Ionophore-Based SERS Sensing for Electrolyte Cations

We present here a surface-enhanced Raman spectroscopy (SERS)-based platform for selectively detecting electrolyte cations. This platform facilitates the reorientation of the chromoionophore I (CHI) molecule positioned on the surface of silver nanoparticles, regulated by the targeted electrolyte cation within the ionophore-based ion-selective sensing framework. When exposed to the target ions, leading to deprotonation, the aromatic plane of the CHI molecule shifts from an endwise to an edgewise configuration on the SERS substrate surface. This reorientation improves the coupling of the induced dipole within the molecule and the induced electromagnetic field normal to the surface, leading to a heightened and more discernible SERS signal. Additionally, NMR data revealed a protonation-dependent conformational change in the CHI molecules. Upon protonation, the side chain of the CHI molecule extends away from its aromatic ring, whereas upon deprotonation, the carbon chain folds back and closely approaches the edge of the aromatic plane, further confirming this conclusion. Using Ca2+ and Na+ as examples, this method shows a detection limit of 0.1 μM for Ca2+ and 1 μM for Na+ with high selectivity. The successful application of the versatile and rapidly advancing SERS technique for electrolyte cation detection shows a promising pathway for enhancing current ion detection capabilities. As a preliminary demonstration, the total Ca2+ concentration in undiluted human serum was successfully determined, with common matrix interference effectively circumvented.