Supramolecular Porphyrin Based Catalysts and Sensors

目前的研究方向是设计非共价连接的超分子卟啉配合物，用于模拟细胞色素c氧化酶活性位点上双氧的四电子催化还原成水，并开发新的高效的双氧检测电化学传感器。为此，我们提出设计、合成和研究离子对卟啉二聚体以及含钴卟啉的环糊精缩合聚合物膜的超分子配合物。用离子对卟啉二聚体修饰的电极作为细胞色素c氧化酶活性位点的模型，在生理pH条件下直接将二氧还原为水。利用在外围取代基上带不同电荷的水溶性卟啉，可以制备Co-Co、Fe-Fe或Mn-Mn等同核卟啉二聚体。平面或非平面环的卟啉可以用来调节二聚体的环间距离。用含钴卟啉的环糊精缩合聚合物膜的超分子络合物修饰电极，设计用于测定溶液中二氧的传感器。无论是中性环糊精聚合物还是阴离子，即羧基甲基化环糊精聚合物，薄膜修饰电极都将被设计和制造，以承载在环外围携带中性、阴离子或阳离子电荷的钴卟啉。通过使用各种电分析和光谱技术，首先，我们将集中在基本的，例如，研究过程的机械和动力学方面。用离子对二聚体和环糊精的超分子配合物修饰的常规微电极随后将被制备。然后，将对这些电极进行专用应用测试。

The present research proposal is focused on designing non-covalently linked supramolecular porphyrin complexes suitable for mimicking the four-electron catalytic reduction of dioxygen to water at the active site of cytochrome c oxidase, and, also to develop new and efficient electrochemical sensors for dioxygen detection. Towards this goal, we propose to design, synthesize, and study ion-pair porphyrin dimers as well as supramolecular complexes of condensation polymer films of cyclodextrins hosting cobaltporphyrins. The electrodes modified with ion-pair porphyrin dimers are targeted as models for the active site of cytochrome c oxidase to perform a direct four-electron reduction of dioxygen to water at physiological pH conditions. Homonuclear porphyrin dimers, such as Co-Co, Fe-Fe or Mn-Mn will be prepared by using water soluble porphyrins bearing different charges on peripheral substituents. Either porphyrin of planar or non-planar rings will be utilized to adjust the inter-ring distance of a dimer. The electrodes modified with supramolecular complexes of condensation polymer films of cyclodextrin hosting cobaltporphyrins will be designed to serve as sensors for determination of dioxygen in solution. Both the neutral cyclodextrin polymer or anionic, i.e., carboxymethylated cyclodextrin polymer, film modified electrodes will be designed and fabricated to host cobaltporphyrins bearing either neutral, anionic or cationic charges on the ring periphery. By using various electroanalytical and spectroscopic techniques, first, we will focus on fundamental, e.g., mechanistic and kinetic aspects of the studied process. Conventional microelectrodes modified with supramolecular complexes of ion-pair dimers and cyclodextrins will subsequently be fabricated. Then, these electrodes will be tested for dedicated applications.