ABSTRACT

The inclusion of 7-diethylamino-coumarin derivatives, bearing an ethyl acetoacetate (CAM1) and a methyl β-ketodithioester moiety (CAM2) in the cavity of cucurbit[7]uril (CB7), leads to different interaction forms with mercuric ions (Hg²⁺).

The interaction between these ions and CAM1, in the presence of CB7, occurs through the lateral ethyl acetoacetate moiety of the keto form of CAM1, leading to the formation of binary assemblies such as Hg²⁺@CAM1 and Hg²⁺@CB7. As a consequence, the metal restricts the insertion of the dye into the CB7 cavity, decreasing the apparent binding constant between them.

Interestingly, for the other derivative CAM2, a mercury-induced desulfurisation reaction of its β-ketodithioester moiety is kinetically accelerated by CB7 (by a factor ≈25), which subsequently leads to the generation of binary and ternary complexes among the analogue oxygenised from CAM2, metal and CB7.

The later effect is a promising strategy that could be considered for the mercury sensing methodology.

摘要

在葫芦[7]尿素（CB7）的空腔中包含带有乙酰乙酸乙酯（CAM1）和甲基β-酮二硫酯部分（CAM2）的7-二乙氨基香豆素衍生物，导致与汞离子（Hg）的相互作用形式不同²⁺）。

在存在CB7的情况下，这些离子与CAM1之间的相互作用是通过CAM1的酮形式的侧乙酰乙酸乙酯部分发生的，从而导致形成二元组装体，例如Hg ²⁺ @ CAM1和Hg ²⁺ @ CB7。结果，金属限制了染料向CB7腔中的插入，从而降低了它们之间的表观结合常数。

有趣的是，对于其他衍生物CAM2，其β-酮二硫酯部分的汞诱导的脱硫反应被CB7动力学加速（约≈25），随后导致在从CAM2氧化的类似物中生成二元和三元络合物。，金属和CB7。

后来的影响是一种有前途的策略，可以将其用于汞感测方法。