Determination of adenosine triphosphate based on the use of fluorescent terbium(III) organic frameworks and aptamer modified gold nanoparticles.

A thiol-labeled adenosine triphosphate (ATP) binding aptamer is covalently linked on the surface of gold nanoparticles (AuNPs). This warrants protection of the red AuNPs from aggregation in high salt condition. The dispersed AuNPs can quench the fluorescence of the Tb(III)-MOFs at 547 nm with the excitation wavelength of 290 nm. This is ascribed to the combined action of inner filter effect, dynamic quenching and fluorescence resonance energy transfer. If the aptamer binds ATP to form folded structures, the AuNPs aggregate in high salt medium and the green fluorescence of the Tb(III)-MOFs is recovered. This method shows good sensitivity and selectivity for ATP, and the linear range is from 0.5 to 10 μM of ATP with the detection limitat of 0.32 μM. It was applied to the determination of ATP in (spiked) human plasma with satisfactory recoveries (from 93.2% to 106.3%). Oppositely, when the unlabeled aptamer is used instead of thiol-labeled aptamer in this process, the ATP-aptamer complexes rather than unlabeled aptamer provide greater protection for AuNPs against salt-induced aggregation. It is found that when the aptamer covalently binds to AuNPs, the steric hindrance is dominant for the stabilization of AuNPs; for unlabeled aptamer, the electrostatic repulsion is responsible for their stability, irrespective of whether ATP is present or not. These two different forces lead to the aggregation or dispersion of AuNPs with addition of target in salt solution. Graphical abstractThe impact of two repulsive forces (electrostatic repulsion and steric repulsion) on the stabilization of gold nanoparticles, and its application in fluorescent terbium metal-organic frameworks as a nanoprobe for adenosine triphosphate.