Theory of the Chemistry of NO, HNO, OONO-, and RSNO

描述（由申请人提供）：本研究项目涉及使用最先进的理论方法对NO及其衍生物的生物相关化学进行计算研究。研究的主要目标是回答以下问题： 1.硫醇是如何形成亚硝基硫醇的，NO是如何释放的？是什么控制了亚硝基硫醇的稳定性，以及在特定条件下NO、NO-和NO+是如何释放或转移的？ 2.一氧化氮二聚体（NO）2在NO的亲电反应中的作用是什么？ 3.二醇二氮盐的分解机制是什么？是什么控制着NO、HNO和N2 O的形成？是否可以预测和创建更好的NO供体？ 4. HNO的物理和化学性质是什么？ 5.当NO合成酶释放NO合成的中间产物N-羟基精氨酸时，发生了什么化学反应？NOS合成NO的最后步骤是什么？ 6.在质子化或与CO2或其他温和的刘易斯酸反应时，OONO-的分解机制以及该物种的自由基和硝化化学是什么？ 是HO.. ONO和NO_2.CO_3-自由基对在水中的参与？

DESCRIPTION (provided by applicant): This research project involves computational studies of the biologically relevant chemistry of NO and derivatives using state-of-the-art theoretical methods. The principal goals of the research are to answer the following questions: 1. How are nitrosothiols formed from thiols, and how is NO released? What controls the stabilities of nitrosothiols and how NO, NO-, and NO+ are released or transferred under specific conditions? 2. What is the role -if any - of the nitric oxide dimer, (NO)2, in the electrophilic reactions of NO? 3. What are mechanisms of decomposition of diazenium diolates, and what controls NO, HNO, and N20 formation? Can better NO donors be predicted and created? 4. What are the physical and chemical properties of HNO? 5. What chemistry occurs when N-hydroxyarginine, an intermediate in NO synthesis by NO synthase, is released from the enzyme? What are the final steps in NO biosynthesis by NOS? 6. What is the mechanism of decomposition of OONO-, as well as radical and nitration chemistry of this species, upon protonation or reactions with CO2 or other mild Lewis acids? Are the HO..ONO and NO2.CO3- radical pairs in water involved?