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    STUDIA CHEMIA - Ediţia nr.2 din 2008  
         
  Articol:   NITRITE LINKAGE ISOMERISM IN BIOINORGANIC CHEMISTRY – A CASE FOR MECHANISTIC PROMISCUITY.

Autori:  RADU SILAGHI-DUMITRESCU, MATEI-MARIA UŢĂ. 		 
       
         
  Rezumat:  Reduction of nitrite to nitric oxide is essential in certain living species, and has even been proposed to be an important secondary function of hemoglobin in humans. In vivo, nitrite reduction is accomplished by metalloenzymes, and involves direct metal-nitrite coordination at iron, copper, and possibly molybdenum. Using density functional (DFT) results, we have proposed that linkage (nitro/nitrito) isomerism is an essential part of the mechanism in one class of nitrite reductase enzymes. Here, DFT data is shown suggesting the generality of nitrite linkage isomerism in bioinorganic chemistry, and experimental data supporting this theory-driven proposal is briefly reviewed. The concept that nitrite reduction may be achieved by a given metalloprotein via two different mechanisms with the same product and comparable efficiencies is considered, as part of our recently-defined mechanistic promiscuity paradigm.  
         
     
         
         
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