Kazan Federal University, A.M. Butlerov Institute of Chemistry, Kremlevskaya, 18, 420008 Kazan, Russia.
Org Biomol Chem. 2013 Feb 28;11(8):1318-25. doi: 10.1039/c2ob27164h.
A new principle of quantitative and qualitative analysis of binary organic mixtures is offered, which is based on an ability of calixarene receptor for specific polymorphic transitions related to the composition of the analyzed guest mixture. The ability of tert-butylcalix[6]arene to remember selectively some guests bound from headspace both of pure liquids and their binary mixtures is used. The image of guest mixture remains written in metastable polymorphs of host after partial or complete guest elimination from clathrates. The memory was read using differential scanning calorimetry as the enthalpy of exothermic polymorphic transition of host collapse. This enthalpy monotonously changes with the variation of guests' ratio in mixture, unlike the enthalpies of endothermic pseudopolymorphic transitions of guest release. So, the composition of volatile binary mixture can be estimated using only one receptor and only one its parameter even in absence of preferential binding from a binary mixture of guests. This is an example of a genuine molecular recognition.
提出了一种用于分析二元有机混合物的定量和定性分析的新原理，该原理基于杯芳烃受体对与被分析客体混合物组成有关的特定多态转变的能力。利用叔丁基杯[6]芳烃从纯液体及其二元混合物的顶空选择性地记忆某些客体的能力。客体混合物的图像在客体从主体笼合物中部分或完全除去后以主体不稳定多态的形式保留。通过差示扫描量热法作为主体崩塌的放热多态转变的焓来读取记忆，该焓与客体释放的吸热假多态转变的焓不同，随混合物中客体比例的变化而单调变化。因此，即使没有二元客体混合物的优先结合，也可以仅使用一种受体和一种其参数来估计挥发性二元混合物的组成。这是真正的分子识别的一个例子。
