The conversion of L-lysine into L-β-lysine: the role of 5'-deoxyadenosyl radical and water-a DFT study.

In the current study, we deal with the crucial role of 5'-deoxyadenosyl radical and water in the mechanism of the conversion of L-lysine into L-β-lysine. The DFT (density functional theory)-B3LYP method coupled with 6-31G(d) basis set has been performed to investigate the optimized structures of transition states (TSs) and intermediates (IMs) of two processes in water: (i) the attack of 5'-deoxyadenosyl radical to complex PLP-L-lysine and (ii) hydrolysis to liberate L-β-lysine. Meanwhile, M062X/6-311++g(3df,2p) level of theory is applied to compute the relative Gibbs energy ΔG. Procedure (i) has undergone various steps but includes two main structural aziridinyl rings TS2 (ΔG = 4.1 kcal/mol) and TS3 (ΔG = 2.3 kcal/mol). In stage (ii), hydroxy group of water would help to break the bond between β-NH2 group of L-lysine and PLP better than that of Tyr389.