J-聚集体生成中阴离子菁与外加盐反离子相互作用的量热瘀电化学活度测量

用量热和反离子活度测量法研究了阴离子菁(Ⅰ)在DMF-水(35%DMF, V/V)中生成J-聚集体时, 染料与外加盐反离子之间的相互作用。当外加盐为CdCl_2或LaCl_3时, 由量热曲线获得J-聚集焓△H_9, 分别为-42.6, -42.0 kJ·mol~(-1), 染料(Ⅰ)束缚的Cd~(2+), La~(3+)量与染料量之比分别为0.48:1和0.31:1。由反离子活度的电化学活度测量获得束缚的Cd~(2+)离子量与染料量之比为0.47:1, 这些结果表明J-聚集体中, 染料与其反离子形成了盐型的总体。

Calorimetric and Electrochemical Activity Measurement on the Interaction Between Anionic Cyanine Dye and Its Counterions in J-Aggregate Formation

In DMF-H_2O(35%DMF, V/V) solution,the interaction between an anionic cyanine dye, 3,3'-di-(γ-sulfoProPyl)-9-ethyl-4, 5,4', 5'-dinaphthothis-carbocyanine triethylamine salt (Ⅰ) and its counterions, which induced J-aggregate formation, was studied by calorimetric and counterion activity measurement method. From calorimetric diagram,it was found,when CdCl_2 and LaCl_3 were added,J-aggregation enthalpy, △H_s, were -42.6, -42.0 kJ·mol~(-1) and the ratios of bounded counterions to the dye (Ⅰ) J-aggregate were 0.48:1, 0.31:1, respectively. It was also obtained from counterion activety measurement that the ratio of bounded Cd~(2+) to dye II) J-aggregase was 0.47:1. Such results indicated that dye (I) and counterions had formed a salt-like totality in the J-aggregate.