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|Title:||Density functional theory calculations on biological S-transfer: Insight into the mechanism of rhodanese|
|Keywords:||Density functional calculations|
|Abstract:||Biological sulfur transfer (S-transfer) is a key step in the synthesis of metabolites, CN- detoxification and assembly of iron-sulfur clusters. Computational results addressing the thermodynamics of the S-transfer reactions from thiosulfate (natural S-donor) to HCN and thiol are presented. These calculations indicate that S-transfer from thiosulfate to HCN and thiol is possible only in the anionic forms of these species. However these species have pKa values significantly higher than physiological pH value (i.e., they are protonated in physiological pH and incapable of S-transfer). In the rhodanese active site, basic residues are present to deprotonate the catalytic cysteine group which accepts the S-atom from thiosulfate. The resultant perthiol species transfer S-atom to CN- in a synchronous S-atom and H+ transfer step facilitated by the two arginine residues present in the rhodanese active site. Based on these calculations, a mechanism is proposed for the rhodanese catalyzed CN- detoxification pathway.|
|Appears in Collections:||IJC-A Vol.50A(09-10) [September-October 2011]|
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|IJCA 50A(09-10) 1457-1462.pdf||234.82 kB||Adobe PDF||View/Open|
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