measurements on Tb(III)-based colloids allowed hydration numbers of 2 and 4 per metal ion to be determined for PSS-[Ln2(TCAi)2] and PSS-[LnCAi] samples, respectively. Longitudinal and transverse water proton relaxivity values measured at 20.8 MHz were remarkably high for the PSS-[GdCAi] colloids but unexpectedly low for the PSS-[Gd2(TCAi)2] ones. 1H fast field cycling nuclear magnetic resonance relaxometry was applied to shed light on the origin of the different relaxation enhancement in the investigated systems. Extremely slo...
               
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