METALLOPORPHYRINS, SPIN AND FULLERENES

描述：（改编自申请人的摘要）本项目探讨了 卟啉和富勒烯的基本化学性质， 发现新的化学，支持分子水平的理解， 生物学和医学。它关注铁的自旋状态，弱相互作用 金属和配体之间的关系，超分子化学和C60的新反应性。 具体的目标包括寻找“失踪”的纯S = 3/2自旋态， 铁卟啉及其配位场反转的研究 OH-和H2O的强度顺序在新的“磁化学系列”与 熟悉的光谱化学系列。超结构金属卟啉， 上升到第一个不溶性复合物的烷烃，将被用来调查 氙的潜在络合物。富勒烯阳离子化学将被探索， 开发富勒烯离子作为C60的清洁单官能化的碳离子。 富勒烯离子的弱的、不稳定的二聚假说，例如形成 [（C60）2]-和[（C60）2]2-，将通过构建 单体和二聚富勒烯部分的超分子陷阱。自我 组装金属卟啉立方体和盒子已经被设计成封装 C60、C70和（C60）2以及它们各自的富勒烯阴离子。阳离子C60 钌和锇的络合物正在制备用于生物测试， 抗病毒和抗癌药物。泛函的结构表征 细胞色素氧化酶的血红素α 3/CuB活性位点的模型将被追求。 所有这些研究的重点将放在确定性的 通过X射线晶体学表征分析纯材料， 电化学方法和各种光谱方法（NMR，IR， 电子光谱学，包括NIR、穆斯堡尔、共振拉曼等）。一个 对这一基本生物无机化学的理解， 治疗金属蛋白紊乱（地中海贫血、镰状贫血）的方法 细胞性贫血等）。富勒烯具有潜在的应用， 放射性药物、抗病毒药物、抗癌药物、光动力疗法 药物和MRI药物。

DESCRIPTION: (adapted from applicant's abstract) This project explores the fundamental chemical properties of porphyrins and fullerenes with the goal of discovering new chemistry that underpins the molecular level understanding of biology and medicine. It focuses on the spin states of iron, weak interactions between metals and ligands, supramolecular chemistry and new reactivity of C60. The specific aims include a search for the 'missing' pure S = 3/2 spin state of iron(III) porphyrins and an investigation into the reversal of ligand field strength order of OH- and H2O in the new "Magnetochemical Series" versus the familiar Spectrochemical Series. A superstructured metalloporphyrin, that gave rise to the first insoluble complex of an alkane, will be used to investigate potential complexes of xenon. Fullerene cation chemistry will be explored to develop fullerenium ions as synthons for clean monofunctionalization of C60. The weak, labile dimerization hypothesis for fulleride ions, e.g. the formation of [(C60)2]- and [(C60)2]2-, will be tested by the construction of supramolecular traps for monomeric and dimeric fullerene moieties. Self assembling metalloporphyrin cubes and boxes have been designed to encapsulate C60, C70 and (C60)2 and their respective fulleride anions. Cationic C60 complexes of ruthenium and osmium are being prepared for biological testing as anti-viral and anti-cancer drugs. The structural characterization of functional models for the heme a3/CuB active site of cytochrome oxidase will be pursued. Emphasis in all of these studies will be placed on the definitive characterization of analytically pure materials by X-ray crystallography, electrochemical methods and a variety of spectroscopic methods (NMR, IR, electronic spectroscopy including NIR, Mossbauer, resonance Raman, etc). An understanding of this fundamental bioinorganic chemistry must underlie medical approaches to the therapy of metalloprotein disorders (thalassemias, sickle cell anemia, etc). Fullerenes have potential applications as radiopharmaceuticals, anti-virals, anti-cancer drugs, photodynamic therapy agents and as MRI agents.