RESUMO
Mixed monolayer-protected gold nanoparticles containing surface-bound triethylene glycol and dipicolylamine groups aggregated in water/methanol, 1 : 2 (v/v) in the presence of nucleotides, if the solution also contained zinc(ii) nitrate to convert the dipicolylamine units into the corresponding zinc complexes. Nanoparticle aggregation could be followed with the naked eye by the colour change of the solution from red to purple followed by nanoparticle precipitation. The sensitivity was highest for adenosine triphosphate (ATP), which could be detected at concentrations >10 µM, and decreased over adenosine diphosphate (ADP) to adenosine monophosphate (AMP), consistent with the typically higher affinity of zinc(ii)-dipicolylamine-derived receptors for higher charged nucleotides. Inorganic sodium diphosphate and triphosphate interfered in the assay by also inducing nanoparticle aggregation. However, while the nucleotide-induced aggregates persisted even at higher analyte concentrations, the nanoparticles that were precipitated with inorganic salts redissolved again when the salt concentration was increased. The thus resulting solutions retained their ability to respond to nucleotides, but they now preferentially responded to AMP. Accordingly, AMP could be sensed selectively at concentrations ≥50 µM in an aqueous environment, even in the presence of other nucleotides and inorganic anions. This work thus introduces a novel approach for the sensing of a nucleotide that is often the most difficult analyte to detect with other assays.
Assuntos
Difosfato de AdenosinaRESUMO
Gold nanoparticles covered with a mixture of ligands of which one type contains solubilizing triethylene glycol residues and the other peripheral zinc(II)-dipicolylamine (DPA) complexes allowed the optical detection of hydrogenphosphate, diphosphate, and triphosphate anions in water/methanol 1:2 (v/v). These anions caused the bright red solutions of the nanoparticles to change their color because of nanoparticle aggregation followed by precipitation, whereas halides or oxoanions such as sulfate, nitrate, or carbonate produced no effect. The sensitivity of phosphate sensing depended on the nature of the anion, with diphosphate and triphosphate inducing visual changes at significantly lower concentrations than hydrogenphosphate. In addition, the sensing sensitivity was also affected by the ratio of the ligands on the nanoparticle surface, decreasing as the number of immobilized zinc(II)-dipicolylamine groups increased. A nanoparticle containing a 9:1 ratio of the solubilizing and the anion-binding ligand showed a color change at diphosphate and triphosphate concentrations as low as 10 µmol/L, for example, and precipitated at slightly higher concentrations. Hydrogenphosphate induced a nanoparticle precipitation only at a concentration of ca. 400 µmol/L, at which the precipitates formed in the presence of diphosphates and triphosphates redissolved. A nanoparticle containing fewer binding sites was more sensitive, while increasing the relative number of zinc(II)-dipicolylamine complexes beyond 25% had a negative impact on the limit of detection and the optical response. Transmission electron microscopy provided evidence that the changes of the nanoparticle properties observed in the presence of the phosphates were due to a nanoparticle crosslinking, consistent with the preferred binding mode of zinc(II)-dipicolylamine complexes with phosphate anions which involves binding of the anion between two metal centers. This work thus provided information on how the behavior of mixed monolayer-protected gold nanoparticles is affected by multivalent interactions, at the same time introducing a method to assess whether certain biologically relevant anions are present in an aqueous solution within a specific concentration range.
RESUMO
The interaction of cyclopeptides bound to the surface of mixed monolayer-protected gold nanoparticles with sulfate anions causes the crosslinking and concomitant precipitation of the nanoparticles from aqueous solutions even in presence of an excess of competing anions, thus allowing the naked eye detection of sulfate in water.
