Thermodynamic equilibrium studies using model systems were carried out on the nature and extent of coordination of twelve different biogenic amines and adenosine-5'-triphosphate (ATP) with the bivalent metal ions, viz., Ca2+ and Zn2+, which occur in the subcellular fractions of the brain, at 25.0 +/- 0.1 degrees C and at an ionic strength of 1.0 (KNO3). In the combined presence of the individual monoamines and ATP the metal ions were predominantly coordinated by ATP in the pH range 3.0 to 6.5 with binding constants (log KML) of 2.84 +/- 0.06 and 3.19 +/- 0.39 for the Ca2+ and Zn2+ chelates, respectively. Each of the monoamines coordinated with the metal-ATP chelate above pH 6. The stabilities of the chelates of some of the amines with Ca2+ -ATP (1:1) system were NE, 2.33 +/- 0.33; AA, 2.24 +/- 0.19; OA, 1.94 +/- 0.29; NMeN, 1.60 +/- 0.22; DA, 2.14 +/- 0.09. Values for the Zn2+-ATP-amine systems were: NE, 8.35 +/- 0.26; OA, 4.53 +/- 0.07; DA, 10.05 +/- 0.39. Absorption spectral studies were carried out in order to examine the nature of coordination of NE, DA, TA, and AA with Cu2+, Fe2+, and Mg2+ ions in the combined presence of ATP. Results of the spectral studies taken together with the (thermodynamic) equilibrium data have indicated that in the pH range of biological interest, the catechol amines (NE and DA) and ATP are both coordinated to the "synaptosomal and vesicular" metal ions. The results further indicated that both the pyrocatechol and the ethanolamine groups of NE might be involved in the coordination of Cu2+. However, the interaction of the ethanolamine group of the NE molecule with the rest of the metal ions was not indicated.