“…These values are similar to those previously reported for other polyelectrolyte-coated lanthanide chelates1742. Their size distribution is narrow even without any prefiltration or fractionizing, which is clearly seen from the polydispersity (PDI) indices.…”
Section: Resultssupporting
confidence: 90%
“…The DLS data reveal the size of hydrated PSS-coated colloids, while their functionality results from the hard cores inside the polyelectrolyte coating174345. The previously published reports1743 highlight hard-soft morphology of the colloids. The TEM image of the dried colloids presented in Fig.…”
Section: Resultsmentioning
confidence: 80%
“…Despite the proven clinical efficacy of Gd-DTPA, Gd-DOTA and other gadolinium-based molecular MRI agents, they suffer from dechelation and transmetallation processes taking place in the presence of chelating anions and endogenous cations, correspondingly1516. At the same time, luminescent function of lanthanide-containing optical labels is quenched in presence of organic background in the biological sample due to antennae-ligands replacement111718.…”
Polyelectrolyte-coated nanoparticles consisting of terbium and gadolinium complexes with calix[4]arene tetra-diketone ligand were first synthesized. The antenna effect of the ligand on Tb(III) green luminescence and the presence of water molecules in the coordination sphere of Gd(III) bring strong luminescent and magnetic performance to the core-shell nanoparticles. The size and the core-shell morphology of the colloids were studied using transmission electron microscopy and dynamic light scattering. The correlation between photophysical and magnetic properties of the nanoparticles and their core composition was highlighted. The core composition was optimized for the longitudinal relaxivity to be greater than that of the commercial magnetic resonance imaging (MRI) contrast agents together with high level of Tb(III)-centered luminescence. The tuning of both magnetic and luminescent output of nanoparticles is obtained via the simple variation of lanthanide chelates concentrations in the initial synthetic solution. The exposure of the pheochromocytoma 12 (PC 12) tumor cells and periphery human blood lymphocytes to nanoparticles results in negligible effect on cell viability, decreased platelet aggregation and bright coloring, indicating the nanoparticles as promising candidates for dual magneto-fluorescent bioimaging.
“…These values are similar to those previously reported for other polyelectrolyte-coated lanthanide chelates1742. Their size distribution is narrow even without any prefiltration or fractionizing, which is clearly seen from the polydispersity (PDI) indices.…”
Section: Resultssupporting
confidence: 90%
“…The DLS data reveal the size of hydrated PSS-coated colloids, while their functionality results from the hard cores inside the polyelectrolyte coating174345. The previously published reports1743 highlight hard-soft morphology of the colloids. The TEM image of the dried colloids presented in Fig.…”
Section: Resultsmentioning
confidence: 80%
“…Despite the proven clinical efficacy of Gd-DTPA, Gd-DOTA and other gadolinium-based molecular MRI agents, they suffer from dechelation and transmetallation processes taking place in the presence of chelating anions and endogenous cations, correspondingly1516. At the same time, luminescent function of lanthanide-containing optical labels is quenched in presence of organic background in the biological sample due to antennae-ligands replacement111718.…”
Polyelectrolyte-coated nanoparticles consisting of terbium and gadolinium complexes with calix[4]arene tetra-diketone ligand were first synthesized. The antenna effect of the ligand on Tb(III) green luminescence and the presence of water molecules in the coordination sphere of Gd(III) bring strong luminescent and magnetic performance to the core-shell nanoparticles. The size and the core-shell morphology of the colloids were studied using transmission electron microscopy and dynamic light scattering. The correlation between photophysical and magnetic properties of the nanoparticles and their core composition was highlighted. The core composition was optimized for the longitudinal relaxivity to be greater than that of the commercial magnetic resonance imaging (MRI) contrast agents together with high level of Tb(III)-centered luminescence. The tuning of both magnetic and luminescent output of nanoparticles is obtained via the simple variation of lanthanide chelates concentrations in the initial synthetic solution. The exposure of the pheochromocytoma 12 (PC 12) tumor cells and periphery human blood lymphocytes to nanoparticles results in negligible effect on cell viability, decreased platelet aggregation and bright coloring, indicating the nanoparticles as promising candidates for dual magneto-fluorescent bioimaging.
“…The aggregation of the PSS-stabilized ultra-small nanoparticles into the nanostructure is facilitated by counter-ion binding, since the PSS-based layer is enriched by sodium ions, which derive from the presence of sodium chloride in synthetic solution. The previously reported DLS results indicate that these nanostructures are very stable, which is evident from the stability of the size-values in time and under the dilution of the colloids 33 . Figure 3 TEM image of dried PSS-coated [Gd(TTA) 3 · 1 ] ( A ) and PSS-Na[Gd· 2 ] ( B ) colloids.…”
Today, nanostructure-based contrast agents (CA) are emerging in the field of magnetic resonance imaging (MRI). Their sensitivity is reported as greatly improved in comparison to commercially used chelate-based ones. The present work is aimed at revealing the factors governing the efficiency of longitudinal magnetic relaxivity (r1) in aqueous colloids of core-shell Gd(III)-based nanoparticles. We report for the first time on hydration number (q) of gadolinium(III) as a substantial factor in controlling r1 values of polyelectrolyte-stabilized nanoparticles built from water insoluble complexes of Gd(III). The use of specific complex structure enables to reveal the impact of the inner-sphere hydration number on both r1 values for the Gd(III)-based nanoparticles and the photophysical properties of their luminescent Tb(III) and Eu(III) counterparts. The low hydration of TTA-based Gd(III) complexes (q ≈ 1) agrees well with the poor relaxivity values (r1 = 2.82 mM−1s−1 and r2 = 3.95 mM−1s−1), while these values tend to increase substantially (r1 = 12.41 mM−1s−1, r2 = 14.36 mM−1s−1) for aqueous Gd(III)-based colloids, when macrocyclic 1,3-diketonate is applied as the ligand (q ≈ 3). The regularities obtained in this work are fundamental in understanding the efficiency of MRI probes in the fast growing field of nanoparticulate contrast agents.
“…The ongoing work to better understand the factors that control the formation of metal clusters should benefit the design of light emitting clusters, as well as refining the magnetic properties of such clusters. The ready functionalisation of the calixarene framework, as well as the many other different classes of these macrocycles that were not covered here [ 52 , 53 ], make for endless possibilities that will require careful and systematic design to achieve the best outcomes.…”
This review aims to provide an overview of recent examples of lanthanoid-calixarene complexes incorporated into light-emitting materials. Background information on the antenna effect and early work on lanthanoid complexes on calixarenes is provided to set the context. Classes of materials discussed include polymers, nanoparticles, and metal clusters.
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