Two redox-active crown ethers, (1,1'- bi-2-naphthyl)-23-crown-6 incorporating 9,10-anthraquinone (BNAQ) and 1,4-benzoquinone (BNBQ), were synthesized and employed in the selective binding of NH(4)(+) over K(+). Their applications to NH(4)(+) detection were studied by cyclic voltammetry and amperometry in aqueous media. The results showed that the magnitude of the quinone redox peak decreased linearly as the concentration of NH(4)(+) increased, indicating the formation of BNAQ-NH(4)(+) and BNBQ-NH(4)(+) complexes. Formation constants of BNAQ-NH(4)(+) and BNBQ-NH(4)(+) complexes were determined to be 4.3 x 10(3) and 4.0 x 10(3) M(-1), respectively, which were 2 orders of the magnitude greater than those of BNAQ-K(+) and BNBQ-K(+) complexes. The (1)H NMR titration method carried out in DMSO-d(6) showed that both complexes possessed 1:1 stoichiometry, and association constants were determined to be 648 +/- 35 and 600 +/- 47 M(-1) for BNAQ-NH(4)(+) and BNBQ-NH(4)(+), respectively. Interference effects from other alkali and alkaline earth metal ions in the analysis of NH(4)(+) were also investigated. The BNAQ-modified sensor showed a linear response from 1.0 microM to 1.0 mM for NH(4)(+), and the detection limit was determined to be 0.9 +/- 0.03 microM.