PEROXYNITRITE IN THE HEMOGLOBIN COMPOSITION
K. V. Simon, A. V. Tulub
St. Petersburg State University, St. Petersburg, Russia
Keywords: структура гемма, неэмпирические расчеты, O/NO химия, hemaglobineа structure, non-empirical calculations, O/NO chemistry
Abstract
Electronic characteristics of trHbN hemoglobin whose composition contains the (ONOO) group with the structure close to the structure of 1) peroxynitrite and 2) a nitrate anion in the gas phase are calculated. Electron correlation is considered by the multiconfigurational self-consistent field (MCSCF) method during the optimization of the geometry of the whole structure. Localized molecular orbitals (MOs) are used as starting ones. In the wave function of the MCSCF method two complete active subspaces (CASs) are set. These are the subspace of iron atom 3 d orbitals and the subspace describing chemical bonds in peroxynitrite (bonding and antibonding MOs plus the orbital of one lone pair on the O2 moiety. The composition of the system involves two water molecules. The peroxynitrite structure is considered in two different spin states that correspond to the singlet and triplet states of this anion in the gas phase where the vibrational spectrum is characterized by frequencies of about (70-30) cm-1. The protective reaction of the active center of the tubercule bacillus is discussed.
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