CHEMICAL REACTIONS IN GAS, LIQUID AND SOLID PHASES: SYNTHESIS, PROPERTIES AND APPLICATION pptx

CHEMISTRY RESEARCH AND APPLICATIONS









CHEMICAL REACTIONS IN GAS,
L
IQUID AND SOLID PHASES:
S
YNTHESIS, PROPERTIES
AND APPLICATION


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CHEMISTRY RESEARCH AND APPLICATIONS








CHEMICAL REACTIONS IN GAS,
L
IQUID AND SOLID PHASES:
S
YNTHESIS, PROPERTIES
AND APPLICATION





G. E. ZAIKOV
AND

R.
M. KOZLOWSKI
EDITORS







Nova Science Publishers, Inc.
New York



Copyright © 2010 by Nova Science Publishers, Inc.


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IBRARY OF CONGRESS CATALOGING-IN-PUBLICATION DATA

Chemical reactions in gas, liquid, and solid phases : synthesis, properties,
and application / editors, G.E. Zaikov, R.M. Kozlowski.
p. cm.
Includes index.
ISBN 978-1-61668-906-3 (eBook)
1. Polymers Biodegradation. 2. Composite materials Biodegradation. I.
Zaikov, Gennadii Efremovich. II. Kozlowski, R. (Ryszard)
QD381.9.D47C54 2009
541'.39 dc22
2010015588

Published by Nova Science Publishers, Inc.
Ô
New York











CONTENTS


Preface ix

Chapter 1 Classification of Polymers in Reactivity Toward Nitrogen Oxides 1
E. Ya. Davydov, I. S. Gaponova, G. B. Pariiskii, T. V. Pokholok
and G. E. Zaikov

Chapter 2 Influence of the Initiation Rate of Radicals on the Kinetic
Characteristics of Quercetin and Dihydroquercetin in the Methyl
Oleate Oxidation 11

L. I. Mazaletskaya, N. I. Sheludchenko and L. N. Shishkina

Chapter 3 An Antioxidant from Hindered Phenols Group Activates Cellulose
Hydrolysis By Celloviridin in a Wide Concentration Range,
Including Ultralow Doses 21

E. M. Molochkina, Yu. A. Treschenkova, I. A. Krylov
and E. B. Burlakova

Chapter 4 a-Tocopherol as Modifier of the Lipid Structure of Plasma
Membranes In Vitro in a Wide Range of Concentrations
Studied by Spin-Probes 29

V. V. Belov, E. L. Maltseva and N. P. Palmina
Chapter 5 Supercritical Carbon Dioxide Swelling of Polyheteroarylenes
Synthesized in N-Methylpyrrolidone 45

Inga A. Ronova, Lev N. Nikitin, Gennadii F. Tereschenko
and Maria Bruma

Chapter 6 Inhibition of 2-Hexenal Oxidation By Essential Oils of Ginger,
Marjoram, Juniper Berry, Black and White Pepper 65

T. A. Misharina, M. B. Terenina, N. I. Krikunova
and I. B. Medvedeva

Chapter 7 The Organophosphorus Plant Growth Regulator Melaphen
as Adaptogen to Low Moisher 75

I. V. Zhigacheva, E. B. Burlakova, T. A. Misharina, M. B.Terenina,
N. I. Krikunova, I. P. Generozova and A. G. Shugaev


Contents
vi
Chapter 8 Antioxidant Properties of Essential Oils from Clove Bud,
Laurel, Cardamom, Nutmeg and Mace 83

T. A. Misharina, M. B. Terenina, and N. I. Krikunova
Chapter 9 Specific Properties of Some Biological Composite Materials 91
N. Barbakadze, E. Gorb and S. Gorb
Chapter 10 Properties and Applications of Aminoxyl Radicals
in Polymer Chemistry 123

E. Ya. Davydov, I. S. Gaponova, G. B. Pariiskii, T. V. Pokholok,
and G. E. Zaikov

Chapter 11 Synthesis of Flexible Manufacturings for Phosphoric Industry
Waste Utilization Based on the Cals-Concept 155

A. M. Bessarabov, A. V. Kvasyuk and G. E. Zaikov
Chapter 12 Practical Hints on the Application of Nanosilvers in Antibacterial
Coating of Textiles 165

S. Dadvar, A. Oroume

and A. K. Haghi
Chapter 13 The Nanostructure and Yield Process of Cross-Linked Epoxy
Polymers 191

Z. M. Amirshikhova, G. V. Kozlov, G. M. Magomedov
and G. E. Zaikov


Chapter 14 Nanostructures in Cross-Linking Epoxy Polymers and Their
Influence on Mechanical Properties 197

Z. M. Amirshikhova, G. V. Kozlov, G. M. Magomedov

and G. E. Zaikov 
Chapter 15 The Degradation Heterochain Polymers in The Presence of
Phosphorus Stаbilizers 205

E. V. Kalugina, N. V. Gaevoy, 
K. Z. Gumargalieva and G. E. Zaikov
Chapter 16 Quantum-Chemical Calculation of Olefins of Cationic
Polymerization Branching in -,- and  Position on Relations to
Double Connection By Method MNDO 221

V. A. Babkin, D. S. Andreev, T. V. Peresypkina and G. E. Zaikov 
Chapter 17 Thermodynamics for Catalase and Hydrogen Peroxide Interaction 227
A. A. Turovsky, A. R. Kytsya, L. I. Bazylyak and G. E. Zaikov
Chapter 18 Dr. Rer. Nat. Wolfgang Fritsche – Scientist and Organizer of
International Science (Secretary General Rtd. of Gesellschaft
Deutscher Chemiker, Honorary President of Federation
of European Chemical Societies) 245

G. E. Zaikov 
Chapter 19 Professor Victor Manuel De Matos Lobo on His 70th Anniversary 249
Gennady E. Zaikov and Artur J. M. Valente 
Contents
vii
Chapter 20 The Scientist Who Outstripped His Time 251
Revaz Skhiladze and Tengiz Tsivtsivadze 

Chapter 21 Prof. Dr. Ryszard Michal Kozlowski: Half a Century in Science
and Technology 263

Gennady Zaikov
Chapter 22 The Second International Conference on Biodegradable Polymers
and Sustainable Composites (BIOPOL-2009) 267

G. E. Zaikov, L. L. Madyuskina and M. I. Artsis 
Index 271













“If you are sixty (or more)
and you are not feeling any pain in your body
when you are getting up in the morning,
it means that you have passed away (already)”
Russian proverb

PREFACE

This epigraph is very correct for the Russian Federation today because the average
lifespan of Russian men in this country is 57 years (Russian women are living on ten years
more). It is statistical data. Russian scientists are an exception. Particularly, the majority of
contributors of this volume are older then 60 and the editor of volume is older then 75.
We can explain this exception (phenomena) if we take in account the next Russian
proverb: “All illnesses are from nerves and only a small amount from pleasure”. We expect
that readers immediately are thinking about sex as a part of pleasure. It is only partly right.
Alcohol, tobacco and narcotics should also be included in the “pleasure” part. Unfortunately,
the Russian people are world champions for drinking. The average Russian man (including
ladies, children and even babies) drinks 18 liters of pure ethyl alcohol (calculation done in
pure alcohol) per year. It is twice more than twice the critical amount (9 liters).
Russian scientists are again an exception because the majority of them have pleasure only
in the case of communication with SCIENCE!
Now we should remember the Kazakh (people living in the Asian part of former USSR)
proverb: “If sixty years are coming the mind (brain, memory) will go back (to childhood
conditions)”. We expect that this proverb is also not correct for Russian scientists. As
evidence of this opinion you can read the chapters of this volume where the most part of
chapters were prepared by scientists from Russian Research Centers and from Research
Centers of former Republics (now independent states) of the USSR.
It is now the right time to remember English proverb: “Please eat one apple every day
and you will not need a physician” (it is a reverse translation from Russian to English). We do
not know exactly if it is enough to eat one apple a day to be permanently healthy or not. We
do know that positive emotions are in favor for good health. We expect that this book can
(should) give only positive emotions to readers and we are waiting for the opinions of readers
in this case.
So, we should stop about proverbs and start about chemical science and application.
This volume includes information about kinetics and mechanism of chemical reactions in
different phases: classification of polymers in reactivity toward nitrogen oxides (polluted
atmosphere), influence of the initiation rate of radicals on the kinetic characteristics of

quercetin and dihydroquercetin in the methyl oleate oxidation, an antioxidant from hindered
Gennady E. Zaikov and R. M. Kozlowski x
phenols group activates cellulose hydrolysis by celloviridin in a wide concentration range,
including ultralow doses, α-tocopherol as modifier of the lipid structure of plasma membranes
in vitro in a wide range of concentrations studied by spin-probes, supercritical carbon dioxide
swelling of polyheteroarylenes synthesized in N-methylpyrrolidone, inhibition of 2-hexenal
oxidation by essential oils of ginger, marjoram, juniper berry, black and white pepper,
specific properties of some biological composite materials, the organophosphorus plant
growth regulator melaphen as adaptogen to low moisher, properties and applications of
aminoxyl radicals in polymer chemistry, synthesis of flexible manufacturings for phosphoric
industry waste utilization based on the cals-concept, practical hints on application of
nanosilvers in antibacterial coating of textiles, the degradation heterochain polymers in the
presence оf phosphorus stаbilizers, quantum-chemical calculation of olefins of cationic
polymerization and antioxidant properties of essential oils.
The nanostructure and yield process of cross-linked epoxy polymers as well as
nanostructures in cross-linking epoxy polymers and their influence on mechanical properties
are discussed in this volume.
Somebody asked Henry Ford: “Which car is better?” Ford answered: “A new one”. No
doubt a new car as well as new scientific information is better than old ones (only old cognac
is better than the new one). We took this idea into account in case preparation of our volume.
So, this volume is a complete guide to the subject of kinetic and mechanisms of chemical
reactions in gas, liquid and solid states. The editors and contributors will be happy to receive
from the readers some comments which we can use in our research in the future.
Once, Agatha Christie was filling out a form. There was a question: “What is your
occupation” and she wrote “A married lady”.
Of course Agatha Christie could write on any form whatever she wanted because
everybody knew her.
What is important for us is that in filling out any form we contributors could write with a
clear conscience – “a scientist.”

Gennady E. Zaikov
N.M. Emanuel Institute of Biochemical Physics
Russian Academy of Sciences
4 Kosygin Str., Moscow 119334, Russia

Ryszard M. Kozlowski
Institute for Engineering of Polymer Materials and Dyes
Torun, Poland
In: Chemical Reactions in Gas, Liquid and Solid Phases… ISBN: 978-1-61668-671-0
Editors: G. E. Zaikov, R. M. Kozlowski, pp.1-10 ©2010 Nova Science Publishers, Inc.






Chapter 1



CLASSIFICATION OF POLYMERS IN REACTIVITY
TOWARD NITROGEN OXIDES


E. Ya. Davydov, I. S. Gaponova, G. B. Pariiskii,
T. V. Pokholok, and G. E. Zaikov
*

N.M. Emanuel Institute of Biochemical Physics,
Russian Academy of Sciences, Moscow, Russia

ABSTRACT

The review is includies information about the kinetics and mechanism of interaction
of nitrogen oxides with carbon-chain polymers, rubbers, aliphatic polyamides and
polyuretanes.

Keywords: nitrogen oxides, reactivity, polymers, classification, kinetics, mechanism.


The general review of influence of the pollutants on polymers has been presented by
Jellinek et al. [1]. Therein the characterization of reactivity of polymeric materials toward
aggressive gases is given. The various polymers were used as films of 20 μ thickness. The
thickness is enough small to exclude in most cases the diffusion as the determining factor of
the pollutant action. The films were investigated under different conditions: 1) the pollutant
action; 2) the oxygen action; 3) UV light action; 4) UV light and oxygen; 5) UV light, oxygen
and pollutants. For NO
2
, the exposure of samples was usually realized under the pressure of
15 mm Hg during 30 hours at 308 K. However, in a case of nylon 66 and butyl rubber, the
NO
2
pressure was lowered up to 1 mm Hg at during 30 min. Polyisoprene and polybutadiene
were exposed to NO
2
during 5 min under a pressure of 1 mm Hg. As a light source (λ > 290
nm), a mercury lamp was used. The intrinsic viscosity of polymer solutions was measured
before and after exposure of samples in the chosen conditions. The rather high concentration

* N.M. Emanuel Institute of Biochemical physics, Russian Academy of Sciences, 4 Kosygin Street, 119334
Moscow, Russia, Fax: (7-495)1374101, E-mail: ,
E. Ya. Davydov, I. S. Gaponova, G. B. Pariiskii et al.
2
of nitrogen dioxide in these experiences was used to be convinced that the certain effects can
be observed for a reasonable time.
The polymers on the basis of their reactivity with respect to NO
2
can be divided into two
main classes [1]. The saturated polymers, for instance, polyethylene (PE) and polypropylene
(PP) belong to the first group, but nylon 66 is not included into this series. The second group
covers elastomers. Butyl rubber undergoes scissions of the main chain, and polybutadiene is
restrictedly cross-linked under the action of NO
2
. These elastomers have approximately the
same reactivity with respect to NO
2
as to ozone. All films exposed to NO
2
become yellow,
and their IR spectra show that nitro groups enter into macromolecules. In polyvinylchloride in
the presence of NO
2
, some decreasing the amount of chlorine along with the appearance of
nitro and nitrite groups are observed from IR spectra.
It is the author’s opinion [1] that some estimations concerning influences of so low
concentration of nitrogen dioxides in an atmosphere (2⋅10
−9
− 2⋅10
−8

mol⋅l
−1
) on polymeric
materials can be obtained from the experiences with using concentrations of the gas of several
orders of magnitude higher. The formulated assumption says that there is linear dependence
of the concentration effect of aggressive pollutants. This means that the effect of aggressive
gases at low concentrations can be determined by the linear extrapolation of results obtained
under the influence of high concentrations. The author pointed out that this procedure
contains an element of risk because scissions of macromolecules in some cases are not always
linearly decreased with the pressure reduction of the aggressive gas, but the rate of breaks can
change drastically at very low concentrations.
The procedure of extrapolation was used for an estimation of the scission average number
S
under the action of aggressive gases at concentrations of 1 − 5ppm within 1 hour [1]. This
value is given by the equation:

1
,
0,
−=
tn
n
DP
DP
S
(I.1)

where
0,n
DP and

tn
DP
,
are lengths of macrochains at t =0 and t correspondingly. On the
basis of these estimations, it was concluded that aggressive gases, for instance NO
2
and SO
2
,
slightly effect on vinyl polymers in concentrations really available in polluted air. Even in a
combination with UV light, the deterioration of these polymers is hardly noticeable.
However, nylon 66 is quite subjected to the action of small concentrations of NO
2
with
essential degradation.


I.1. INTERACTION OF CARBON-CHAIN POLYMERS WITH NO
2

Pioneering studies of the reaction of nitrogen dioxide with polyethylene (PE) and
polypropylene (PP) have been carried out by Ogihara et al. [2, 3]. Using IR spectroscopy,
they have found that nitrogen dioxide cannot abstract secondary and tertiary hydrogen atoms
from PE and PP at 298 K. It can only add to the vinylene and vinylidene units that are formed
Classification of Polymers in Reactivity Toward Nitrogen Oxides
3
in the synthesis of the polymers. These reactions resulted in dinitro compounds and nitro
nitrites:

C=C + NO

2
C
C
H
NO
2
(I.2)
C
C
H
NO
2
+ NO
2
C
C
H
NO
2
O
2
N
C
C
H
NO
2
ONO

(I.3)



(I.4)

At T > 373 K, nitro, nitrite, nitrate, carbonyl and hydroxy groups are formed in these
polymers. The following reaction mechanism at high temperatures was proposed:

RH + NO
2
→ R
•
+ HNO
2
(I.5)

R
•
+ NO
2
→ RNO
2
(I.6)

R
•
+ ONO → RONO (I.7)

RONO → RO

•
+ NO (I.8)

RO
•
+ NO
2
→ RONO
2
(I.9)

RH + RO
•
→ R
•
+ ROH (I.10)

~CH
2
-CH
2
-CH
2
-O
•
→ ~CH
2
-CH
2
-CHO + H (I.11)

This scheme allows rationalization of the accumulation of the nitro groups, which
proceeds at a constant rate and autoaccelerated formation of nitrates, alcohols and carbonyl
compounds.
However, it provides no explanation for S-shaped dependence of the accumulation of
nitrites.
The activation energies for the NO
2
addition to the double bonds of PE are 8-16 kJ⋅mol
−1
.
The activation energy for hydrogen abstraction is within of 56 and 68 kJ⋅mol
−1
for PE and 60
kJ⋅mol
−1
for PP.
At room temperature and at NO
2
concentrations of 5.4⋅10
−4
– 5.4⋅10
−3
mol⋅l
−1
, the
characteristics of PE, PP, polyacrylonitrile and polymethylmethacrylate (PMMA) are changed
only slightly even if they simultaneously undergo to a combined action of NO
2
, O

2
and UV
radiation [4]. Reactions of NO
2
with polyvinylchloride and polyvinyl fluoride resulted in a
slight decrease in the content of chlorine and fluorine atoms, respectively [1, 4].
E. Ya. Davydov, I. S. Gaponova, G. B. Pariiskii et al.
4
In the temperature range of 298−328 K nitrogen dioxide (7.8⋅10
−3
−3.4⋅10
−2
mol⋅l
−1
) can
abstract tertiary hydrogen atoms from polystyrene (PS) molecules to introduce nitro and
nitrite groups into macromolecules in result of subsequent reactions [1]. This process
proceeds at low rates and is accompanied by chain scissions [1, 5, 6]. The number of chain
scissions on time α(t) was determined from intrinsic viscosity using the equation (I.1). The
experiments have been carried out at the temperature range of 298-328 K. According to
Jellinek, the dependence of the decrease in the degree of polymerization of PS on the
exposure time in NO
2
has three linear regions: initial, middle and final. A decrease in the
apparent degradation rate was observed in the middle region of the dependence. Presumably
this was related to the association of the macromolecules in solution, which is due to the
effect of polar groups and can affect the results of viscosimetric measurements. Subsequent
increase in the apparent degradation rate was attributed to the consumption of these nitrogen-
containing groups and to a decrease in the degree of association of the macromolecules. PS
films were also simultaneously exposed to NO

2
(1.1·10
−4
mol·l
−1
) and light (λ > 280 nm) [6].
No polymer degradation was observed in the initial stage during 10 h. Then chain scission
occurred at a constant rate.
An attempt to determine quantitative characteristics of the ageing of PS and poly-t-
butylmethacrylate (PTBMA) under the action of NO
2
has been undertaken by Huber [7]. The
samples were exposed to a stream of air containing NO
2
(2.5⋅10
−6
– 3.7⋅10
−5
mol⋅l
−1
) at 300 K
and simultaneously irradiated with light (λ>290 nm). The number of chain scission per 10000
monomer units α(t) can be described by the empirical equation:

()
1exp −=α Qt
Q
P
(I.12)

where P and Q are constants. This equation describes an autocatalytic process. At Q → 0,
degradation occurs at a constant rate. Autocatalytic process is more pronounced for thin films.
Degradation of thin PS films under the same conditions occurs slower than that of the
PTBMA films and its autocatalytic nature is more pronounced.
The autocatalytic path of degradation of PTBMA was associated [7] with the photo-
induced formation of isobutylene, which reacts with NO
2
, thus initiating free-radical
degradation processes of macromolecules. The IR spectrum of PS exposed toNO
2
and light
exhibits two bands at 1686 and 3400 cm
−1
corresponding to the carbonyl and hydroxyl
groups, respectively. The formation of nitrogen-containing products has not been observed in
both PTBMA and PS. The following reactions have been proposed [7] in PS:

~ CH
2
−C(Ph)H ~ + NO
2
→ HNO
2
+ ~ CH
2
−C
•
(Ph) ~ (R
1
•

) (I.13)

R
1
•
+ O
2
→ R
1
O
2
•
(I.14)

R
1
O
2
•
+ RH → ROOH + R
1
•
(I.15)


Classification of Polymers in Reactivity Toward Nitrogen Oxides
5

R
1

+ NO
2
R
1
NO
2
R
1
ONO
(I.16)

(I.17)

R
1
ONO
⎯
→
⎯
νh
R
1
O
•
+ NO (I.18)

R
1
OOH + NO → R
1

O
•
+
•
OH + NO (I.19)

R
1
OOH
⎯
→
⎯
νh
R
2
•
+
•
OH (I.20)

R
1
O
•
→ R
2
•
+ degradation products (I.21)

It is believed that the decomposition of hydroperoxides exposed to NO

2
and light leads to
autocatalytic degradation of PS.


I.2. INTERACTION OF RUBBERS WITH NO
2

Rubbers are much more susceptible to NO
2
than the polymers containing no double
bonds. First, this is due to the ability of NO
2
to add reversibly to carbon-carbon double bonds
to give nitroalkyl radicals (reaction (I.2)), thus initiating free radical conversions of
elastomers. Second, nitrogen dioxide is able of abstracting hydrogen atoms in β−position to
the double bond to give allyl radicals, which then recombine with NO
2
[8]. Depending on the
structure of the alkene, the reaction resulting in the formation of the allyl radical can be either
weakly exothermic or weakly endothermic. For instance, the strength of the weakest C−H
bond in the structure CH
2
=C(CH
3
)CH
2
−H is only 314 kJ·mol
−1
[9].

The exposure of polyisoprene and polubutadiene to nitrogen dioxide leads to both
degradation and cross-linking of macromolecules, whereas butyl rubber (BR) (a copolymer of
36% isobutylene and 54% isoprene units) only undergoes degradation [10]. The detailed
study of the ageing BR exposed to NO
2
(5.2⋅10
−7
– 5.2⋅10
−5
mol⋅l
−1
) alone, an NO
2
−O
2

mixture and an NO
2
−O
2
mixture plus UV light (λ > 280 nm) at 298−358 K has been
performed by Jellinek et al.[11, 12]. IR spectra before and after the exposure of samples show
that the band at 1540 cm
−1
of ~ C=C ~ bonds disappears, and the new band at 1550 cm
−1

arises. The latter belongs to nitro groups appearing as a result of addition to double bonds by
the reaction (I.2).
The chain scission process in BR causes by the following scheme:

~C(CH
3
)=CH~ + NO
2
k
1
k
2
~C
CH~
NO
2
CH
3
k
3
chain scission
+ NO
2
+ NO
2
(I.22)
R


Then the rate of scissions is:
E. Ya. Davydov, I. S. Gaponova, G. B. Pariiskii et al.
6
]][NOR[

]'[
23
⋅
=− k
d
t
nd
(I.23)

where
'n is a number of isoprene units in BR. After integration of (I.23) taking into account
a stationary concentration of R
•
, the following equation for the degradation degree is derived:

]NO[(][
]NO[]'[
2320
2031
kkn
tnkk
+
=α
(I.24)

where
0
]'[n and
0
][n are the initial concentrations of isoprene units and all units. The

amount of double bonds remains practically constant because only a small number of those
are destroyed. Really, only 1/50 of macromolecules of BR are subjected to scissions. Taking
into account low concentrations of NO
2
, the linear dependence on time is obtained:

tk
exp
=α
(I.25)

where
exp
k is the experimentally determined constant. This constant is represented by the
following Arrhenius equation:
RT
ek
/74502
exp
108.3
−
−
⋅= , h
−1
.
The degradation of BR in a polluted atmosphere runs in three directions: 1) the action of
NO
2
alone, 2) the action of O
2

, 3) the combined (synergetic) action of these gases. The
general scheme of the process can be represented as follows:

RH + O
2

⎯
→
⎯
4
k
R
•
+ HO
2
(I.26)

R
•
+ O
2

⎯
→
⎯
5
k
RO
2
•

(I.27)

RO
2
•
+ RH
⎯
→
⎯
6
k
ROOH + R
•
(I.28)

ROOH
⎯
→
⎯
7
k
stable products (I.29)

k
8
k
9
k
10
chain scission products

+ O
2
+ O
2
[cage
1
]ROOH
(I.30)

The effect of NO
2
+ O
2
:

ROOH + NO
2

⎯
⎯
→
⎯
11
k
NO
2
−ROOH (I.31)

Classification of Polymers in Reactivity Toward Nitrogen Oxides
7

NO
2
-ROOH
k
12
k
13
[cage
2
]
k
14
chain scission products
(I.32)
2 R
•

⎯
⎯
→
⎯
15
k
[cage
3
] (I.33)

[cage
3
] + O

2

⎯
⎯
→
⎯
16
k
2 R
•
(I.34)

[cage
3
]
⎯
⎯
→
⎯
17
k
R−R (I.35)

The synergetic action of NO
2
and O
2
can be seen from the scheme:

~CH

2
C(CH
3
)=CHCH
2
CH
2
~ + O
2
→ ~CH
2
C(CH
3
)=CHCH(OO
•
)CH
2
~ + HO
2
•
(I.36)

~CH
2
C(CH
3
)=CHCH(OO
•
)CH
2

~ + RH → ~CH
2
C(CH
3
)=CHCH(OOH)CH
2
~ + R (I.37)


~CH
2
C(CH
3
)=CHCH(OOH)CH
2
~ + NO
2
→ ~CH
2
C(CH
3
)=C(NO
2
)CH(OOH)CH
2
~ (I.38)

BR is not sensitive to UV light (λ > 290 nm) alone. Probably, UV light in the presence of
NO
2

effects on nitro groups of macromolecules.


I. 3. INTERACTION OF NITROGEN DIOXIDE WITH ALIPHATIC
POLYAMIDES AND POLYURETHANES

Polymers containing amide and urethane groups form a particular class of materials
sensitive to NO
2
. Jellinek et al. [13, 14] showed that exposure of nylon-66 films of different
morphology to NO
2
(10
−5
− 2.6⋅10
−1
mol⋅l
−1
) causes main-chain scission in the polymers. The
degradation of nylon is a diffusion-controlled reaction. Its rate and depth depend essentially
on the degree of crystalline of samples and on the size of crystallites. The degradation is
accelerated in the presence of air and UV light in addition to NO
2
. The following mechanism
for the polymer degradation under the action of NO
2
was proposed:

C
O

N
H
+ NO
2
+ HNO
2
CH
2
CH
2
C
O
N CH
2
CH
2
NO
2
C
O
N CH
2
CH
2
NO
2
C
O
N CH
2

+ CH
2
(I.39)


The degradation process is inhibited by small amounts of benzaldehyde or benzoic acid.
It is believed that these compounds block the amide groups and that only a few of them, not
involved in hydrogen bonding, enter into the reaction:

E. Ya. Davydov, I. S. Gaponova, G. B. Pariiskii et al.
8
C
O
NH
CH
2
+
Ph
C
O
OH
C
N
O
H
H O
O
C
Ph
(I.40)

Jellinek et al. [14, 15] studied the effect of NO
2
on films of linear polyurethane
synthesized from tetramethylene glycol and hexamethylene diisocyanate. It was found that
the degradation of polyurethanes is accompanied by cross-linking of macromolecules and that
the degree of degradation and the yield (the weight percentage) of the gel fraction are
complex functions of the exposure time. For instance, the yield of the gel fraction initially
increases up to 20% and then decreases down to nearly zero at 330 K and NO
2
concentration
of 10
−3
mol⋅l
−1
. The number of chain scissions in the sol fraction (the degree of degradation)
increases initially, then decreases and eventually increases again; however, the final
degradation rate is lower than the initial one. Exposure of the polyurethane films to NO
2
is
accompanied by release of CO
2
. The IR spectra of the films allow assessment of the
consumption of NH bonds (ν = 3300 cm
−1
).
The reaction mechanism proposed [15, 16] involves the abstraction of hydrogen atoms
from two types of structures, namely, a carbamate structure (A) and a tertiary amide structure
(B):

C
O
NH
CH
2
O
C
O
N
CH
2
O
ZH
A
B


where Z is a side alkyl group. The next stages are represented as follows:
A
NO
2
C
O
N
CH
2
O
+ HNO
2
R

1
B
NO
2
C
O
N
CH
2
O
+ HNO
2
R
2
Z
R
1
+ NO
2
R
1
NO
2
R
1
N
H
2
C
+

C
O
O
CH
2
R
3
R
3
CO
2
+
H
2
C
R
1
+
R
2
cross-linking product
(I.41)
(I.42)
(I.43)
(I.44)
(I.45)
(I.46)

Classification of Polymers in Reactivity Toward Nitrogen Oxides
9

According to the Jellinek, recombination of R
1
•
and R
2
•
radicals leads to cross-linking of
the polymer chains, while decomposition of R
1
•
radicals results in the degradation of
macromolecules and the CO
2
release. Energetically, the decomposition of the R
1
•
radicals
seems to be improbable since this reaction results in the formation of terminal macroradical
R
3
•
and a nitrene, which is a very reactive species. On the other hand, the R
1
•
decomposition
reaction involving cleavage of C−C or C−O is more bonds produce no alkoxycarbonyl
macroradicals R
3
•
, which can undergo decarboxylation [16]. Therefore, the ageing of

polyurethanes in an NO
2
atmosphere can be represented as follows [17]:

Reaction (I.41)

Reaction (I.42)

B
NO
2
C
O
N
CH-CH
2
O
+ HNO
2
R
4
ZH
(I.47)


R
4
R
3
+ HZ- N=CH

(I.48)


R
3
CO
2
+ CH
2
(I.49)


2R
i
+ NO
2
nitration products
(I.50)


2R
i
cross-linking products
(I.51)


where i = 1−4.
This scheme expresses the degradation accompanied by cross-linking of macromolecules,
the consumption of NH groups of the polymer as well as the release of carbon dioxide upon
degradation.

The investigations performed earlier characterize in general the reactivity of polymers of
different classes in their reactions with nitrogen dioxide. However, mechanisms of free
radical processes proposed on basis of the results considered are enough formal. As a rule
they take account of changing molecular weights and the composition of final molecular
products of the nitration. In connection with this, the study of structures of free radicals
forming in primary and intermediate stages of polymer conversions attracts an especial
interest. Such researches allow drawing conclusions on the mechanism of initiation of free
radical conversions dependent on nature of functional groups of macromolecules. As is
shown by ESR measurements, different stable nitrogen containing macroradicals are formed
on exposure of polymers to NO
2
[17]. The analysis of the radical composition from ESR
spectra gives an opportunity for estimation of the polymer stability by the quite simple
method [18].
E. Ya. Davydov, I. S. Gaponova, G. B. Pariiskii et al.
10
REFERENCES

[1] Jellinek H. H. D. Degradation and Stabilization of Polymers. New York: Elsevier,
1978.
[2] Ogihara T Bull. Chem. Soc. Jap. 1963, 31, 58-
[3] Ogihara T., Tsuchiya S., Kuratani K. Bull. Chem. Soc. Jap. 1965, 38, 978-
[4] Jellinek H. H. D. The 2nd International Symposium on Degradation and Stabilization of
Polymers (Abstracts of Reports), Dubrovnik, 1978.
[5] Jellinek H. H. D., Toyoshima Y. J. Polym. Sci. A-1. 1967, 5, 3214-
[6] Jellinek H. H. D., Flajsman F. J. Polym. Sci. A-1. 1969, 7, 1153-
[7] Huber A. Diss. Doktor Naturwiss. Stutgart: Fakultät Chemie der Universität Stutgart,
1988.
[8] Giamalva D. H., Kenion G. B., Church D. F., Pryor W. A. J. Am. Chem. Soc. 1987,
108, 7059-7063.

[9] Rånby B., Rabek J. F. Photodegradation, Photo-oxidation and Photostabilization of
Polymers. London: Wiley, 1975.
[10] Jellinek H. H. D., Flajsman F., Kryman F. J. J. Appl. Polym. Sci. 1969, 13, 107-
[11] Jellinek H. H. D., Flajsman F. J. Polym. Sci. A-1. 1970, 8, 711-
[12] Jellinek H. H. D., Hrdlovič P. J. Polym. Sci. A-1. 1971, 9, 1219-
[13] Jellinek H. H. D., Chandhuri A. J. Polym. Sci. A-1. 1972, 10, 1773-
[14] Jellinek H. H. D., Yokata A. R., Itoh Y. Polym. J. 1973, 4, 601.
[15] Jellinek H. H. D., Wang A. T. J. W.
J. Polym. Sci., Polym. Chem. Ad
. 1973, 11, 3227
[16] [Jellinek H. H. D., Martin F. H., Wegener H. J. Appl. Polym. Sci. 1974, 18, 1773-
[17] Pariiskii G. B., Gaponova I. S., Davydov E. Ya. Russ. Chem. Rev. 2000, 69, 985-999.
[18] Zaikov G.E. Success in chemistry and biochemistry, New York, Nova Science
Publishers, 2009
In: Chemical Reactions in Gas, Liquid and Solid Phases… ISBN: 978-1-61668-671-0
Editors: G. E. Zaikov, R. M. Kozlowski, pp.11-20 ©2010 Nova Science Publishers, Inc.






Chapter 2



INFLUENCE OF THE INITIATION RATE OF
RADICALS ON THE KINETIC CHARACTERISTICS OF
QUERCETIN AND DIHYDROQUERCETIN IN THE
METHYL OLEATE OXIDATION

L. I. Mazaletskaya
*
, N. I. Sheludchenko and L. N. Shishkina
Emanuel Institute of Biochemical Physics of Russian Academy of Sciences,
Moscow, Russia


ABSTRACT

The antioxidant activity of quercetin (Q) and dihydroquercetin (QH
2
) is studied by
the methyl oleate autooxidation model at 323 K in thin layers, and also the antiradical
activity of these substances is investigated by the initiated oxidation of methyl oleate at
333 K. It is shown that the rate constant of the inhibition for Q is equal 1.7×10
5
dm
-3
mol
-1
s
-1
, that is 2.2 times greater than k
ing
for QH
2
(7.9×10
4

dm
3
mol
-1
s
-1
). Under the
autooxidation condition the inhibitory effectiveness of Q is also 1.6 times greater than
that for QH
2
. The existence of the direct correlation between the induction period of the
methyl oleate autooxidation in the presence of flavonoids and the Q and QH
2

concentrations indicates their primary interaction with peroxyl radicals.

Keywords: autooxidation, initiated oxidation, kinetics, flavonoids, methyl oleate.


AIMS AND BACKGROUND

Flavonoids are the compounds within the group of the vitamin P and of interest as the
biologically active substances with a wide spectrum of action. Biological activity of
flavonoids is associated with their ability to inhibit of oxidation processes by the reaction

* Emanuel Institute of Biochemical Physics of Russian Academy of Sciences, 4 Kosygin st., 119334, Moscow,
Russia e-mail:
L. I. Mazaletskaya, N. I. Sheludchenko and L. N. Shishkina
12
with reactive oxygen species, as well as free radicals [1-6]. In addition to the use of

flavonoids as drugs and the component of the biologically active additives for the
stabilization of the food products, cosmetics, preparations, etc, from the air oxygen oxidation
is of the great practical interest, because the number permitted to be used for this purpose
synthetic antioxidants is extremely limited.
Many investigations are made to examine the antioxidant activity of flavonoids and their
content in food product consistent by using the different methods. Advantages and
disadvantages of these methods are discussed in detail in review [7].
The analysis of the available literature data shows that the parameters characterizing the
antioxidant activity as well as the rate constant of the antiradical activity of flavonoids
obtained under different conditions substantially differ and depend on many factors, including
the chemical structure of flavonoids and the oxidation model. Thus, one would expect that the
antioxidant activity of the two closest to the structure of flavonoids - quercetin (Q) and
dihydroquercetin (QH
2
), the molecule structure of which is the presence or absence of the C
2
-
C
3
double bond, will be little different, because their rate constants with oxygen anion-
radicals are close and equal 1.7×10
5
dm
3
mol
-1
s
-1
and 1.5×10
5

dm
3
mol
-1
s
-1
, correspondingly
[8]. However, the effectiveness of Q is more 2 times greater than that for QH
2
, when it is
determined by the NADPH- and CCl
4
-dependent lipid peroxidation in microsomal
membranes of the rat liver
8
. On the contrary, the greatest antioxidant activity has QH
2
that
follows from the results of the comparative tests presented in the paper [9].
As shown, the antiradical activity of flavonoids significantly changes depending on the
oxidizing substrate and the oxidation conditions. So, the rate constants of their interaction
with peroxyl radicals obtained in the initiated oxidation reaction of diphenylmethane
10
significantly higher than that obtained by methyl linoleate oxidation in the homogenous and
micellar solutions [11]. Besides, as noted in Ref. 10 - 11, flavonoids did not behave as the
classical antioxidants and the constant of their antiradical activity depends on the initial
concentrations of both flavonoid and the oxidation substrate.
To use flavonoids as stabilizers from the spontaneous oxidation of foods, cosmetics and
medicinal agents, it is necessary to establish the regularities of their antioxidant action under
the autooxidation conditions, which simulates the natural aging process taking place under the

air oxygen action. As known, it is the side-reactions of antioxidants (InH) play the most
substantial role under the degenerate branching chain in the autooxidation process, they
proceed with the participation of the initial molecules of antioxidants and products of their
oxidative conversion and lead to loss of the effectiveness of the antioxidant action. For this
reason, there may exist substantial differences in regularities of the antioxidant action of these
substances between the autooxidation reactions and reactions with the constant rate of the free
radical initiation. So, for example, the deviation from linearity is observed for the dependence
of the induction period on the initial concentration for the natural antioxidant α-tocopherol
(TP) under the autooxidation conditions, and, in some cases, this dependence can be
extremal
12
. On the contrary, the linear relation between these parameters was detected by both
the initial oxidation and autooxidation for the hindered phenols, radicals of which are
practically not consumed in side-reactions [13,14].
The aim of our research was to study the influence of the quercetin and dihydroquercetin
concentrations on the effectiveness of their inhibitory action and the antiradical activity
depending on the oxidation conditions of the same substrate – methyl oleate.
Influence of the Initiation Rate of Radicals on the Kinetic Characteristics…
13
EXPERIMENTAL

Autooxidation of methyl oleate is carried out by the atmospheric oxygen in a thin layer at
323 K. The course of oxidation was followed by the accumulation of hydroperoxides
(ROOH), the concentration of which was determined by iodometric titration. The error of the
ROOH concentration determination did not exceed 1.5%. The antioxidant effectiveness was
evaluated by τ values, which were graphically determined from the kinetic curves of the
ROOH accumulation during the methyl oleate autooxidation in the absence and presence of
InH. As duration of the oxidation induction period (τ), we took the interval from zero to the
perpendicular dropped on the X axis from point of intersection of the linear plots of kinetic
curve of the ROOH accumulation: the initial oxidation rate within the induction period and

the maximal rate of the ROOH accumulation.
The initiated oxidation of methyl oleate in a mixture (1:1) with an inert solvent
(chlorobenzene) was performed by the air oxygen at 333 K. The reaction mixture containing
methyl oleate, chlorobenzene and the initiator – dinitrile of azoizobutyric acid, placed in
oxidative cell equipped with a magnetic mixer. The reaction mixture was thermostated at 333
K, and then InH was injected and measured the kinetics of oxygen uptake by using the
volumetric method. The initiation rate and the InH concentration were varied. The initial rate
of oxidation, as well as the value of the induction period τ, were determined from the kinetic
curves of oxygen absorption by method described in Ref. 15. The interval from the beginning
of the experience to the point of intersection of two straight lines for which tg α
1
= 2 tg α
2
was
taken as τ in the presence of InH. The first line is an extension to a straight of the oxygen
uptake, when the reaction rate is constant after the complete consumption of InH. The second
line is tangent to the kinetic curve of the oxygen uptake in the point, the reaction rate of
which is twice less than that in the absence of inhibitor.
The concentration of Q was determined spectrophotometrically at the wavelength λ
max
=
368 nm. The formation of the intermediate product is recorded by the absorption spectrum at
the wavelength λ
max
= 526 nm. To prepare the InH solutions, their sample is dissolved in
ethanol and then diluted by chlorobenzene. The proportion of ethanol in the oxidative cell is
not exceeded about 1.3 % (v/v). Methyl oleate was purified by vacuum distillation.
Dihydroquercetin and Quercetin (Sigma) were used without additional purification.
The kinetic data were processed by KINS program given in Ref. 16.

RESULTS AND DISCUSSION

Methyl oleate is one of the most used model system for the analyzing the antioxidant
properties of different individual InH and their mixtures, but the employment of the methyl
oleate autooxidation in the thin layer is rare. For this reason, in our research it was used the
methyl oleate autooxidation in thin layer. It is obtained that Q and QH
2
were effectively
inhibited this process (Fig. 1). The dependence of τ on the initial concentration of these
antioxidants is closely to linear in the studied range of concentrations. The slope of
dependences of τ on the [InH]
0
concentrations for Q and QH
2
is significantly different.
Besides, there is a need to note that the antioxidant activity of Q is 1.6 times greater than for
QH
2
(Fig. 1). The similar results were obtained during the oxidation of lard
17
: it was shown
L. I. Mazaletskaya, N. I. Sheludchenko and L. N. Shishkina
14
that τ
Q
is 1.4 times greater then τ
QH2
.

Besides, our results are also consistent of the data
presented in Ref. 18 about the antioxidant activity of the two flavonoids – fisetin and fustin,
the molecular structure of which is also characterized by presence or absence of the C
2
– C
3
double bond. According to Ref.18, the IC
50
values for fisetin and fustin during the NADPH-
dependent microsomal lipid peroxidation are equal 20.8 and 66 μmol, correspondingly, e. i.
their antioxidant activities differ about 3.2 times.

0
50
100
150
200
250
300
00,511,522,53
1
2
3
τ, h
[InH]
0
×10
4
, mol dm
-3

Figure 1. Dependence of the induction period (τ) on the antioxidant concentrations during
autooxidation of methyl oleate 1 – Q; 2 – QH
2
; 3 – TP
Hence, the obtained results and the literature data point to the fact that the presence of the
C
2
– C
3
double bond in the C-ring caused the conjugation at all rings in the flavonoid
molecule results in the increase of their antioxidant activity.
In order to clear the behavior of flavonoids during the oxidation, a detail computer
analysis of the kinetics of the methyl oleate autooxidation in the absence and presence of
flavonoids was performed. It was showed that, in all cases, the peroxide accumulation is well
described by the exponential law: [ROOH] = a×exp(kt), the correlation coefficients of which
are equal 0.99 – 1.0. Earlier the similar relationship was revealed for the methyl oleate
autooxidation when the oxygen concentration provides the oxidation in the kinetic range
14
.
The exponential index k, the value of which is proportional to the total oxidation rate
14
, is not
reliable differ for Q and QH
2
and is not depend on their concentrations: k = (5.3 ± 0.6)×10
-2
h
-
1

and k = (4.94 ± 0.04)×10
-2
h
-1
for Q and QH
2
, correspondingly. Thus, the results of
computations indicate the complete consumption of flavonoids within the induction period.
The preexponential factor a of the kinetic curves of the peroxide accumulation, the values of
which are due to the rates of radical initiation and the chain propagation [14], is substantially
less in the presence of flavonoids than the same during the methyl oleate autooxidation.