SYNTHETIC PROBES OF HEME AND CHLOROPHYLL BIOCHEMISTRY

血红素和叶绿素生物化学的合成探针

• 批准号: 3280388
• 负责人: ANDREW D HAMILTON
• 金额: $ 13.37万
• 依托单位: UNIVERSITY OF PITTSBURGH AT PITTSBURGH
• 依托单位国家: 美国
• 财政年份: 1988
• 资助国家: 美国
• 起止时间: 1988-08-01 至 1990-07-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/3280388
• 关键词: binding proteins; chemical models; chemical structure function; chlorin; chlorophyll; chromophore; dimer; electrochemistry; electron transport; enzyme model; fluorescence; heme; microorganism metabolism; photosynthesis; porphyrins; tetrapyrroles

This proposal concerns the preparation and study of synthetic models of heme- and chlorophyll- containing proteins. In particular, we plan to investigate the role of specifically ordered aggregates to tetrapyrroles in such key biological processes as photosynthesis and electron transfer. We have developed a new strategy for the construction of covalently-linked multiple tetrapyrroles with different distances and orientations between the rings. In this application we propose to extend this approach to model more closely the structure of multiple tetrapyrrole sites in biology. Our primary targets are tetrameric and hexameric analogs of the known structure of bacterial photosynthetic reaction centers. These models will, respectively, contain the dimer-bis(monomer) and dimer-bis(monomer)-bis(non-metallated monomer) structure of the reaction centers. By varying the synthesis used we will be able to generate a series of compounds with different although related structures. Thorough physical investigation of these derivatives, using electrochemical, fluoresence and picosecond optical techniques, will provide details of the photoinduced electron transfer and charge separation processes occurring between the pigments. This will allow us, for the first time to probe the effect of chromophore distance and orientation on key aspects of the photosynthetic process. We will also construct simple linear arrays of photoactive redox partners as comparisons to the biomimetic models. In later model compounds we will introduce chlorin and bacteriochlorin macrocycles in place of the porphyrin building blocks. Model studies of this type will lead to an understanding of protein control of reactivity that is crucial for solving the medical problems associated with tetrapyrrole biochemistry.

该建议涉及合成的准备和研究 血红素和叶绿素含有蛋白质的模型。 在 特别是，我们计划调查特定有序的作用 在此类关键生物学过程中汇总到四吡咯的聚集 光合作用和电子传输。 我们已经开发了一个新的 建造共价链接的策略 具有不同距离和方向的四吡咯 戒指。 在此应用程序中，我们建议扩展这种方法 更仔细地模拟多个四吡咯部位的结构 在生物学中。 我们的主要目标是四聚体和六聚体类似物 细菌光合反应中心的已知结构。 这些模型将分别包含二聚体双（单体） 和二聚体 - 双（单体）-BIS（非符号单体）结构 反应中心。 通过改变所使用的合成我们将是 能够生成一系列具有不同的化合物 相关结构。 对这些的彻底调查 衍生物，使用电化学，荧光和皮秒 光学技术将提供照片诱导的详细信息 电子转移和电荷分离过程发生 在颜料之间。 这将使我们第一次 探测发色团距离和方向对钥匙的影响 光合过程的各个方面。 我们还将构建 简单的光活动氧化还原合作伙伴的线性阵列作为比较 到仿生模型。 在以后的型号化合物中，我们将 引入氯蛋白和细菌蛋白大环代替 卟啉构建块。 这种类型的模型研究将导致 了解至关重要的反应性蛋白质控制 解决与四吡咯有关的医疗问题 生物化学。