Selective Lanthanide Sensing with Gold Nanoparticles and Hydroxypyridinone Chelators

Abstract

The octadentate hydroxypyridinone chelator 3,4,3-LI(1,2-HOPO) is a promising therapeutic agent because of its high affinity for f-block elements and noncytotoxicity at medical dosages. The interaction between 3,4,3-LI(1,2-HOPO) and other biomedically relevant metals such as gold, however, has not been explored. Gold nanoparticles functionalized with chelators have demonstrated great potential in theranostics, yet thus far, no protocol that combines 3,4,3-LI(1,2-HOPO) and colloidal gold has been developed. Here, we characterize the solution thermodynamic properties of the complexes formed between 3,4,3-LI(1,2-HOPO) and Au 3+ ions and demonstrate how under specific pH conditions the chelator promotes the growth of gold nanoparticles, acting as both reducing and stabilizing agent. 3,4,3-LI(1,2-HOPO) ligands on the nanoparticle surface remain active and selective toward f-block elements, as evidenced by gold nanoparticle selective aggregation. Finally, a new colorimetric assay capable of reaching the detection levels necessary for the quantification of lanthanides in waste from industrial processes is developed based on the inhibition of particle growth by lanthanides.

Single Excited Dual Band Luminescent Hybrid Carbon Dots-Terbium Chelate Nanothermometer

“…Among luminescent nanomaterials, photoluminescent carbon dots (CDs) have emerged as important materials in sensing and cell imaging [23,24] since the high surface charge of CDs results from the nature of the hydrophilic exterior layer and is predominantly constituted by chelating anions. This is the reason for its high affinity to counter-ions, including metal ions [25,26]. This is the reason for using CDs as effective optical sensors [27][28][29], although the sensitivity of CDs to any changes in their counter-ion environment restricts their applicability in accurate intracellular thermal sensing [30].…”

Efficient discrimination of transplutonium actinides by in vivo models

“…17 In order to overcome the limitations of DTPA salts as decorporation agents, the octadentate hydroxypyridinonebased chelator 3,4,3-LI(1,2-HOPO) was developed. 18 This synthetic chelating molecule shows high binding affinity for actinides and lanthanides, 19,20 selectivity for f-block elements over biologically-relevant cations, 21,22 formation of excretable complexes with these elements, 23 and biocompatibility at therapeutic dosages. 23 In vivo studies have demonstrated the superior decorporation performance of 3,4,3-LI(1,2-HOPO) for multiple elements, including U(VI), Np(V), and Pu(IV), when compared to DTPA and other chelating agents.…”

Development of a Flexible Tripodal Hydroxypyridinone Ligand with Cyclohexane Framework: Complexation, Solution Thermodynamics, Spectroscopic and DFT Studies

“…The detection of lanthanides in industrial waste by novel colorimetric assay was achieved by inhibition of gold nanoparticle selective aggregation by LI(1,2-HOPO) was described. [15] The starting elements of lanthanide series, e. g., lanthanum has eight coordination number, the terminal lanthanides such as Lu has nine, whereas the midrange lanthanides like Gd have equilibrium coordination between eight and nine coordination number. The first ligand developed by Raymond et.…”