Alkali Metal Ion Sensing in Aqueous Media by a Dibenzo-16-crown-5 Chromoionophore

A new chromoionophore sym-(decyl)(2-hydroxy-5-nitrobenzyloxy)-dibenzo-16-crown-5 (1) has been synthesized for $Na^+$ photometry in aqueous media. Apparent $pK_a$ values of 1 in the presence of 0.10 M LiCl, NaCl, and KCl were measured by spectrophotometry in 50% 1,4-dioxane-50% water (v/v) and compared with the $pK_a$ of 8.68 in the presence of 0.10 M TMACl. A significant $pK_a$ shift to a lower pH was only observed for $Na^+$ (${\Delta}pH=1.31$) due to selective binding of 1 with $Na^+$. Based upon this $pK_a$ shift, chromoionophore 1 was found to selectively respond to $Na^+$ with a detection limit of $10^{-3}M$ and no interference from $K^+$ up to 0.05 M for detection of 10.0 mM $Na^+$ in 50% 1,4-dioxane-50% water (v/v).