Synthetic catalytic pores

被引:67
作者
Sakai, N [1 ]
Sordé, N [1 ]
Matile, S [1 ]
机构
[1] Univ Geneva, Dept Organ Chem, CH-1211 Geneva, Switzerland
关键词
D O I
10.1021/ja029845w
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Catalytic activity of a synthetic multifunctional pore is studied in large unilamellar vesicles under conditions where substrate and synthetic catalytic pore (SCP) approach the membrane either from the same side (cis catalysis) or from opposite sides (trans catalysis). A synthetic supramolecular rigid-rod β-barrel with excellent ion channel characteristics is identified as SCP using 8-acetoxypyrene-1,3,6-trisulfonate (AcPTS) as model substrate. The key finding is that application of supportive membrane potentials increases the initial velocity of AcPTS esterolysis (v0). This results in an increase of Vmax beyond experimental error (+30%), whereas KM increases less significantly. Long-range electrostatic steering by the membrane potential, possibly guiding substrates into the transmembrane catalyst and, more importantly, accelerating product release (foff = 1.3) is discussed as one possible explanation of this global reduction of catalyst saturation. Control experiments show, inter alia, that similarly strong changes do not occur with opposing membrane potentials. Copyright © 2003 American Chemical Society.
引用
收藏
页码:7776 / 7777
页数:2
相关论文
共 19 条
  • [1] Baumeister B, 2002, HELV CHIM ACTA, V85, P2740, DOI 10.1002/1522-2675(200209)85:9<2740::AID-HLCA2740>3.0.CO
  • [2] 2-C
  • [3] p-octiphenyl β-barrels with ion channel and esterase activity
    Baumeister, B
    Sakai, N
    Matile, S
    [J]. ORGANIC LETTERS, 2001, 3 (26) : 4229 - 4232
  • [4] Toward p-octiphenyl β-barrel RNases
    Baumeister, B
    Matile, S
    [J]. MACROMOLECULES, 2002, 35 (05) : 1549 - 1555
  • [5] Stochastic sensors inspired by biology
    Bayley, H
    Cremer, PS
    [J]. NATURE, 2001, 413 (6852) : 226 - 230
  • [6] Fluorometric detection of enzyme activity with synthetic supramolecular pores
    Das, G
    Talukdar, P
    Matile, S
    [J]. SCIENCE, 2002, 298 (5598) : 1600 - 1602
  • [7] Fersht A., 1985, ENZYME STRUCTURE MEC
  • [8] Synthetic models of cation-conducting channels
    Gokel, GW
    Mukhopadhyay, A
    [J]. CHEMICAL SOCIETY REVIEWS, 2001, 30 (05) : 274 - 286
  • [9] REACTION OF DIPHTHERIA-TOXIN CHANNELS WITH SULFHYDRYL-SPECIFIC REAGENTS - OBSERVATION OF CHEMICAL-REACTIONS AT THE SINGLE-MOLECULE LEVEL
    MINDELL, JA
    ZHAN, HJ
    HUYNH, PD
    COLLIER, RJ
    FINKELSTEIN, A
    [J]. PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 1994, 91 (12) : 5272 - 5276
  • [10] Synthetic multifunctional pores:: deletion and inversion of anion/cation selectivity using pM and pH
    Sakai, N
    Sordé, N
    Das, G
    Perrottet, P
    Gerard, D
    Matile, S
    [J]. ORGANIC & BIOMOLECULAR CHEMISTRY, 2003, 1 (07) : 1226 - 1231