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

描述(申请人提供)：这项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。这项研究的主要目标是回答以下问题： 1.亚硝硫醇是如何由硫醇形成的，NO是如何释放的？是什么控制着亚硝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.如果有的话，一氧化氮二聚体(NO)2在NO的亲电反应中的作用是什么？ 3.重氮二酸盐的分解机制是什么，是什么控制了NO、HNO和N20的形成？没有捐赠者能更好地被预测和创造吗？ 4.HNO的物理和化学性质是什么？ 5.当一氧化氮合酶合成一氧化氮的中间产物N-羟基精氨酸从酶中释放出来时，会发生什么化学作用？一氧化氮合酶生物合成NO的最后步骤是什么？ 6.在质子化或与二氧化碳或其他温和的Lewis酸反应时，Oono-以及该物种的自由基和硝化化学的分解机制是什么？水中的HO..ONO和NO2.CO3-自由基对是否参与其中？

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?