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Bulletin of the Korean Chemical Society v.25 no.10, 2004년, pp.1477 - 1483   피인용횟수: 1

Tandem Mass Spectrometric Evidence for the Involvement of a Lysine Basic Side Chain in the Coordination of Zn(II) Ion within a Zinc-bound Lysine Ternary Complex

Yu, Sung-Hyun    (Department of Chemistry, Sogang University   ); Lee, Sun-Young    (Department of Chemistry, Sogang University   ); Chung, Gyu-Sung    (Department of Chemistry, Konyang University   ); Oh, Han-Bin    (Department of Chemistry, Sogang University  );
  • 초록

    We present the tandem mass spectrometry applications carried out to elucidate the coordination structure of Zn(II) bound lysine ternary complexes, $(Zn+Lys+Lys-H)^+$ , which is a good model system to represent a simple (metallo)enzyme-substrate complex (ES). In particular, experimental efforts were focused on revealing the involvement of a lysine side chain ${\varepsilon}$ -amino group in the coordination of $Zn^{2+}$ divalent ions. MS/MS fragmentation pattern showed that all the oxygen species within a complex fell off in the form of $H_2O$ in contrast to those of other ternary complexes containing amino acids with simple side chains (4-coordinate geometries, Figure 1a), suggesting that the lysine complexes have different coordination structures from the others. The participation of a lysine basic side chain in the coordination of Zn(II) was experimentally evidenced in MS/MS for $N{\varepsilon}$ -Acetyl-L-Lys Zn(II) complexes with acetyl protection groups as well as in MS/MS for the ternary complexes with one $NH_3$ loss, $(Zn+Lys+Lys-NH_3-H)^+$ . Detailed structures were predicted using ab initio calculations on $(Zn+Lys+Lys-H)^+$ isomers with 4-, 5-, and 6-coordinate structures. A zwitterionic 4-coordinate complex (Figure 7d) and a 5-coordinate structure with distorted bipyramidal geometry (Figure 7b) are found to be most plausible in terms of energy stability and compatibility with the experimental observations, respectively.


  • 주제어

    Tandem mass spectrometry .   Zinc ion .   Lysine amino acid .   Metal ion coordination .   Binding structures.  

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  • 이 논문을 인용한 문헌 (1)

    1. 2008. "" Bulletin of the Korean Chemical Society, 29(2): 450~462     

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