Protons and Porphyrins

描述（由申请人提供）：本提案的主要重点是质子（H+）、酸和氢键的化学性质。金属卟啉是一个额外的兴趣。广泛的目标是发现基本的新化学，为化学和生物系统中质子和血红素蛋白质的分子水平理解提供基础。基础化学知识对现代医学的分子基础很重要。具体目标包括（i）质子（H5 O2+，H7 O3+，H9 O 4+等）的连续水合物的表征，并了解其独特的和特有的红外光谱特性（ii）目前可访问的范围外的酸强度的测量，使新认识到的碱性抑制现象可以量化，（iii）红外？NH碱度标度为？碱（芳烃，烯烃，炔），（iv）新的分叉H-键的探索，（v）与碳硼烷酸的烷烃的活化，以及（vi）利用强，碳硼烷为基础的亲电分离新的dications。在卟啉研究中，具体目标包括：（i）质疑铁（III）卟啉中量子力学混合S = 3/2，5/2自旋态的长期接受的概念;（ii）研究铁（III）卟啉中磁化学系列中的场强与轴向配体的结合强度之间是否存在关系。该研究计划利用碳硼烷阴离子作为弱配位阴离子和碳硼烷酸的超弱共轭碱的特殊性质。这些研究的重点是通过X射线晶体学和各种光谱方法，特别是NMR和IR光谱对纯材料进行明确的表征。公共卫生相关性：质子的研究是基础化学的核心，而基础化学又是现代生物医学科学的隐藏引擎。基础化学为疾病控制的分子水平理解奠定了基础，因此对公共卫生至关重要。除了扩大知识基础外，NIH资助的基础化学是培养下一代科学家解决化学科学问题的极其重要和异常肥沃的土壤，鼓励他们中最优秀的人从事化学和生物医学科学的职业。

DESCRIPTION (provided by applicant): The main focus of this proposal is the chemistry of the proton (H+), in acids and hydrogen bonding. Metalloporphyrins are an additional interest. The broad objective is to uncover fundamental new chemistry that provides a basis for the molecular level understanding of protons and hemoproteins in chemical and biological systems. A knowledge base of fundamental chemistry is important to the molecular underpinnings of the modern medicine. Specific aims include (i) the characterization of successive hydrates of the proton (H5O2+, H7O3+, H9O4+ etc. up to Haq+) and understanding their distinctive and peculiar IR spectral properties (ii) the measurement of acid strength outside presently accessible ranges so that the newly recognized phenomenon of basicity suppression can be quantified, (iii) the development of an infrared ?NH basicity scale for ? bases (arenes, alkenes, alkynes), (iv) the exploration of new bifurcated H-bonds, (v) the activation of alkanes with carborane acids, and (vi) the exploitation of strong, carborane-based electrophiles to isolate novel dications. In porphyrin research, specific aims include (i) questioning the long-accepted concept of quantum mechanically admixed S = 3/2,5/2 spin states in iron(III) porphyrins and (ii) investigating whether there is a relationship between field strength in the Magnetochemical Series and the binding strength of axial ligands in iron(III) porphyrins. The research plan exploits the special properties of carborane anions as weakly coordinating anions and as superweak conjugate bases of carborane acids. Emphasis in these studies is placed on the definitive characterization of pure materials by X-ray crystallography and a variety of spectroscopic methods, particularly NMR and IR spectroscopies. PUBLIC HEALTH RELEVANCE: The study of the proton is central to fundamental chemistry which, in turn, is the hidden engine of modern biomedical science. Fundamental chemistry gives foundation to the molecular level understanding of disease control and thus, is critical to public health. As well as expanding the knowledge base, NIH-funded fundamental chemistry is a critically important and exceptionally fertile ground for training the next generation of scientists in problem solving in the chemically-based sciences, encouraging the best of them to pursue careers in chemistry and biomedical science.