Ion and pH Sensing with Colloidal Nanoparticles: Influence of Surface Charge on Sensing and Colloidal Properties

Ion sensors based on colloidal nanoparticles (NPs), either as actively ion‐sensing NPs or as nanoscale carrier systems for organic ion‐sensing fluorescent chelators typically require a charged surface in order to be colloidally stable. We demonstrate that this surface charge significantly impacts the ion binding and affects the read‐out. Sensor read‐out should be thus not determined by the bulk ion concentration, but by the local ion concentration in the nano‐environment of the NP surface. We present a conclusive model corroborated by experimental data that reproduces the strong distance‐dependence of the effect. The experimental data are based on the capability of tuning the distance of a pH‐sensitive fluorophore to the surface of NPs in the nanometer (nm) range. This in turn allows for modification of the effective acid dissociation constant value (its logarithmic form, pKa) of analyte‐sensitive fluorophores by tuning their distance to the underlying colloidal NPs. Tuning pH sensitivity: The charged surface of nanoparticles in colloidal solutions, shifts the original pH sensitivity range or so‐called pKa of the indicator molecule in a distance‐dependant manner. By using different length spacers for the conjugation, the distance between indicators and the nanoparticle can be adjusted, thus tuning the indicator's pH sensitivity (see figure).