【摘要】 用分子轨道对称性规则阐明生物体系NO与 ·O- 2、·NO2、·OH、LOO· 反应动力学及其生物学意义。从分子轨道、电子结构、化学键的稳定性、诱导效应以及极化与反极化作用 ,阐明ONOOH的极不稳定性。用量子化学MO理论建立ONOO- 、ONOOH键合模型 ,从理论和实验事实论证模型的唯一合理性。提出ONOO- 和ONOOH存在特殊共轭大π键 ,推出它们的π分子轨道能级顺序和示意图 ,从而能很好解释ONOO- 和ONOOH的氧化性、硝化性、分解性能及ONOOH分子重排。指出激发态共振结构〔HO··NO2〕、〔HO- + NO2〕和〔HO+ - NO2〕的实质是ONOOH存在特殊离域大π键(Π44-1sH)45 。进一步证明ONOO -、ONOOH中 -O2 -基团以π*2p 而不是O2p参与成键。更多还原

【Abstract】 The molecular orbital symmetry rule are applied to expounding the kinetics of reactions between NO and ,NO2 ,·OH,LOO· in the biological system and their biological meanings as well. The extreme unstability of ONOOH has been explained in the light of the molecular orbital, the electronic structure, the stability of the chemical bond, the inductive effect and the effect of polarization and antipolarization. Besides, the models of chemical bond stereostructure of ONOO- and ONOOH are established out of the quantum chemistry MO theory. And then the only logic of these models can be explounded and proved by the theory and experimental facts. Moreover, it has been raised that there are a special conjugated π bond in ONOO- and ONOOH, and their energy level order and sketch of the π molecular orbital have also been concluded. And the conclusion offers a good explanation to the oxidation, nitration, decomposition property of ONOO- and ONOOH, the molecular rearrangement of ONOOH. Farthermore, it has been pointed out that the essence of the resonance structures in excited state 〔HO··NO2〕,〔HO-+NO2〕and 〔HO+-NO2〕is that there is a special delocalized pi bond in ONOOH. It has been proved farther that O2 group in ONOO- and ONOOH is participating in the binding bond through π2p insleal of O 2p orbitals.更多还原