Kinetic characteristics of the reaction of resveratrol with peroxyl radicals and natural thiols in aqueous medium

Article abstract of DOI:10.1007/s11172-017-1995-1

The method of competing reactions was used to determine the rate constants of the reaction of resveratrol (RVT) with peroxyl radicals formed on decomposition of the azoinitiator in aqueous solutions at 37 °С. The polymethine dye A (3,3′-di-γ-sulfopropyl-9-metylthiacarbocyanine-betaine pyridinium salt) was used as a competing acceptor of radicals. It was found that resveratrol can be involved in the reaction with natural thiols, glutathione (GSH) and cysteine (CSH), in aqueous solutions at 37 °С. The reaction of RVT with thiols (thiol—еne reaction) follows a chain mechanism and accelerates in the presence of Н₂О₂. The results obtained can be useful for understanding the physiological role of thiols in oxidation processes.

Full text of DOI:10.1007/s11172-017-1995-1

Russian Chemical Bulletin, International Edition, Vol. 66, No.11, pp. 2145—2151, November, 2017
2145
Kinetic characteristics of the reaction of resveratrol
with peroxyl radicals and natural thiols in aqueous medium
K. M. Zinatullina,a,b,c N. P. Khrameeva, O. T. Kasaikinaa,c,d B. I. Shapiro, and V. A. Kuzmin
b
b
b,d
аN. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences,
4
ul. Kosygina, 119991 Moscow, Russian Federation
b
N. M. Emanuel Institute of Biochemical Physics, Russian Academy of Sciences,
4
ul. Kosygina, 119991 Moscow, Russian Federation
c
P. G. Demidov Yaroslavl State University,
1
4 ul. Sovetskaya, 150000 Yaroslavl, Russian Federation.
Fax: +7 (495) 651 2191. Eꢀmail: karinazinat11@gmail.com
M. V. Lomonosov Moscow State University, Department of Chemistry,
Build. 3, 1 Leninskie Gory, 119991 Moscow, Russian Federation
d
The method of competing reactions was used to determine the rate constants of the
reaction of resveratrol (RVT) with peroxyl radicals formed on decomposition of the azoinitiꢀ
ator ААРН in aqueous solutions at 37 °С. The polymethine dye A (3,3´ꢀdiꢀγꢀsulfopropylꢀ9ꢀ
metylthiacarbocyanineꢀbetaine pyridinium salt) was used as a competing acceptor of radicals.
It was found that resveratrol can be involved in the reaction with natural thiols, glutathione
(
(
GSH) and cysteine (CSH), in aqueous solutions at 37 °С. The reaction of RVT with thiols
thiol—еne reaction) follows a chain mechanism and accelerates in the presence of Н О .
2
2
The results obtained can be useful for understanding the physiological role of thiols in oxidaꢀ
tion processes.
Key words: resveratrol, thiol—еne reaction, glutathione, cysteine, antioxidants, kinetics.
transꢀResveratrol (RVT, 3,5,4´ꢀtrihydroxystilbene) is
known as phytoalexin, which is present in grapes and red
wines in relatively large amounts. A high content of resꢀ
veratrol in red wine (0.1—15 mg L–1) is believed to be
related to the soꢀcalled "French paradox", an unusually
low level of cardiovascular and oncological diseases obꢀ
served in some regions of France with a highꢀcalorie diet,
which includes a large amount of fats and a regular conꢀ
phatidylcholine initiated by various oxidants; while in the
work23 the authors suppose that RVT and αꢀtocopherol
form a synergistic mixture, in which RVT reduces the
tocopheroxyl radical. At the same time, it is RVT that is
regarded to be responsible for the "antioxidant power" of
red wine, although it is not its main phenolic comꢀ
ponent.2
4
The studies of the antiradical activity of transꢀ and
cisꢀisomers of RVT and some other hydroxylꢀsubstituted
1
—4
sumption of red wine.
It is known that resveratrol preꢀ
5
—9
vents the development of atherosclerosis,
has antiꢀ
inflammatory, neuroprotective, cardioprotective, and
stilbenes in the homogeneous solutions in oxidizing styꢀ
1
0
25,26
rene
showed that these phenolic compounds are meꢀ
1
1,12
antitumor activity.
The protective effect of resveraꢀ
dium strength inhibitors terminating the oxidation chains:
the reaction rate constant of RVT with the peroxyl radiꢀ
trol is associated with the antioxidant properties of pheꢀ
nolic compounds. It was found that RVT inhibits lipid
5
–1
–1
26
cal did not exceed 1.5•10 mol L s (at 30 °С). In
1
3
peroxidation in blood cells treated with peroxynitrite
aqueous media, the antiradical activity of RVT has been
1
4,15
and in cell membranes;
proteins.1
inhibits oxidation of lipoꢀ
studied mainly with respect to hydroxyl radicals formed
6—19
27—30
under γꢀradiolysis conditions
generated by the
The data on the reactivity of RVT in the reactions
Fenton reaction,31 as well as by laser flash photolysis.32
In the present work, we study the kinetics of the reacꢀ
tion of RVT with hydrogen peroxide and peroxyl radicals
formed upon decomposition of 2,2´ꢀazobis(2ꢀmethylꢀ
propionamidine) dihydrochloride (ААРН) in aqueous
solutions. Since, unlike most phenolic antioxidants,
RVT contains an unsaturated bond conjugated with two
phenolic fragments, it can exist in transꢀ and cisꢀform
with active oxygen species (peroxyl and hydroxyl radiꢀ
–
cals, radical anion О ) are very contradictory. Thus, in
2
the works2
0,21
RVT is called a strong lipophilic antiꢀ
2
2
oxidant comparable in activity with αꢀtocopherol;
1
4
in the work the authors present the evidence that
RVT is considerably weaker than both αꢀtocopherol
and trolox in of the oxidation of liposomes of phosꢀ
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2145—2151, November, 2017.
066ꢀ5285/17/6611ꢀ2145 © 2017 Springer Science+Business Media, Inc.
1

2
146
Russ. Chem. Bull., Int. Ed., Vol. 66, No. 11, November, 2017
Zinatullina et al.
and actively react with thiyl radicals.33—35 This was the
reason that we paid special attention to the study of the
reaction of resveratrol with natural thiols, cysteine (CSH)
and glutathione (GSH), which, similarly to resveratrol,
are bioantioxidants. The antioxidant functions of thiols
are manifested in the reaction with hydroxyl radicals,
reduction of hydrogen peroxide, hydroperoxides, and disꢀ
ulfide bonds —S—S—, prevention of oxidation of proꢀ
khimprom) were used without preliminary purification. The
azoinitiator AAPH (2,2´ꢀazobis(2ꢀmethylpropionamidine) diꢀ
hydrochloride, Fluka) was used for generation of peroxyl radiꢀ
cals. The anionic polymethine dye А, (3,3´ꢀdiꢀγꢀsulfopropylꢀ9ꢀ
metylthiacarbocyanineꢀbetaine pyridinium salt, Gosniikhimꢀ
fotoproekt)41 was used as the spectrokinetic probe.
Bidistilled water was used for preparation of base solutions
of the dye, H O , CSH, GSH and as a reaction medium. Base
2
2
solutions of resveratrol were prepared in ethanol (Medkhimꢀ
prom). The reactions were carried out in aqueous medium with
the addition of base solutions of reagents (1—10 μL). The conꢀ
centration of resveratrol and the polymethine dye was regisꢀ
tered spectrophotometrically: RVT has a characteristic absorpꢀ
teins.3
6—39
In the work, the rate constants of the reacꢀ
40
tion of CSH and GSH with peroxyl radicals were deterꢀ
mined by the method of competing reactions using a polyꢀ
methine dye and it was found that thiyl radicals are formed
in low yield during reduction of hydrogen peroxide with
thiols. In the present work, this procedure was used for
determining the kinetic characteristics of the reaction of
resveratrol with peroxyl radicals and studying the reaction
between resveratrol and thiols CSH and GSH (thiol—еne
reaction). It should be noted that in recent years the numꢀ
ber of works (especially in the field of medical chemistry)
on the reactions of unsaturated substrates with thiols as a
method for the synthesis of heterochain compounds has
increased dramatically. However, the thiolꢀene reactions
of natural thiols remain practically uninvestigated.
5
–1
–1
tion band at 304—308 nm (ε = 0.3•10 L mol cm ), the dye
А absorbs at 543 nm (ε = 0.77•10 L mol cm–1).40,41 The
5
–1
concentration of H O in the base solution was controlled by
2
2
the iodometric method.
All the reactions were carried out at a physiological temꢀ
perature of 37 °С in a glass thermostated cell and/or directly in
thermostated quartz cells of Ultraspec 1100 Pro (l = 1 cm) and
Shimadzu 3101 spectrophotometers (the "New Materials and
Technologies" MultiꢀAccess Center of the N. M. Emanuel Inꢀ
stitute of Biochemical Physics of the Russian Academy of Sciꢀ
ences). The experimental error in determination of kinetic charꢀ
acteristics of the reaction of resveratrol with thiols did not exꢀ
ceed 10%.
Results and Discussion
Figure 1, a shows the change in the absorption spectra
of RVT during reaction with peroxyl radicals formed upon
decomposition of ААРН (the spectra were recorded every
1
min) and practically parallel kinetic curves of its conꢀ
sumption at different initial concentrations (see Fig. 1, b).
According to the theory,2
2,42,43
the independence of the
rate of the phenol consumption (a free radical scavenger)
from the initial concentration indicates that in this conꢀ
centration range all the radicals generated by the initiator
are accepted by the phenol. The rate of the phenol conꢀ
sumption is
–
d[PhOH]/dt = W /f,
i
where W = k [AAPH] is the rate of generation of radicals
i
i
upon initiator decomposition, f is the stoichiometric coꢀ
•
efficient indicating how much RO2 in total reacts with
one molecule of PhOH. In aqueous solutions, the rate
constant value for the decomposition of AAPH into radiꢀ
–
6 –1 44,45
cals at 37 °С is equal to k = 1•10
s
.
In Fig. 1, b, it
i
–
5
–1
is seen that at a concentration [RVT] > 0.7•10 mol L
resveratrol is consumed at
a practically constant rate of 0.9•10 mol L
–
8
–1 –1
and W = 1.8•10 mol L
s
i
–
8
–1 –1
s , which
Dye A
is 0.5 W . This means that under the experimental condiꢀ
i
tions, the stoichiometric coefficient for RVT is equal to 2.
The rate constant of the reaction of resveratrol with
peroxyl radicals was determined by the method of comꢀ
peting reactions tested in the work for evaluation of the
antiradical activity of natural thiols. A waterꢀsoluble polyꢀ
Experimental
4
0
transꢀResveratrol (RVT, ABCR GmbH), glutathione (GSH),
and cysteine (CSH) (SigmaꢀAldrich), hydrogen peroxide (Usol´ꢀ

Kinetics of resveratrol reaction
Russ. Chem. Bull., Int. Ed., Vol. 66, No. 11, November, 2017 2147
D
D
a
1
1
0
0
0
0
.2
.0
.8
.6
.4
.2
1.0
0
0
0
0
.8
.6
.4
.2
2
95
345
395 λ/nm
5
–1
[
RVT]•10 /mol L
300 350
400 450 500 550 600 λ/nm
b
6
5
4
3
2
1
Fig. 2. The overꢀtime changes in the absorption spectra of an
–
5
–1
aqueous solution containing 1.1•10
mol L
of dye А,
–
5
–1
–3
–1
1
.1•10 mol L of RVT, and 18•10 mol L of ААРН at
5
4
3
37 °С (the spectra were recorded every 1 min).
RO2• + А → А (k )
•
A
(
W is the rate of consumption of А)
(3)
А
2
1
RO2• + PhO → Products
•
(
recombination/disproportionation)
(4)
(5)
1
2
3
4
5
6
t/min
Fig. 1. (а) Consumption of RVT (3.66•10–5 mol L–1) at the
•
•
А + А → Products
reaction with radicals formed upon decomposition of ААРН
–
1
(
18 mmol L ) in aqueous medium at 37 °С (the spectra were
recorded every 1 min). (b) Kinetic curves of consumption of
•
•
А + PhO → Products.
(6)
–
1
RVT in the reaction with radicals, [ААРН] = 18 mmol L
;
5
–1
[
RVT]•10 mol L : 0.7 (1), 0.99 (2), 2.72 (3), 3.66 (4), and
.82 (5).
Since at the rate of radical initiation W
3•10 mol L
PhOH] > 5•10 mol L the dye and RVT intercept all
≤
i
4
–
8
–1 –1
≤
[
s
and the concentrations [A] and
–
6
–1
methine dye А with known spectral characteristics40,41
the radicals, the disproportionation reaction of radicals
RO • was excluded. It is obvious that reactions (4) and
and rate constant of the reaction with peroxyl radicals
2
•
(5) proceed at high rates and provide for resveratrol
RO2 initiated by ААРН in aqueous medium served as
4
0,41
a stoichiometric coefficient f = 2 and for dye А f = 1.
In reaction (6), the alkyl radical А reacts with phenoxyl
a spectrokinetic probe (a base comparison acceptor). At
4
–1 –1
•
3
7 °С, k = 5.4•10 L mol
s , the stoichiometric coꢀ
A
radical, therefore the rate constant of this reaction can be
high enough to compete with reaction (4).
efficient f = 1. At close concentrations of resveratrol and
dye in the presence of AAPH, consumption of both comꢀ
ponents is observed (Fig. 2). At a constant rate of radical
initiation, the rate of the dye consumption decreases upon
addition of RVT, i.e., the latter acts as a competing acꢀ
ceptor of radicals.
If W(6) >>W(4), we can assume that W = W
PhOH
+ WA.
i
In this case, the concentration of the peroxyl radicals is
•
[
RO ] = W /{k [А] + k [PhOH]} and kef = kPhOH. If
i
А
ef
2
W(6) << W(4), than k = 2 kPhOH.
ef
The rate of the dye consumption with the addition of
PhOH is expressed by the equation
The kinetic scheme describing the generation of the
radicals (1), their reaction with two acceptors PhOH (2)
and A (3), and quadratic termination in recombinaꢀ
tion and/or disproportionation reactions (4—6) looks as
follows:
W = k [A] [RO2•] =
A
A
= (k [A] W )/{k [А] + k [PhOH]}.
(7)
A
i
А
ef
AAPH → RO2• (initiation, W = k [AAPH])
(1)
To analyze the experimental data, it is convenient to
transform Eq. (7) to the form
i
i
RO2• + PhOH → PhO + ROОH
•
(
kPhOH, reaction with resveratrol)
(2)
1/W = (1 + (k /k )•([PhOH]/[A]))/W .
(8)
A
ef
A
i

2
148
Russ. Chem. Bull., Int. Ed., Vol. 66, No. 11, November, 2017
Zinatullina et al.
Table 1. The rates of consumption of dye А and RVT in the reaction with radicals formed upon decomposition of ААРН
5
–1
WPhOH•10 /mol L s–1
8
–1
5
–1
W •10 /mol L s–1
8
–1
Entry
[PhOH]•10 /mol L
[A]•10 /mol L
[PhOH] : [A]
A
1
2
3
4
5
6
7
0
0
1.07
0.94
0.63
0.44
1.03
0.31
0.82
1.51
1.06
0.54
0.33
0.59
0.14
0.22
—
0.61
0.65
0.91
0.91
1.15
1.91
0.77
1.06
1.37
0.91
1.31
1.32
0.64
1.04
2.04
0.89
4.43
2.31
Equation (8) was used in the work40 for analysis of
experimental data and determination of the rate constants
of the reaction of peroxyl radicals with thiols.
the ordinate axis, while the value k = 11.7•10 mol L s–1
4
–1
ef
can be calculated from the slope of the line tgϕ =
= k /(k •W ).
ef
A
i
Table 1 shows the experimentally measured rates of
consumption of dye A and RVT for different concentraꢀ
tion ratios [PhOH] : [A]. From Fig. 3, it is seen that the
dependence of the rate of dye A consumption on the conꢀ
centrations of both reagents is linearized in the coordiꢀ
Since the absorption spectra of resveratrol and the dye
practically do not overlap (see Fig. 2), the rates of the
resveratrol consumption were measured simultaneously
with the measurements of the dye consumption rate. From
the analysis of equations (1)—(6), it follows that the ratio
of rates is proportional to the ratio of their concentraꢀ
tions:
nates of Eq. (8). The segment equal to 1/W is cut off on
i
08/WA
1
a
WPhOH/W = (k
[PhOH])/(k [A]).
(9)
A
PhOH
A
8
Figure 3, b shows that the experimental data are linꢀ
earized in the coordinates of Eq. (9). Taking into account
6
4
2
the slope of the resulting straight line (tgϕ = k
/k =
PhOH
–1
A
4
–1
=
1.96), the value kPhOH = tgϕ•k = 10.6•10 mol L s
A
was calculated. The k and k
values are similar within
ef
PhOH
a 10% error. This means that peroxyl radicals are conꢀ
sumed mainly in parallel reactions with the dye and resꢀ
veratrol. It is noteworthy that the rate constant of the
reaction of resveratrol with peroxyl radicals in aqueous
5
–1
–1
solution equal to (1.1±0.1)•10 mol L s is close to
1
2
3
4
[PhOH] : [A]
25,26
the values obtained in oxidizing styrene
and characꢀ
terizes RVT as a medium strength inhibitor.
The hydroxy group at position 4´ of resveratrol is preꢀ
dominantly involved in the reactions with peroxyl radiꢀ
WPhOH/WA
b
1
0
9
8
7
6
5
4
3
2
1
25,26,29
cals.
More active and less selective hydroxyl radiꢀ
•
cals (НО ), along with the hydrogen atom abstraction
from the phenolic hydroxyls, adds to the double bond,
which results in the formation of resveratrol desintegraꢀ
tion products, рꢀhydroxybenzaldehyde and 3,4ꢀdihydrꢀ
oxybenzoic aldehyde and acid.2
7,28
It is also known that
thiyl radicals readily undergo addition to the double
bonds.3
3,34
These reactions lie in the basis of the reacꢀ
tions of thiols with unsaturated compounds, which are
4
6—50
called clickꢀchemistry thiol—еne reactions,
mainly
used for the synthesis of linear and branched heterochain
polymers. It was noted that terminal double bonds are
more active in the addition of thiols, therefore, comꢀ
pounds with one or more terminal unsaturated bonds were
used as the ene monomer component for the synthesis of
1
2
3
4
[PhOH] : [A]
Fig. 3. (а) The dependence of the rate of dye A consumption
W ) on the ratio of concentrations of RVT and A ([PhOH] : [А])
in the coordinates of Eq. (8). (b) The dependence of the ratio of
rates of consumption of RVT and the dye (WPhOH/W ) on the
ratio of their concentrations ([PhOH] : [А]) in the coordinates
(
А
A
5
1,52
polymers. In the works,
we observed the reaction of
of Eq. (9).
mercaptoethanol and glutathione with βꢀcarotene, the

Kinetics of resveratrol reaction
Russ. Chem. Bull., Int. Ed., Vol. 66, No. 11, November, 2017 2149
Wmax = а[RVT][CSH]0.7
,
molecule of which contain 11 conjugated unsaturated
bonds. It was noted that the rate of its consumption with
the addition of glutathione without hydroperoxide addiꢀ
tives is relatively low. Since the resveratrol molecule conꢀ
tains a double bond, though not terminal but activated
by the conjugation with the phenol rings, it was of interꢀ
est to investigate its reactions with GSH and more
where the parameter а = 0.003 (mol L–
1 –0.7
)
s–1
.
Resveratrol reacts with glutathione much slower (see
Fig. 4, а, curve 2), but the reaction is accelerated by the
addition of hydrogen peroxide. In the work,4 it was
shown that radicals are formed in low yield in the reacꢀ
tion of GSH with H2O2 and a specific rate of the radical
formation in this reaction was determined
0
4
0
active CSH.
Figure 4, a shows the kinetic curves of the resveratrol
consumption in the reaction with these thiols. It can be
seen that the reaction of RVT with CSH proceeds much
faster than with GSH. The kinetic curve with CSH is
Sꢀshaped, which indicates a complex autoꢀaccelerated
character of the process. The maximum reaction rate,
determined by the slope of the tangent at the inflection
point (Wmax), has a complex dependence on the initial
concentrations of CSH and RVT. From the slope of these
dependences in logarithmic coordinates (Fig. 4, b), it
follows that the kinetic equation for Wmax has the form
ϖ = W /{[Н О ][GSH]} = 0.07•10 mol–1 L s–1
–3
.
i
2
2
Figure 5 (curve 1) shows the dependence of the initial
rate of resveratrol consumption on the rate of radical iniꢀ
tiation with the additives of glutathione with Н2О2
(Wi = ϖ[Н2О2][GSH]).
It is seen that the dependence is nonlinear, but beꢀ
comes a straight line in logarithmic coordinates (see Fig. 5,
curve 2). From Fig. 5 it follows that: 1) the rate of RVT
consumption is an order of magnitude higher than Wi;
2
) the order of the reaction in W determined from the
i
slope of curve 2 is equal to 0.7 (WRVT ∼ (Wi)0 ). These
data is an evidence in favor of the chain mechanism of
RVT consumption (the chain length ν = |d[RVT]/dt|/Wi ∼
.7
D
a
1
0
0
0
.0
.8
.6
.4
∼
10—100). In the absence of oxygen, the mechanism of
2
the thiol—ene process in an excess of glutathione can be
represented by the following reactions (Scheme 1).
According to Scheme 1, the rate of RVT consumption
WRVT ∼ (Wi)0 . Under aerobic conditions, the RVT*•
.5
radicals can add О , while the resulting peroxyl radicals
2
can be involved in the chain termination. Apparently, the
proportionality WRVT ∼ (Wi)0 observed in the experiꢀ
ment can be explained by this circumstance, since all the
reactions were conducted in air. It is possible that the
autocatalytic unfolding of the reaction of RVT with cysꢀ
teine (see Fig. 4), which is much more active than gluꢀ
1
.7
2
0
40
60
80
100 t/min
1
0 + lgWmax
b
8
–1
1
1
1
1
1
1
1
.8
.7
.6
.5
.4
.3
.2
9 + lgWRVT
WRVT•10 /mmol L s–1
9
–1
0
0.5 1.0 1.5 2.5 W •10 /mmol L s–1
i
2
1
1
.8
6
1.6
1
5
1
1
1
.4
.2
.0
2
4
3
2
1
0
0.8
0
0
0
.6
.4
.2
0
0
.4
0.6
0.8
1.0
6 + lg[RVT], 3 + lg[CSH]
Fig. 4. (а) Kinetic curves of the consumption of RVT in the
reaction with 25 mmol L of cysteine (1) and glutathione (2).
–
1
0
0.5 1.0
1.5 2.5 3.0 11 + lgWi
(
(
=
[
b) The dependence of the maximum rate of RVT consumption
Wmax) on the concentrations of CSH (1) at [RVT] =
Fig. 5. The dependence of the rate of RVT consumption (WRVT) on
the initiation rate (W ) in normal (1) and logarithmic (2) coorꢀ
i
–
1
–5
–1
0.032 mmol L and on the concentrations of RVT (2) at
dinates; an aqueous medium, 37 °С. [RVT] = 2•10 mol L ,
–
1
[GSH] = 5 mmol L , [H O ] = 0.22—27 mmol L–1.
–1
CSH] = 25 mmol L , 37 °С, an aqueous solution.
2
2

2
150
Russ. Chem. Bull., Int. Ed., Vol. 66, No. 11, November, 2017
Zinatullina et al.
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9
. Z. Meng, H. Jing, L. Gan, H. Li, B. Luo, Am. J. Transl. Res.,
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016, 8, 2641.
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1
1
0. B. N. Zordoky, I. M. Robertson, J. R. Dyck, Biochim. Bioꢀ
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Biol. Med., DOI: 10.1016/j.freeradbiomed.2016.08.006.
RVT*• is an alkyl radical resulting from the addition of the thiyl
radical to the double bond of resveratrol.
tathione in the reactions with oxygen and radicals, is also
caused by the effect of oxygen, which generates radicals
and then hydrogen peroxide in the reactions:
13. B. Olas, P. Nowak, J. Kolodziejczyk, M. Ponczek, B. Waꢀ
chowicz, J. Nutr. Biochem., 2006, 17, 96.
4. B. Tadolini, C. Juliano, L. Piu, F. Franconi, L. Cabrini, Free
Rad. Res., 2000, 33, 105.
5. Y. J. Cai, J. G. Fang, L. P. Ma, L. Yang, Z. L. Liu, Biochim.
Biophys. Acta, 2003, 1637, 31.
6. L. Frémont, L. Belguendouz, S. Delpal, Life Sci., 1999,
1
1
1
1
1
1
CSH + O → CS + HO2•
•
2
HO2• + HO2• → H O + O
2
2
2
6
4, 2511.
7. P. Brito, L. M. Almeida, T. C. Dinis, Free Rad. Res., 2002,
6, 621.
The formation of Н О increases the rate of initiation
2
2
in the system RVT—CSH and, consequently, the rate of
resveratrol consumption. The studies of the thiol—еne
reactions under anaerobic conditions, as well as the inꢀ
fluence of oxygen and medium on the rate and mechaꢀ
nism of these important for bioantioxidants reactions, is
the subject of our future research.
3
8. D. Pietraforte, L. Turco, E. Azzini, M. Minetti, Biochim.
Biophys. Acta, 2002, 1583, 176.
9. H. Berrougui, G. Grenier, S. Loued, G. Drouin, A. Khalil,
Atherosclerosis, 2009, 207, 420.
20. B. Fauconneau, P. WaffoꢀTeguo, F. Huguet, L. Barrier,
A. Decendit, J.ꢀM. Merillon, Life Sci., 1997, 61, 2103.
21. D. G. Soares, A. C. Andreazza, M. Salvador, J. Agric. Food
Chem., 2003, 51, 1077.
22. E. T. Denisov, T. G. Denisova, Handbook of Antioxidants,
CRC Press, Boca Raton, 2000.
In conclusion, we found that resveratrol reacts with
peroxyl radicals in aqueous media. The reaction rate conꢀ
5
–1
–1
stant was determined ((1.1±0.1)•10 mol L s ), which
is similar to the values obtained in oxidizing styrene25,26
and characterizes RVT as a medium strength inhibitor. It
was established for the first time that resveratrol actively
reacts with cysteine in aqueous solutions. The reaction
with glutathione is slower and accelerates with the addiꢀ
tion of hydrogen peroxide. The thiolꢀene reaction with
resveratrol follows a chain mechanism with a chain length
of several dozen. These results may be important for
understanding the physiological role of thiols in the overꢀ
all oxidation process.
2
3. J.ꢀG. Fang, M. Lu, Z.ꢀH. Chen, H.ꢀH. Zhu, Y. Li, L.Yang,
L.ꢀM Wu, Z.ꢀL. Liu, Chem. Eur. J., 2002, 8, 4191.
4. A. M. Alonso, C. Domínguez, D. A. Guill e´ n, C. G. Barroso,
J. Agric. Food. Chem., 2002, 50, 3112.
2
25. A. Amorati, F. Ferroni, G. F. Pedulli, L.Valgimigli, J. Org.
Chem., 2003, 68, 9654.
26. R. Amorati, M. Lucarini, V. Mugnaini, G. Franco Pedulli,
J. Org. Chem., 2004, 69, 7101.
2
2
2
7. L. Camont, F. Collin, M. Couturier, P. Thérond, D. Jore,
M. GardèsꢀAlbert, D. BonnefontꢀRousselot, Biochimie,
2
012, 94, 741.
This work was financially supported by the Russian
Science Foundation (Project No. 14ꢀ23ꢀ00018ꢀP).
8. L. Camont, C. H. Cottart, Y. Rhayema, V. NivetꢀAntoinea,
R. Djelidi , F. Collin, J. L. Beaudeuxa, D. BonnefontꢀRousꢀ
selot, Anal. Chim. Acta, 2009, 634, 121.
9. Y. Rhayem, P. Therond, L. Camont, M. Couturier, J.ꢀL.
Beaudeux, A. Legrand, D. Jore, M. GardesꢀAlbert, D. Bonꢀ
nefontꢀRousselot, Chem. Phys. Lipids, 2008, 155, 48.
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Received June 21, 2017;
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in revised form August 10, 2017