Yakimova Luidmila S, Ziganshin Marat A, Sidorov Vladimir A, Kovalev Vladimir V, Shokova Elvira A, Tafeenko Viktor A, Gorbatchuk Valery V
Institute of Chemistry, Kazan State University, Kremlevskaya 18, Kazan 420008, Russia.
J Phys Chem B. 2008 Dec 11;112(49):15569-75. doi: 10.1021/jp804277u.
The parameters of stability, guest binding reversibility, and Gibbs energy of guest inclusion were determined for clathrates of adamantylcalix[4]arene (1). These data provide a new insight into the structure-property relationships in vapor sensor applications of clathrate-forming hosts. A thin layer of 1, used in the quartz microbalance (QCM) sensor, demonstrates a selectivity for organic vapors, which depends on the regeneration technique after the guest binding. Complete regeneration of 1 on the sensor surface was reached through the exchange of bound guest with ethanol vapor, which forms an unstable clathrate with 1. The efficiency of the used regeneration technique was proved by comparing the QCM data with the isotherms of guest vapor sorption by guest-free host 1 and with the data of simultaneous thermogravimetry and differential scanning calorimetry for the saturated clathrates of 1. In sensor, the extent of host regeneration without guest exchange depends on the guest molecular structure. This extent, or guest-binding reversibility parameter, being determined in a combination with the sensor responses of completely regenerated 1 to guest vapors, increases the recognition capability of single sensor device. Using this technique, 13 of 15 studied guests were discriminated. The structural hints on the suitable sensor properties of 1 were found in the determined X-ray monocrystal data for clathrate of this host with toluene.
测定了金刚烷基杯[4]芳烃（1）包合物的稳定性参数、客体结合可逆性以及客体包合的吉布斯自由能。这些数据为包合物形成主体在蒸汽传感器应用中的结构-性质关系提供了新的见解。在石英微天平（QCM）传感器中使用的一层薄薄的1，对有机蒸汽表现出选择性，这取决于客体结合后的再生技术。通过用乙醇蒸汽交换结合的客体，在传感器表面实现了1的完全再生，乙醇蒸汽与1形成不稳定的包合物。通过将QCM数据与无客体主体1对客体蒸汽的吸附等温线以及1的饱和包合物的同步热重分析和差示扫描量热法数据进行比较，证明了所用再生技术的效率。在传感器中，无客体交换的主体再生程度取决于客体分子结构。该程度或客体结合可逆性参数，与完全再生的1对客体蒸汽的传感器响应相结合来确定，提高了单个传感器装置的识别能力。使用该技术，对15种研究客体中的13种进行了区分。在该主体与甲苯的包合物的X射线单晶数据中发现了关于1合适传感器性质的结构线索。
