Martijn A. J. Veld

Lactone size dependent reactivity in Candida antarctica lipase B: A molecular dynamics and docking study

Size matters: Lactones have extensively been studied as monomers in enzymatic polymerization reactions. Large lactones showed an unexpectedly high reactivity in these reactions. A combination of docking and molecular dynamics studies have been used to explain this high reactivity in terms of productive binding due to the transoid nature of the ester bond in these substrates.

Sterically demanding benzene-1,3,5-tricarboxamides: tuning the mechanisms of supramolecular polymerization and chiral amplification

Benzene-1,3,5-tricarboxamide (BTA) derivatives with one or three phenylalanine octyl ester (PheOct) moieties were synthesized and their supramolecular polymerization and chiral amplification behavior were investigated in mixing experiments between enantiomer pairs and in mixing with another, achiral BTA component. The incorporation of PheOct moieties is shown to have a major impact on the supramolecular self-assembly.

Consequences of Cooperativity in Racemizing Supramolecular Systems

Saluting the sergeant: Phg-BTA (see scheme) cooperatively self-assembles into helical aggregates and shows unprecedented racemization behavior in the presence of base. In thermodynamically controlled conditions, the addition of a small amount of chiral auxiliary to this mixture results in a deracemization reaction and a final enantiomeric excess of 32 %. A theoretical model is presented to understand in detail the results obtained.

Hydrolases Part I: Enzyme Mechanism, Selectivity and Control in the Synthesis of Well-Defined Polymers

Lipases are highly activity in the polymerization of a range of monomers. Both ring-opening polymerization of cyclic esters and polycondensation reactions of AA–BB and AB monomers have been investigated in great detail. This paper reviews the increased understanding in enzymatic strategies for the production of well-defined polymers. Major advantages of enzymatic catalysts are the relatively mild reaction conditions, and the often-observed excellent regio-, chemo-, and enantioselectivity that allow for the direct preparation of functional materials. However, as a result of the monomer activation mechanism, polymers of low polydispersity and low quantitative degree of endgroup functionality are difficult to attain. A wide variety of (co)polymers have been synthesized and explored in a variety of applications using lipase catalysts.