DOI QR코드

DOI QR Code

Electrostatic and Hydrophobic on Recognition and Deacylation of an Anionic Ester by Ni(II)-Macrocyclic Complexes Built on Poly(ethylenimine)

  • Suh, Jung-Hun (Department of Chemistry, Seoul National University) ;
  • Kim, No-Won (Department of Chemistry, Seoul National University)
  • Published : 1993.04.20

Abstract

Three derivatives of poly(ethylenimine) (PEI) are prepared by Ni(II)-template condensation with glyoxal(GO): PEI[Ni(II)-GO]$_{0.08}$ (1), PEI[Ni(II)-GO]$_{0.03}$ (2), and lau$_{0.18}$PEI[Ni(II)-GO]$_{0.03}$ (3). The contents of Ni(II)-macrocyclic center of 1-3 are 8%, 3%, or 3%, respectively, of the monomer residues, and 18% of monomer residues for 3 are laurylated. The pH profiles for k$_{cal}$ and k$_m$ for the deacylation of 4-carboxy-2-nitrophenyl acetate are measured. The relative magnitude of the parameters for 1-3 and different shapes of the pH profiles for 1-3 are explained in terms of the electrostatic and the hydrophobic effects exerted by the metal centers and lauryl groups. For the artificial metalloenzymes built on PEI, therefore, the ionization of functional groups and the affinity toward counter-anions can be controlled by adjusting charge density and the content of hydrophobic groups.

Keywords

References

  1. Molecular Recognition: Chemical and Biochemical Problems S. M. Roberts(ed.)
  2. Enzyme Mechanisms M. L. Bender;M. I. Page(ed.);A. Williams(ed.)
  3. Calixarenes C. D. Gutsche
  4. Cyclophanes F. Diedriech
  5. Crown Ethers and Cryptands G. Gokel
  6. J. Am. Chem. Soc. v.114 V. Jubian;R. P. Dixon;A. D. Hamilton
  7. Adv. Phys. Org. Chem. v.17 T. Kunitake;S. Shinkai
  8. Enzyme Mechanisms I. M. Klotz;M. I. Page(ed.);A. Williams(ed.)
  9. Acc. Chem. Res. v.25 J. Suh
  10. J. Am. Chem. Soc. v.113 J. Suh;Y. Cho;K. J. Lee
  11. J. Am. Chem. Soc. v.114 J. Suh;S. H. Lee;K. D. Zoh
  12. Proc. Nat. Acad. Sci. U.S.A. v.68 I. M. Klotz;G. P. Royer;I. S. Scarpa
  13. Biopolymers v.18 T. Takagishi;I. M. Klotz