Complexation of neurotransmitters ‒ dopamine, serotonin and melatonin ‒ with a DTPA-based cyclophane of high rigidity: 1H NMR shift and line-broadening

AbstractThe 1H NMR signals of the titled neurotransmitters undergo up-field shift accompanied by line-broadening in NMR titration with the DTPA-based cyclophane at pD 7.3; the cyclophane consists of a 4,4′-bis(1,1′-biphenyl-4,4′-dihydroxy)dianiline unit cyclised by a DTPA (diethylenetriaminepentaacetate) group through two amide linkages. Changes in chemical shifts of dopamine indicate the formation of a 1:1 complex with the formation constant K1 400 M−1; the complex of serotonin is likely to form a 2:1 host‒guest complex with β2 ≈ 105 M−2; melatonin does not form a complex with definite stoichiometry. The primary binding forces in the dopamine and serotonin complexes are electrostatic interaction between cationic neurotransmitter and anionic cyclophane molecules, and the resulting ionic pairs are stabilised by encapsulation. The electrostatic interaction is weakened by electrolytes; in 0.1 M Trizma buffer, dopamine does not yield a definite complex, and serotonin forms a 1:1 complex with K1 80 M−1. Extrem...