Protons and Porphyrins

描述(由申请人提供)：本提案的主要重点是酸中质子(H+)的化学和氢键。金属卟啉是另一个令人感兴趣的东西。其广泛的目标是揭示基本的新化学，为在分子水平上理解化学和生物系统中的质子和血红素蛋白提供基础。基础化学的知识基础对现代医学的分子基础很重要。具体目标包括(I)表征质子的连续水合物(H5O2+、H7O3+、H9O4+等直到HAq+)，并了解它们独特而独特的红外光谱性质；(Ii)测量目前可达范围之外的酸强度，以便能够量化新发现的碱度抑制现象；(Iii)开发红外？NH碱度标度？(4)探索新的分叉氢键，(5)碳硼酸活化烷烃，以及(6)开发基于碳硼烷的强亲电体以分离新的配位化合物。在卟啉研究中，具体目标包括(I)质疑长期被接受的量子力学掺杂的S=3/2，5/2自旋态的概念，以及(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作为碳硼酸的超弱共轭碱的特殊性质。这些研究的重点是通过X射线结晶学和各种光谱方法，特别是核磁共振和红外光谱来确定纯材料的特征。与公共健康相关：对质子的研究是基础化学的核心，而基础化学反过来又是现代生物医学科学的隐藏引擎。基础化学为从分子水平理解疾病控制奠定了基础，因此对公众健康至关重要。除了扩大知识库，NIH资助的基础化学是培训下一代科学家在以化学为基础的科学中解决问题的极其重要和特别肥沃的基础，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.