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A. Stepanova et al.

/ Free Radical Biology and Medicine 120 (2018) S45–S166 S55

Background: In Type 2 Diabetes Mellitus (T2DM) high blood glucose levels P-35
increases oxidative stress. Metformin is a first-choice antidiabetic drug for
T2DM patients to lower blood glucose levels, oxidative stress and provide
better lipid profiles. Free-radical fragmentation reactions of biomolecules
Objectives: This study was planned to detect antioxidant vitamin (E and C) involving C-C, C-O and C-N bond cleavage
levels in T2DM patients at the time of diagnose (t ¼0) and after 6 months
of monotherapy (t¼ 180).
O.I. Shadyro
Methods: A total of 17 patients were recruited. Blood samples (10 ml)
were taken when patients were first diagnosed with T2DM and after six
months of Metformin usage. We also had an age and sex matched control Belarusian State University, Minsk, Belarus
group.
Results: Vitamin C levels of T2DM patients t ¼0 was significantly lower
than the healthy controls (p ¼ 0.000). At t ¼ 180, Vitamin C levels of pa- Among a wide variety of homolytic transformations taking place in
tients almost reached the Vitamin C levels of controls and this elevation biomolecules, the oxidation processes occurring in the cell membrane
was found to be significant between t¼ 180 and t¼ 0 (p ¼ 0.001). On the lipids have been the most thoroughly studied ones. For such processes to
other hand, Vitamin E levels of healthy controls and T2DM patients be realized, the presence of oxygen is necessary. At low O2 concentrations
t ¼ 0 were not significantly different. At t ¼ 180, Vitamin E levels of T2DM the probability of oxidation processes decreases, enabling other types of
patients were detected as significantly lower than healthy controls free-radical reactions to occur in biomolecules.
(p ¼0.267). In our studies, a concept is being developed focusing on the important
Conclusion: Our data suggests that there is an inverse correlation between contribution of free-radical fragmentation reactions involving C-C, C-O and
Vitamin C and Vitamin E levels of T2DM patients under monotherapy for C-N bond rupture in organic molecules to the biosystem damage. Such
6 months period processes can take place without participation of oxygen and may lead not
E-mail address: ceylan_h@yahoo.com only to destruction and modification of biologically relevant compounds
but to accumulation of physiologically active products as well.
The reactions resulting in the C-C, C-O or C-N bond ruptures occurring
http://dx.doi.org/10.1016/j.freeradbiomed.2018.04.180
in an organism are known to be catalyzed by lyases. Many of these reac-
tions proceed according to a free-radical mechanism.
The report will be focused on discussion of the above-named frag-
mentation reactions of biomolecules and the possible consequences of their
P-34 realization in an organism.
E-mail address: shadyro@tut.by

Kinetics and biological consequences of quinone-in-


duced protein adduction http://dx.doi.org/10.1016/j.freeradbiomed.2018.04.182

Nan Shu, Lasse G. Lorentzen, Michael J. Davies

P-36
Department of Biomedical Sciences, Panum Institute, University of
Copenhagen, Denmark
Investigation of the effect of biologically active sup-
plements on oxidative stability of flaxseed oil
Quinones are a major class of toxicological compounds, that can both
generate radicals, and act as Michael acceptors with nucleophiles in-
Irina Edimecheva, Anna Sosnovskaya, Oleg Shadyro
cluding Cys residues on proteins. This study aimed to quantitatively assess
quinone-protein reactions and examine the relationship between quinone
adduction and protein dysfunction. A range of quinones were incubated Belarusian State University, Research Institute for Physical Chemical
with glyceraldehyde-3-phosphate dehydrogenase (GAPDH), creatine ki- Problems of the Belarusian State University, Minsk, Belarus
nase (CK), papain, bovine serum albumin (BSA), and human serum albu-
min (HSA), with both the kinetics of adduction and effects on protein
structure and activity determined. Adduction rate constants at Cys re- The influence of added vitamins and other biologically active sub-
sidues, which were dependent on the quinone and protein structures, and stances (BAS) (α-tocopherol, α-tocopherol acetate, cholecalciferol, β-car-
thiol pKa, were in the range 103 -105 M-1s-1. p-Benzoquinone (BQ) in- otene, lutein, zeaxanthin, coenzyme Q10, selenomethionine) on resistance
duced dimerization of GAPDH and CK (but not BSA, HSA, or papain) in a of flaxseed oil to oxidation, was investigated. For this purpose, kinetic data
dose- and time-dependent manner, as well as a loss of enzyme activity. were obtained on accumulation of primary and secondary oxidation pro-
Glutathione (GSH) reacts competitively with BQ, and can thereby reverse ducts, free fatty acids in flaxseed oil, as well as the consumption of BAS
the activity loss and dimerization of GAPDH and CK. Mass spectrometry, during the storage of flaxseed oil enriched with supplements. It was shown
after digestion to peptide, showed that BQ preferentially forms adducts that the supplements used to enrich flaxseed oil could exhibit both anti-
with GAPDH at Cys149 and Cys244. These data suggest that quinones can oxidant and pro-oxidant properties depending on their chemical structure
induce toxicity by rapidly and selectively forming adducts with Cys re- and concentration. The fat-soluble esters of ascorbic acid and their com-
sidues in proteins. positions with natural antioxidants based on legumes have shown to be
E-mail address: shunan@sund.ku.dk effective and safe stabilizers of BAS enriched flaxseed oil, which enable to
substantially inhibit the oxidation and oxidative destruction of flaxseed oil
lipids, to reduce the losses of BAS, and, therefore, to extend the storage
http://dx.doi.org/10.1016/j.freeradbiomed.2018.04.181
period of the oil. Basing on the investigation results, the formulas of new,
oxidation-resistant functional food products based on flaxseed oil have
been developed, and their production has been organized.
E-mail address: irina.edimecheva@gmail.com

http://dx.doi.org/10.1016/j.freeradbiomed.2018.04.183

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