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Simulation of the induction of oxidation of low-density lipoprotein by high copper concentrations: evidence for a nonconstant rate of initiation.

Abstract：

:Kinetic simulation can help obtain deeper insight into the molecular mechanisms of complex processes, such as lipid peroxidation (LPO) in low-density lipoprotein (LDL). We have previously set up a single-compartment model of this process, initiating with radicals generated externally at a constant rate to show the interplay of radical scavenging and chain propagation. Here we focus on the initiating events, substituting constant rate of initiation (Ri) by redox cycling of Cu2+ and Cu+. Our simulation reveals that early events in copper-mediated LDL oxidation include (1) the reduction of Cu2+ by tocopherol (TocOH) which generates tocopheroxyl radical (TocO.), (2) the fate of TocO. which either is recycled or recombines with lipid peroxyl radical (LOO.), and (3) the reoxidation of Cu+ by lipid hydroperoxide which results in alkoxyl radical (LO.) formation. So TocO., LOO., and LO. can be regarded as primordial radicals, and the sum of their formation rates is the total rate of initiation, Ri. As experimental information of these initiating events cannot be obtained experimentally, the whole model was validated experimentally by comparison of LDL oxidation in the presence and absence of bathocuproine as predicted by simulation. Simulation predicts that Ri decreases by 2 orders of magnitude during lag time. This has important consequences for the estimation of oxidation resistance in copper-mediated LDL oxidation: after consumption of tocopherol, even small amounts of antioxidants may prolong the lag phase for a considerable time.

journal_name

Chem Res Toxicol

journal_title

Chemical research in toxicology

authors

Abuja PM,Albertini R,Esterbauer H

doi

10.1021/tx9700073

subject

Has Abstract

pub_date

1997-06-01 00:00:00

pages

644-51

issue

6

eissn

0893-228X

issn

1520-5010

pii

tx9700073

journal_volume

10

pub_type

杂志文章

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