Protons and Porphyrins

质子和卟啉

基本信息

批准号：
8067103
负责人：
CHRISTOPHER A REED
金额：
$ 30.25万
依托单位：
UNIVERSITY OF CALIFORNIA RIVERSIDE
依托单位国家：
美国
项目类别：
财政年份：
1978
资助国家：
美国
起止时间：
1978-06-01 至 2013-04-30
项目状态：
已结题

项目摘要

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.

描述（由申请人提供）：该提案的主要重点是质子（H+）的化学，在酸和氢键中。金属磷脂是一个额外的兴趣。广泛的目标是发现基本的新化学，这为化学和生物系统中质子和血蛋白的分子水平理解提供了基础。基本化学的知识基础对于现代医学的分子基础很重要。具体目的包括（i）质子连续水合的表征（H5O2+，H7O3+，H9O4+等，直至HAQ+），并了解它们的独特和特殊的红外光谱特性（ii）测量酸强度外部外部可访问的范围，以便可以量化新认可的碱性抑制现象，（iii）红外碱性量表的发展？碱（竞技场，烷烃，炔烃），（iv）探索新的分叉H键，（v）用碳酸盐激活烷烃，以及（vi）（vi）剥削强的，carborane的电力液以隔离新颖的分解。在卟啉研究中，具体目的包括（i）质疑量子的长期质量概念s = 3/2,5/2在铁（III）卟啉中旋转状态，以及（ii）研究场强度之间是否存在关系在铁（III）卟啉中轴向配体的磁化学系列和轴向配体的结合强度。该研究计划利用了卡堡阴离子的特殊特性，是弱配位阴离子和碳酸盐酸的超级缀合物碱基。这些研究中的重点放在X射线晶体学和多种光谱方法（尤其是NMR和IR光谱法）的确定性表征上。公共卫生相关性：对质子的研究对于基本化学是核心，反过来是现代生物医学科学的隐藏引擎。基本化学为疾病控制的分子水平理解为基础，因此对公共卫生至关重要。除了扩大知识库外，NIH资助的基本化学是一个至关重要且异常肥沃的基础，用于培训下一代科学家在化学科学中解决问题，鼓励他们最好的人从事化学和生物医学领域的职业。科学。

项目成果

期刊论文数量（33）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

The R3O+···H+ hydrogen bond: toward a tetracoordinate oxadionium(2+) ion.

DOI：
10.1021/ja209942s
发表时间：
2012-01-11
期刊：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
影响因子：
15
作者：
Stoyanov, Evgenii S.;Gunbas, Gorkem;Hafezi, Nema;Mascal, Mark;Stoyanova, Irini V.;Tham, Fook S.;Reed, Christopher A.
通讯作者：
Reed, Christopher A.

Evidence for C-H hydrogen bonding in salts of tert-butyl cation.

叔丁基阳离子盐中 C-H 氢键的证据。