Delépine Anne-Sophie, Tripier Raphaël, Handel Henri
UMR CNRS 6521, Chimie, Electrochimie Moléculaire et Analytique, Université de Bretagne Occidentale, C. S. 93837, 6 avenue Victor Le Gorgeu, 29238, Brest, Cedex 3, France.
Org Biomol Chem. 2008 May 21;6(10):1743-50. doi: 10.1039/b719514a. Epub 2008 Mar 26.
The behaviour of two cyclen-based bismacrocycles linked by aromatic spacers as receptors of adenosine monophosphate (AMP), adenosine diphosphate (ADP) and adenosine triphosphate (ATP) anions is explored. The two bismacrocycles differ from one another by the nature of their spacers, which are respectively 1,3-dimethylbenzene (BMC), or 2,6-dimethylpyridine (BPyC). Potentiometric investigations supported by (1)H and (31)P NMR measurements were performed over a wide pH range to characterize and understand the driving forces implicated in the supramolecular assemblies. A comparison is also carried out with the results presented in this work and those obtained previously with these two ligands and inorganic phosphates. The comparison exhibits the importance of pi-stacking capability of the organic anions in the binding and hydrogen-bonding network. For BPyC, NMR studies highlight two coordination schemes depending on the protonation of the nitrogen atom of the pyridinyl spacer, which acts in acidic media as a supplementary anchoring point.
研究了通过芳族间隔基连接的两个基于环烯的双大环化合物作为单磷酸腺苷（AMP）、二磷酸腺苷（ADP）和三磷酸腺苷（ATP）阴离子受体的行为。这两个双大环化合物因其间隔基的性质不同而有所差异，间隔基分别为1,3 - 二甲基苯（BMC）或2,6 - 二甲基吡啶（BPyC）。在较宽的pH范围内进行了由¹H和³¹P NMR测量支持的电位滴定研究，以表征和理解超分子组装中涉及的驱动力。还将本工作的结果与先前使用这两种配体和无机磷酸盐获得的结果进行了比较。比较结果显示了有机阴离子的π-堆积能力在结合和氢键网络中的重要性。对于BPyC，NMR研究突出了两种配位方案，这取决于吡啶基间隔基中氮原子的质子化情况，该氮原子在酸性介质中作为一个额外的锚定点。
