X-Ray and Chemical Studies of Metalloporphyrins

描述（由申请人提供）：提出了多种新型金属卟啉化合物的合成和表征。这项工作将强调，但不限于，铁卟啉衍生物。大多数拟研究的化合物类别都与血红蛋白衍生物有关，这些衍生物具有广泛的生物学功能，包括氧利用、储存和运输、一氧化氮信号传导、电子传递、药物代谢和其他酶促过程。三维x射线晶体结构测定方法将应用于确定金属卟啉立体化学的分子结构和各个细节方面。核共振振动光谱（NRVS）新技术正被用于确定生物分子中的铁动力学。NRVS方法允许观察所有有铁运动的振动模型。NRVS已经获得了其他任何技术都无法获得的有趣的振动数据，包括六坐标咪唑连接的CO衍生物的Fe-Im模式的检测。这将使我们了解蛋白质环境如何改变铁动力学，从而改变反应模式。其他适当应用的方法包括通过体温相关磁化率和电子顺磁共振（EPR）测量、穆斯堡尔、振动和紫外可见光谱以及电化学性质来表征磁性。从最广泛的角度来看，研究目标是实现金属卟啉的结构和物理性质的合成，特别是因为这些关系与理解基于血红蛋白的生物过程有关。研究铁卟啉酸盐包括一些六坐标衍生物，[Fe(Por)(XO)(Im)] (XO = O2， CO， NO)，以研究Fe-Im振动随对配体变化的变化，这对于理解血红蛋白氧结合协同性的问题很重要。其他项目包括高自旋五配位铁（II）的结构和电子结构的详细研究，附加的亚硝基配合物，细胞色素b和c的合成类似物，以显示轴向配体取向如何影响它们的电子结构和氧化还原性能。

DESCRIPTION (provided by applicant): The synthesis and characterization of a variety of new metalloporphyrin compounds is proposed. The work will emphasize, but will not be limited to, iron porphyrinate derivatives. Most classes of compounds proposed for study are related to hemoprotein derivatives, which carry out a wide range of biological functions including oxygen utilization, storage and transport, NO-based signaling, electron transport, drug metabolism and other enzymatic processes. The methods of three-dimensional X-ray crystal structure determination will be applied to define molecular structures and various detailed aspects of metalloporphyrin stereochemistry. The new technique of nuclear resonance vibrational spectroscopy (NRVS) is being used to define iron dynamics in biomolecules. The NRVS method allows the observation of all vibrational models in which there is movement of the iron. NRVS has already yielded interesting vibrational data not available by any other technique including the detection of the Fe-Im mode in six-coordinate imidazole-ligated CO derivatives. It will allow an understanding of how the protein environment can change iron dynamics and hence reactivity patterns. Other methodologies to be applied, as appropriate, include characterization of magnetic properties by bulk temperature-dependent susceptibility and electron paramagnetic resonance (EPR) measurements, Mossbauer, vibrational and UV-vis spectroscopy, and electrochemical properties. The research objectives, stated in the broadest terms, are to achieve a synthesis of the structural and physical properties of metalloporphyrins, particularly as these relationships pertain to an understanding of hemoprotein-based biological processes. Iron porphyrinates to be studied include a number of six-coordinate derivatives, [Fe(Por)(XO)(Im)] (XO = O2, CO, NO), in order to examine changes in the Fe-Im vibrations as the opposite ligand is changed, important for understanding issues in hemoglobin oxygen-binding cooperativity. Other projects include detailed study of structure and electronic structure of high-spin five coordinate iron(II) species, additional nitrosyl complexes, synthetic analogues of cytochromes b and c to show how axial ligand orientation affects their electronic structure and oxidation-reduction properties.