2,6-二氨基吡啶衍生物作为过渡金属离子荧光探针的研究

2,6-二氨基吡啶(DAPD)衍生物都有较强的荧光。除DMHND(2,4-二甲基-7-羟基-1,8-萘啶)外，2,4-二甲基-7-胺基-1,8-萘啶(DMAND)和2,4-二甲基-7-丙烯酰胺基-1,8-萘啶(DMAAN)在加入过渡金属离子后，荧光强度增强，发射光谱红移，可以作为过渡金属离子的荧光探针。根据Irving-Williams顺序，以过渡金属中络合能力较强的Cu2+为代表，求算了DMAND和DMAAN与Cu2+的结合比，通过非线性拟合计算了结合常数，比较了它们与金属离子结合的强弱，DMAND较DMAAN为更灵敏的过渡金属离子荧光探针。

Study of Derivatives of 2,6 -Diaminopyridine as Fluorescence Probe of Transition Metal Ions

Three derivatives of 2, 6-diaminopyridine were synthesized with naphthyridine ring and -NH2, -OH and -NHCOCHCH2 groups. They are 2, 4-dimethyl-7-hydroxyl-1, 8-naphthyridine (DMHND), 2, 4-Dimethyl-7-amino-1, 8-naphthyridine (DMAND) and DMAAN. The binding ability of the derivatives of 2, 6-diaminopyridine for metal ions in acetonitrile was investigated using UV-Vis and fluorescence spectrometry. The changes of the dyes spectra were observed in the presence of transition metal ions, but were not observed in the presence of K+ , Na+ , Mg2+ , Ca2+ and Pd2+. Except for DMHND that has weak binding ability for Cu2+, two dyes can bind with Cu2+ at the ratios of DMAAN : Cu2+ = 1 : 1, DMAND : Cu2+ = 1 : 1. The resulting binding curves were analyzed by nonlinear regression methods, giving the association constant for DMAAN to be about 4.4 x 10(5) L x mol(-1), and about 6.3 x 10(6) L x mol(-1) for DMAND. DMAND contains an electron-donating group (amino group) conjugated to an electron-withdrawing group (the pyridine ring), and undergoes intramolecular charge transfer from the donor to the acceptor upon excitation by light. When Cu2+ interacting with the N of the pyridine ring enhances the electron-withdrawing character of this group, the spectrum is thus red-shifted and the intensity is increased. DMAND displayed a high sensitivity among the three derivatives of 2, 6-diaminopyridine as the fluorescence probe of transition metal ions.