Hydrolysis of p-nitrophenyl esters of picolinic acid and N-protected amino acids by metalloenzyme models in vesicular assemblies

John G.J. Weijnen, Arie Koudijs, Paul G.J.A. Tap, Johan F.J. Engbersen

    Research output: Contribution to journalArticleAcademicpeer-review

    6 Citations (Scopus)


    Mixed vesicles of N‐dodecyl‐N,N‐dimethyl‐1‐octadecanaminium bromide (C18C12) and functionalised 1,10‐phenanthroline ligands having two long alkyl chains and a nucleophilic hydroxymethyl (1), (S)‐2‐(hydroxymethyl)pyrrolidine (2) or ephedrine group (3, 4) at the α position, were investigated for their catalytic activities and enantioselectivities in the hydrolysis of 4‐nitrophenyl esters of picolinic acid (PNPP) and N‐protected leucine [D(L)‐Z‐Leu‐PNP and D(L)‐C12‐Lcu‐PNP] in the presence of metal ions. The ZnII complex of the chiral ligand 2 in C18C12 vesicles exhibits the highest activity toward PNPP. The highest enantioselectivity in the stereoselective hydrolysis of D(L)‐C12‐Lcu‐PNP (kLa,obs/kDa,obs = 3.6) was attained with the metallocatalyst 2‐ZnII, whereas with 2‐CuII an inversion of stereoselectivity was observed (kLa,obs/kDa,obs = 0.68). The composition of the matrix in which catalyst and substrate are concentrated, affects the rate of hydrolysis but not the enantioselectivity. The rate of hydrolysis and the stereoselectivity are discussed in terms of the structure of the ligand, coordination geometry of the metal ion and the position of the metalloamphiphile in the surfactant aggregate.
    Original languageEnglish
    Pages (from-to)525-530
    JournalRecueil des travaux chimiques des Pays-Bas
    Issue number10
    Publication statusPublished - 1993


    Cite this