Enzymatic Synthesis of Poly(caprolactone): A QM/MM Study
authors Figueiredo, PR; Almeida, BC; Dourado, DFAR; Sousa, AF; Silvestre, AJD; Carvalho, ATP
nationality International
journal CHEMCATCHEM
author keywords biodegradable polyesters; polycaprolactone; enzymatic synthesis; CalB; AfEST; QM; MM MD simulations
keywords RING-OPENING POLYMERIZATION; ANTARCTICA LIPASE-B; THERMOPHILIC ESTERASE; ALIPHATIC POLYESTERS; CRYSTAL-STRUCTURE; LACTONES; SEQUENCE; FORMS
abstract Our reliance on synthetic polymers (plastics) is causing immeasurable damage to the environment. Better alternatives are actively being sought-after, such as biodegradable polyesters obtained by enzymatic synthesis. Here we compare in detail the catalytic mechanisms for poly(caprolactone) synthesis by the enzymesArchaeoglobus fulgiduscarboxylesterase (AfEST) andCandida antarcticalipase B (CalB) using Quantum Mechanics/Molecular Mechanics Molecular Dynamics simulations. In the ring-opening step (rate-limiting) the significantly higher free energy barrier found for AfEST is a consequence of the larger distance between the histidine-aspartate pair and the oxygen of the lactone, and a shorter distance to the serine nucleophile, favouring the reverse reaction towards the initial reactants. Our results give important insights towards the design of enzymatic variants which combine high activity and high thermostability in the synthesis of poly(caprolactone), which due to its bioresorbability is of great importance for biomedical applications.
publisher WILEY-V C H VERLAG GMBH
issn 1867-3880
year published 2020
digital object identifier (doi) 10.1002/cctc.202000780
web of science category Chemistry, Physical
subject category Chemistry
unique article identifier WOS:000555272500001
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journal analysis (jcr 2019):
journal impact factor 4.853
5 year journal impact factor 4.769
category normalized journal impact factor percentile 68.868
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