Supramolecular Porphyrin Based Catalysts and Sensors

超分子卟啉基催化剂和传感器

• 批准号: 6357547
• 负责人: FRANCIS D'SOUZA
• 金额: $ 14.32万
• 依托单位: WICHITA STATE UNIVERSITY
• 依托单位国家: 美国
• 财政年份: 2001
• 资助国家: 美国
• 起止时间: 2001-07-01 至 2004-06-30
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/6357547
• 关键词: active sites; biomimetics; biosensor device; biotechnology; catalyst; chemical synthesis; cyclodextrins; cytochrome oxidase; dimer; electrochemistry; electrodes; metalloporphyrins; microelectrodes; oxidation reduction reaction; polymers; water solubility

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.

本研究旨在设计非共价键连接的超分子卟啉配合物，模拟细胞色素c氧化酶活性位点上的四电子催化还原反应，并开发新型高效的电化学传感器。为了实现这一目标，我们建议设计，合成和研究离子对卟啉二聚体以及超分子复合物的环糊精的缩聚物膜托管钴卟啉。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条件下进行直接四电子还原。利用水溶性卟啉配体的外围取代基上带有不同的电荷，可以制备钴-钴、铁-铁或锰-锰等均卟啉二聚体。平面或非平面环的卟啉将用于调节二聚体的环间距离。环糊精与钴卟啉的缩聚物膜的超分子复合物修饰的电极将被设计作为传感器，用于测定溶液中的分子氧。中性环糊精聚合物或阴离子，即，羧甲基化环糊精聚合物，膜修饰电极将被设计和制造，以容纳在环周边上带有中性、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，我们将专注于基本的，例如，研究过程的机械和动力学方面。传统的微电极改性的离子对二聚体和环糊精的超分子复合物将随后制造。然后，这些电极将被测试用于专用应用。

项目成果

Fluorophore(s) appended fullerene dyads and triads for probing photoinduced energy transfer: syntheses, electronic structure, and fluorescence studies.

荧光团附加富勒烯二元组和三元组，用于探测光诱导能量转移：合成、电子结构和荧光研究。

• DOI: 10.1007/s11120-005-5450-z
• 发表时间: 2006
• 期刊: Photosynthesis research
• 影响因子: 3.7
• 作者: Deviprasad,GollapalliR;Smith,PhillipM;Zandler,MelvinE;Rogers,LisaM;D'Souza,Francis
• 通讯作者: D'Souza,Francis

Binding, electrochemical activation, and cleavage of DNA by cobalt(II) tetrakis-N-methylpyridyl porphyrin and its beta-pyrrole brominated derivative.

• DOI: 10.1021/bc060153x
• 发表时间: 2006-11
• 期刊: Bioconjugate chemistry
• 影响因子: 4.7
• 作者: S. Yellappa;J. Seetharamappa;Lisa M. Rogers;R. Chitta;R. Singhal;F. D’Souza