Polymer Composites1

In: Polymer and Composites ISBN 978-1-61728-038-2
Editors: G.V. Kozlov, A.K. Mikitaev and G.E.Zaikov © 2011 Nova Science Publishers, Inc.
Copyright © 2011. Nova Science Publishers, Inc. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under
Chapter 11
EPOXY POLYMERS AS NATURAL NANOCOMPOSITES:

STRUCTURAL ANALYSIS OF MECHANICAL
PROPERTIES
G.M. Magomedov*1, Z.M. Amirshikhova1, G.V. Kozlov1,

and G.E. Zaikov2
1. GOU VPO Dagestan State Pedagogical University,
Makhachkala, Russian Federation
2. N.M. Emanuel Institute of Biochemical Physics
of Russian Academy of Sciences,
MoscowRussian Federation
ABSTRACT
The methods of nanostructures adjustment in cross-linked epoxy polymers were
considered. The large potential of these materials mechanical properties change by
nanoclusters relative fraction variation was shown.
Keywords: Epoxy polymer, nanostructures, mechanical properties, solid-state extrusion,

annealing.
U.S. or applicable copyright law.
AIM AND SCOPE

The present paper aim is nanostructures regulation modes and the influence of the latter
on rarely cross-linked epoxy polymer properties study. The scope of this article is a polymers
and polymer nanocomposites study.
*
Corresponding address: GOU VPO Dagestan State Pedagogical University, Makhachkala-367003, Yaragskii st.,
57, Russian Federation
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BACK GROUND
As a theoretical back ground in this paper the cluster model of polymers amorphous state
structure was used, which allows to consider cross-linked polymers as natural
nanocomposites.
INTRODUCTION
At present it is generally accepted [1] that macromolecular formations and polymer
systems by virtue of their structure features are always natural nanostructural systems. In this
connection the question of using this feature for polymer materials properties and operating
characteristics improvement arises. It is obvious enough that for structure-properties
relationships receiving the quantitative nanostructural model of the indicated materials is
necessary. It is also obvious that if the dependence of specific property on material structural
state will be unequivocal one, then there will be quite sufficient modes achieve this state. The
cluster model of polymer amorphous state structure [2, 3] is the most suitable for this state
structure description. It has been shown, that this model basic structural element (cluster) is a
nanoparticle (nanocluster). The cluster model was used successfully for cross-linked epoxy
polymers structure and properties description [5]. Therefore the present paper purpose is
nanostructures regulation modes and the influence of the latter on rarely cross-linked epoxy
polymer properties study.
EXPERIMENTAL PART
The studied object is an epoxy polymer on the basis of resin UPS-181, cured by iso-
methyltetrahydrophtaleic anhydride in the ratio by mass 1:0.56. After intermixing and
exposure under vacuum of components at room temperature and pressure 10-20 mm of
mercury up to air bubbles disappearance during 15-30 min mixture is poured into the heated
up to ~ 343 K fluoropolymer molds and cured according to the experimentally selected
temperature regime.
Testing specimens were obtained by the hydrostatic extrusion method. The indicated
method choice is due to the fact, that high hydrostatic pressure exestion in deformation
process prevents the defects formation and growth, resulting to the material failure [6].
Hydroextrusion was realized for one passage on an apparate of pistoncylinder system at room
temperature. The extrusion strain εe is equal to 0.14, 0.25, 0.36, 0.43 and 0.52. εe value was
calculated according to the formula [7]:
d12 − d 22
εe = , (1)
d12
where d1, d2 are diameters of intermediate product and extrudate, accordingly (the last is
equal to 12 mm).
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The stress-strain characteristics were studied in conditions of uniaxial compression on a

testing machine FRZ-100/1 of the firm Heckert at testing temperature 293 K and strain rate ~
10-3 s-1 (the specimens diameter is equal to 10 mm, height – to 15 mm). No less than five
specimens were tested for each εe value. The arithmetical mean of the obtained data totality
was accepted as measurements result.
Specimens density was measured by hydrostatic weighing method to a precision of the
fourth sign after comma. Further their values were expressed accounting for measurements of
arithmetical mean error.
The obtained by hydrostatic extrusion specimens were annealed at maximum temperature
353 K during 15 min, after that they were also tested on uniaxial compression.
RESULTS AND DISCUSSION

The hydrostatic extrusion and subsequent annealing of epoxy polymer (EP) result to very
essential changes of its mechanical behaviour and properties, moreover unexpected enough.
The qualitative changes of EP mechanical behaviour can be monitored according to the
corresponding changes of the stress-strain (σ-ε) diagrams, shown in Figure 1. The initial EP
shows the expected enough behaviour and its elasticity modulus E and yield stress σY are
typical for such polymers at testing temperature T separating from glass transition
temperature Tg on about 40 K [8]. The small (~ 3 MPa) stress decay ΔσY behind yield stress is
observed, that is also typical of amorphous polymers [5]. However, EP extrusion up to
εe=0.52 results to stress decay ΔσY (“yield tooth”) disappearance and the essential E and σY
lessening. Besides, the diagram σ-ε itself is more like analogous diagram for rubber, than for
glassy polymer. This specimen annealing at maximum temperature Tan=353 K gives no less
strong, but diametrically opposite effect – yield stress and elasticity modulus increase sharply
(the latter increases in about 2 times in comparison with the initial EP and more that one order
in comparison with the extruded specimen). Besides, the pronounced “yield tooth” appears. It
is necessary to note that specimen shrinkage at annealing is small (~ 10 %), that is equal to
about 20 % of εe.
The general picture of parameters E and σY change as a function of εe is presented in
Figs. 2 and 3, accordingly. As one can see, both indicated parameters showed common
tendencies at εe change: up to εe≈0.36 inclusive E, and σY weak increase at εe growth is
observed, moreover their absolute values for extruded and annealed specimens are close, but
at εe>0.36 the pronounced antibatness of these parameters for the indicated specimen types is
displayed. The cluster model of polymers amorphous state structure and elaborated within its
frameworks polymers yielding treatment allows to explain such behaviour of the studied
samples [2, 3].
The cluster model supposes that polymers amorphous state structure presents the local
order domains (nanoclusters), surrounded by loosely-packed matrix. Nanoclusters consist of
several collinear densely-packed statistical segments of different macromolecules and in
virtue of this they offer the analogue of crystallite with extended chains. There are two types
of nanoclusters: stable, consisting of a relatively large segments number, and nonstable,
consisting of a less number of such segments [9].
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Figure 1. The stress-strain (σ-ε) curves for initial (1), extruded up to εe=0.52 (2) and annealed (3) EP.
Figure 2. The dependences of elasticity modulus E on extrusion strain εe for extruded (1) and annealed
(2) EP.
At temperature increase or mechanical stress application nonstable clusters are

disintegrated in the first place, that results to the two well-known effects. The first of them is
known as two-stage glass transition process [10] and it supposes that at Tg' =Tg-50 K
disintegration of nonstable clusters, restraining loosely-packed matrix in glassy state, occurs
that defines devitrification of the latter [2, 3]. The well-known rapid polymers mechanical
properties decrease at approaching to Tg is consequence of this [8]. The second effect consists
of nonstable clusters decay at σY under mechanical stress action, loosely-packed matrix
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mechanical devitrification and, as consequence, glassy polymers rubber-like behaviour on

cold flow plateau [9]. The stress decay ΔσY behind yield stress is due to namely nonstable
nanoclusters decay and therefore ΔσY value serves as characteristic of these nanoclusters
fraction [9]. Proceeding from this brief description, the experimental results, adduced in Figs.
1-3, can be interpreted.
The rarely cross-linked polymer on the basis of resin UPS-181 has low glass transition
temperature Tg, which can be estimated according to shrinkage measurements data as equal to
~ 333 K. This means that the testing temperature T=293 K and Tg' for it are close, that small
ΔσY value for the initial EP confirms. This supposes nanoclusters (nanostructures) small
relative fraction ϕcl [2, 3] and, since these nanoclusters have arbitrary orientation, εe increase
results rapidly enough to their decay, that defines loosely-packed matrix mechanical
devitrification at εe>0.36. Devitrificated loosely-packed matrix gives insignificant
contribution in E [11], equal practically to zero, that results to sharp (discrete) elasticity
'
modulus decrease. Besides, at T> Tg ϕcl rapid decay is observed, i.e. segments number
decrease in both stable and nonstable nanoclusters [3]. Since just these parameters (E and ϕcl)
are defined σY value, then their decreasing defines yield stress sharp lessening. Now extruded
at εe>0.36 EP presents as a matter of fact rubber with high cross-linking degree, that its
diagram σ-ε (Figure 1, curve 2) reflects.
The polymer oriented chains shrinkage occurs at the extruded EP annealing at
temperature higher than Tg. Since this process realizes in a narrow temperatures range and
during a small time interval, then a large number of nonstable nanoclusters is formed. This
effect is intensified by the available molecular orientation, i.e. by preliminary favourable
segments building, and it is reflected by ΔσY strong increase (Figure 1, curve 3). ϕcl increase
results to E growth (Figure 2) and ϕcl and E combined enhancement – to σY considerable
growth (Figure 3).
The considered structural changes can be described quantitatively within the frameworks
of a cluster model. The nanoclusters relative fraction ϕcl can be calculated according to the
methodics, stated in paper [12]. The shown in Figure 4 dependences ϕcl(εe) have the character
expected from the adduced above description and are its quantitative confirmation. The
adduced in Figure 5 dependence of density ρ of EP extruded specimens on εe is simbate to the
dependence ϕcl(εe), that should be also expected, since densely-packed segments fraction
decrease should be reflected in ρ lessening.
In paper [13] the supposition was made that ρ change can be due to microcracks network
formation in specimen that results ρ lessening at large εe (0.43 and 0.52), which are close to
the limiting ones. ρ relative change (Δρ) estimation according to the equation is:
ρ max − ρ min
Δρ = , (2)
ρ max
where ρmax and ρmin are the greatest and the least density values, accordingly, shows that
Δρ≈0.01. This value can be reasonable for free volume increase, which is necessary for
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loosely-packed matrix devitrification [3] (accounting for closeness of T and Tg' ), but it is
obviously small, if to assume as real microcracks formation. As the experiments have shown,
EP extrusion at εe>0.52 is impossible owing to specimens cracking in extrusion process.
Therefore the critical dilatation Δδcr value, which is necessary for microcracks cluster
formation, can be estimated [14] as follows:
2(1 + ν )(2 − 3ν )
Δδcr = , (3)
11 − 19ν
where ν is Poisson’s ratio.
Accepting the average value ν≈0.35, we obtain Δδcr≈0.60 that is essentially higher than
the estimation Δρ made earlier. These calculations assume that ρ decrease at εe=0.43 and 0.52
is due to nonstable nanoclusters decay and corresponding to EP structure loosening.
Figure 3. The dependences of yield stress σY on extrusion strain εe for extruded (1) and annealed (2) EP.
The stated above data give a clear example of large possibilities of polymer properties
operation through its nanostructure change. From the plots of Figure 2 it follows that
annealing of EP, extruded up to εe=0.52, results to elasticity modulus increase in more than 8
times and from data of Figure 3 yield stress increase in 6 times follows. From the practical
point of view extrusion and subsequent annealing of rarely cross-linked epoxy polymers
allow to obtain materials, which are just as good as by stiffness and strength to densely cross-
linked EP, but exceeding the latter by plasticity degree. Let us note, that besides extrusion and
annealing the other modes of polymers nanostructure operation exist: plasticization, filling,
films obtaining from different solvents and so on.
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Figure 4. The dependences of nanoclusters relative fraction ϕcl on extrusion strain εe for extruded (1)
and annealed (2) EP.
Figure 5. The dependence of specimens density ρ on extrusion strain εe for extruded (1) and annealed
(2) EP.
CONCLUSIONS
The present paper results demonstrated that neither cross-linking degree nor molecular
orientation level defined cross-linked polymers final properties. The proof, controlling
properties, is a state of supersegmental (nanocluster) structure, which, in its turn, can be goal-
directly regulated by molecular orientation and thermal treatment application.
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REFERENCES
[1] Ivanchev S.S., Ozerin A.N. A nanostructures in polymer systems. Vysokomolek. Soed.
B, 2006, v. 48, № 8, p. 1531-1544.
[2] Kozlov G.V., Novikov V.U. The cluster model of polymer amorphous state. Uspekhi
Fizicheskikh Nauk, 2001, v. 171, № 7, p. 717-764.
[3] Kozlov G.V., Zaikov G.E. Structure of the Polymer Amorphous State. Utrecht-Boston,
Brill Academic Publishers, 2004, 465 p.
[4] Mikitaev A.K., Kozlov G.V., Zaikov G.E. Polymer Nanocomposites: Variety of
Structural Forms and Applications. New York, Nova Science Publishers, Inc., 2008,
319 p.
[5] Kozlov G.V., Beloshenko V.A., Varyukhin V.N., Lipatov Yu.S. Application of cluster
model for the description of epoxy polymer structure and properties. Polymer, 1999, v.
40, № 4, p. 1045-1051.
[6] Kozlov G.V., Beloshenko V.A., Slobodina V.G., Prut E.V. The structure of ultra-high-
molecular polyethylene change at solid-state extrusion. Vysokomolek. Soed. B, 1996, v.
38, № 6, p. 1056-1060.
[7] Aloev V.Z., Kozlov G.V. Physics of Orientational Phenomena in Polymeric Materials.
Nal’chik, Polygraphservice and T, 2002, 288 p.
[8] DiBenedetto A.T., Trachte K.L. The brittle fracture of amorphous thermoplastic
polymers. J. Appl. Polymer Sci., 1970, v. 14, № 11, p. 2249-2262.
[9] Kozlov G.V., Beloshenko V.A., Gazaev M.A., Novikov V.U. The yield and forced
high-elasticity mechanisms of cross-linked polymers. Mekhanika Kompozitnukh
Materialov, 1996, v. 32, № 2, p. 270-272.
[10] Belousov V.N., Kotsev B.Kh., Mikitaev A.K. Two-stage glass transition of amorphous
polymers. Doklady AN SSSR, 1985, v. 280, № 5, p. 1140-1143.
[11] Shogenov V.N., Belousov V.N., Potapov V.V., Kozlov G.V., Prut E.V. The glassy
polyarylatesulphone stress-strain curwes description within the frameworks of high-
elasticity conceptions. Vysokomolek. Soed. A, 1991, v. 33, № 1, p. 155-160.
[12] Kozlov G.V., Burya A.I., Shustov G.B. The rotating electromagnetic field effect on
glass transition and structure of carbon plastics on the basis of phenylone. Fizika i
Khimiya Obrabotki Materialov, 2005, № 5, p. 81-84.
[13] Pakter M.K., Beloshenko V.A., Beresnev B.I., Zaika T.P., Abdrakhmanov L.A., Bezay
N.I. The hydrostatic treatment effect on structural organization formation of densely
cross-linked epoxy polymers. Vysokomolek. Soed. A, 1990, v. 32, № 10, p. 2039-2046.
[14] Balankin A.S. Synergetics of Deformable Body. Moscow, Publishers of Ministry
Defence SSSR, 1991, 404 p.
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Chapter 12
EPOXY POLYMERS AS NATURAL NANOCOMPOSITES:

THE YIELD PROCESS STRUCTURAL TREATMENT
G.M. Magomedov1, Z.M. Amirshikhova1, G.V. Kozlov1,

and G.E. Zaikov*2
1. GOU VPO Dagestan State Pedagogical University,
Makhachkala, Russian Federation
2. N.M. Emanuel Institute of Biochemical Physics
of Russian Academy of Sciences,
MoscowRussian Federation
ABSTRACT
The absence of simbatness between yield stress and elasticity modulus for epoxy
polymers was shown. This is due to thermodynamically nonequilibrium structure of
amorphous polymers, that requires two order parameters for their properties description,
as a minimum. The cluster model of polymers amorphous state structure allows to correct
quantitative estimation of yield stress.
Keywords: Epoxy polymer, structure, nanoclusters, yield stress, elasticity modulus.
AIM AND SCOPE

The aim of the present paper is a theoretical description of cross-linked epoxy polymers
yield stress. The scope of this article is a polymers and polymer nanocomposites study.
*
N.M. Emanuel Institute of Biochemical Physics of Russian Academy of Sciences, Moscow-119334, Kosygin st.,
4, Russian Federation.
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BACK GROUND
As a theoretical back ground in this paper the cluster model of polymers amorphous state
structure was used, which allows to consider cross-linked polymers as natural
nanocomposites.
INTRODUCTION
At present it becomes obvious that polymer systems in virtue of their structure features
are always nanostructural systems [1]. However, such structure treatment can be a different
one. So, the authors [2] used for this purpose the cluster model of polymers amorphous state
structure [3], which supposes, that the indicated structure consists of local order domains
(clusters), immersed in loosely-packed matrix. In this case the latter is considered as natural
nanocomposite matrix and clusters – as nanofiller. The cluster presents itself a set of several
densely-packed collinear segments of different macromolecules, having the size up to several
nanometers [3]. It has been shown that such clusters are true nanoparticles – nanoworld
objects (nanoclusters) [2].
The yield process presents an important phenomenon in polymers mechanics and its main
characteristic (yield stress) from the practical point of view restricts from above an
exploitation region of plastic polymers used as engineering materials [4]. The purpose of the
present paper is a theoretical description of cross-linked epoxy polymers yield stress within
the frameworks of cluster model.
EXPERIMENTAL
Cross-linked epoxy polymers (EP) based on diglycidyl ether of bisphenol A (DGEBA)
were used. The curing was performed by 3,3’-dichloro-4,4’-diaminodiphenylmethane (EP-1
composition) and iso-methyltetrahydrophtalic anhydride in the presence of a catalyst tris
(dimethylaminomethyl)-2,4,5-phenol (EP-2 composition). The ratio of a curing agent to
epoxy oligomer reactive groups Kst varied at 0.50-1.50. Thus it was possible to obtain 20 EP
specimens with different topologies of cross-linked networks.
Thermomechanical analysis (TMA) was performed under the uniaxial compression at the
pressure of 1.2 MPa and at the temperature change rate of 2 K/min. According to TMA data
we determined the glass transition temperature Tg and the mean statistical molecular weight
Ws of the chain part between the cross-links nodes [5]:
3ρRThe Δε
Ws = , (1)
Ph0
where ρ is epoxy polymer density, which is equal to about 1250 kg/m3; R is universal gas
constant; The is the initial temperature of the forced high elasticity, K; Δε is quasiequilibrium
high elastic strain; h0 is the specimen initial height; P is the specific load on the specimen.
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Further one can calculate the effective density of the cross-linked network νs according to
the following equation [5]:
2 ρN A
νs = , (2)
3 Ws
where NA is Avogadro number.

As the value νs estimations according to the equation (2) have shown, it varies within the
range of (2-19)×1026 m-3. The stress-strain characteristics of epoxy polymers were obtained
under the uniaxial compression tests at temperature 293 K and strain rate of 5×10-3 s-1. The
density of the indicated specimens was determined by hydrostatic weighing method with
precision up to four decimal places.

The studied epoxy polymers are characterized by plastic failure type under the uniaxial
compression tests. In this case the clearly expressed yield stress, yield tooth and cold flow
plateau are observed on stress-strain curves. At present the point of view, assuming elasticity
modulus E and yield stress σY simbate change at different kinds of actions on polymer
predominates, that gives in the end linear correlation σY(E) [6]. In Figs. 1 and 2 the
dependences E(Kst) and σY(Kst) are adduced for the studied epoxy polymers, which have
principally differing character. So, if for the elasticity modulus adduced in Figure 1 the
dependence has extreme character with minimum at Kst=1.25 or 1.0, then yield stress in Kst
considered range remains practically constant (Figure 2). The comparison of Figs. 1 and 2
exludes E and σY behaviour simbatness for the studied epoxy polymers.
Figure 1.The dependence of elasticity modulus E on curing agent-oligomer ratio Kst for epoxy polymers
EP-1 (1) and EP-2 (2).
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The cluster model of polymers amorphous state structure [3] was used in the present
paper for the explanation of the indicated nonsimbatness and theoretical description of epoxy
polymers yield stress.
Figure 2. The dependence of yield stress σY on curing agent-oligomer ratio Kst for epoxy polymers EP-1
(1) and EP-2 (2).
Within the frameworks of this model segments, included in nanoclusters, are considered
as structure linear defects (analog of dislocations in crystalline lattices), that allows to use for
yield stress theoretical determination mathematical calculus of dislocations theory. Within the
frameworks of such approach the relationship between σY and E is expressed by the equation
[3]:
3Eb ρ d
σYt = , (3)
4π(1 + ν )
where b is Burgers vector, ρd is linear defects density, ν is Poisson’s ratio.

Let us consider the estimation methods of the parameters included in the equation (3).
The Burgers vector value b for polymeric materials is given by the following formula [3]:
1/ 2
⎛ 60.2 ⎞
b = ⎜⎜ ⎟⎟ , Å, (4)
⎝ C∞ ⎠
where C∞ is characteristic ration, which is the polymer chain flexibility indicator and is
determined as follows [3]:
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2d f 4
С∞ = +
d (d − 1)(d − d f )
, (5)
3
where d is dimension of Euclidean space, in which a fractal is considered (it is obvious, that
in our case d=3), df is fractal dimension of epoxy polymer structure, determined according to
the equation [7]:
d f = (d − 1)(1 + ν ) , (6)
where Poisson’s ratio ν is estimated according to the mechanical tests results with the aid of
the relationship [8]:
σY 1 − 2ν
= , (7)
E 6(1 + ν )
The linear defects density ρd was determined according to the equation [3]:
ϕcl
ρd = , (8)
S
where ϕcl is nanoclusters relative fraction, S is macromolecule cross-sectional area, which for
the studied epoxy polymers is equal to ~ 32 Å2 [9].
The value ϕcl was calculated according to the following percolation relationship [3]:
ϕcl = 0.038(Tg − T )
0.55
, (9)
where Tg and T are glass transition and testing temperatures, accordingly.
In table 1 the comparison of the obtained experimentally σY and calculated according to

the considered above methods σYt values of yield stress for the studied epoxy polymers was
adduced. As one can see, a good correspondence of theory and experiment was obtained
σYt
(average discrepancy of σY and makes up 6.6 %, that is comparable with mechanical

tests error).
The stated above results suppose that σY and E values simbatness as a function of some
parameter (testing temperature, cross-linking density and so on) can be a special case only.
The equation (3) demonstrates that the indicated simbatness realization condition is criterion
ρd=const or, as follows from the equation (8), ϕcl=const. In other words, σY and E change
simbatness realization condition is polymer nanostructure invariability. Let us note that
amorphous polymers are thermodynamically nonequilibrium solids, for which description, as
minimum, two parameters of order are required according to the Prigogine-Defay principle. It
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is obvious, that the equation (3) satisfies this principle, whereas linear correlation σY(E) does
not.
Table 1. The structural and mechanical characteristics of epoxy polymers
Epoxy Kst νs×10-26, ϕcl E, GPa σY, MPa σYt ,

polymer m-3
MPa
0.50 2 0.300 4.3 140 148
0.75 6 0.334 3.9 140 148
EP-1 1.0 17 0.611 2.3 142 151
1.25 12 0.655 2.0 131 140
1.50 8 0.405 3.0 128 138
0.50 4 0.351 3.2 120 128
0.75 10 0.407 2.8 120 129
EP-2 1.0 11 0.508 2.5 131 140
1.25 10 0.409 3.0 129 138
1.50 8 0.429 2.7 121 128
CONCLUSIONS
Thus, the present paper results have shown, that yield stress and elasticity modulus
change simbatness is a special case in virtue of key reason, namely, polymers structure
thermodynamical nonequilibrium. At the same time cluster model of polymers amorphous
state structure gives the correct quantitative description of yield stress value.
REFERENCES
[1] Ivanchev S.S., Ozerin A.N. A nanostructures in polymer systems. Vysokomolek. Soed.
B, 2006, v. 48, № 6, p. 1531-1544.
[2] Mikitaev A.K., Kozlov G.V., Zaikov G.E. Polymer Nanocomposites: Variety of
Structural Forms and Applications. New York, Nova Science Publishers, Inc., 2008,
319 p.
[3] Kozlov G.V., Zaikov G.E. Structure of the Polymer Amorphous State. Utrecht-Boston,
Brill Academic Publishers, 2004, 465 p.
[4] Bartenev G.M., Frenkel S.Ya. Physics of Polymers. Leningrad, Khimiya, 1990, 432 p.
[5] Kozlov G.V., Beloshenko V.A., Varyukhin V.N., Lipatov Yu.S. Application of cluster
model for the description of epoxy polymer structure and properties. Polymer, 1999, v.
40, № 4, p. 1045-1051.
[6] Milagin M.F., Shishkin N.I. The elasticity and strength of non-oriented semicrystalline
polymers. Mekhanika Polymerov, 1975, № 6, p. 963-968.
[7] Balankin A.S. Synergetics of Deformable Body. Moscow, Publishers of Ministry
Defence SSSR, 1991, 404 p.
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[8] Kozlov G.V., Sanditov D.S. Anharmonic Effects and Physical-Mechanical Properties
of Polymers. Novosibirsk, Nauka, 1994, 261 p.
[9] Kozlov G.V., Beloshenko V.A., Kuznetsov E.N., Lipatov Yu.S. A epoxy polymers
molecular parameters change in their curing process. Doklady NAN Ukraine, 1994, №
12, p. 126-128.
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Chater 13
THE CHARACTERIZATION OF NOVEL

BIODEGRADABLE BLENDS BASED ON
POLYHYDROXYBUTYRATE
Yu.N. Pankova1, A.N. Shchegolikhin2, A.L. Iordanskii*1,

A.L. Zhulkina1, A.A. Ol’khov3, and G.E. Zaikov2
1 N.Semenov’s Institute of Chemical Physics. RAS. Moscow,
2N.Emanuel’s Institute of Biochemical Physics. RAS. Moscow.
3 D.Mendeleev’s Academy of Fine Chemical Technology. Moscow.
ABSTRACT
The present paper focuses on the study of novel blends based on poly(3-
hydroxybutyrate) (PHB) and polymers with different hydrophilicity (PELD and PA).
Polymer blends were produced from five ratios of PHB/PELD in an effort to regulate the
resistance to hydrolysis or (bio)degradation through the control of water permeability.
The relation between the water transport and morphology (TEM data) shows the impact
of polymer component ratio on the regulating water flux in hydrophobic matrix. To
elucidate the role of hydrophilicity of second component presenting in the PHB blends,
we studied the PHB/PA blends where PA is the polyamide resin composed of statistical
copolymer of hexamethyleneadipinate and ε-caprolactam in ratio 1:1. The complex of
techniques including DCS and FTIR-imaging (for T-scale) demonstrates the interaction
between PHB and PA in the temperature ranges of crystallization and melting. The
general approach based on Flory-Huggins equation is presented as the way to choice the
pairs of compatible or partly compatible polymers. Blending PHB with PA could be a

simple and effective method to design new matrices for drug delivery in medicine, while
the same procedure applied for PHB-PELD system with better resistance again
hydrolysis and lower price than initial PHB could be used as novel bioerodible packaging
materials.
*
aljordan08@gmail.com.
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Copyright © 2011. Nova Science Publishers, Inc. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under 106 Yu. N. Pankova, A. N. Shchegolikhin, A. L. Iordanskii et al.
Keywords: polyhydroxybutyrate, biodegradation, blends, properties, kinetics, diffusion.
INTRODUCTION
The families of biodegradable polymers, namely poly-α-hydroxyacides (PLA, PGA, and
their copolymers, PLGA) as well as poly-β-hydroxyalkanoates (PHA): poly(3-
hydroxybutyrate) [PHB] and its copolymers, especially with hydroxyvaleriate [PHBV], have
superior performance characteristics sufficient to replace a significant portion of petroleum-
based plastics used currently in medicine, packaging and food-service industry [1-3]. Along
with biodegradability, the PHAs and their principal member PHB are biocompatible and
friendly environmental [4-6]. In living organism and soil their macromolecules decompose to
form the nontoxic intermediates and final products included in carbohydrate metabolism.
Besides, bacterial PHB and its copolymers have also proved to be useful as model materials
for investigating the physical properties such as crystallization and diffusion.
However, the mechanical deficiency, a narrow processing window as well as yet the high
cost of PHB/PHA restrict its application as the friendly environmental, biomedical material.
For solution of the above-mentioned three problems, we propose the specific blending of
PHB, as a pivotal component, and the set of synthetic (LDPE and polyamide-66) and with a
different macromolecule polarity to design the (bio)degradable blends/compositions with
improved transport and physical characteristics which are useful for description of
biodegradation [7] and drug delivery [8].
EXPERIMENTAL
In the current study we used PHB in the powder form which was kindly supplied by
Biomer Co Krailing (Germany) Lot #216 with Mw = 206 kDa, density 1,248 g/c3. The blend
films were produced using a) the low density polyethylene (LDPE) namely commercial
product (RF 15803-020 grade) in the form of granules with Mη = 2.0*105 Da; and b) the
polyamide resin composed of statistical copolymer of hexamethyleneadipinate and ε-
caprolactam in ratio 1:1 with Мn= (1,94 ± 0,06)·104 Da and containing 38% of amide groups
at content of terminal groups equals 5,0 ± 0,1·10-2 mol/kg for -NH2 groups and 5,3 ±0,1·10-2
mol/кg for -COOH groups. The blends were prepared by solvent casting from chloroform-
ethanol solvent combination (both solvents of medical grade quality) and by melt/solid
extrusion with single-screw extruder. A series of LDPE–PHB blends were prepared with the
following component ratios (w/w): 68 : 32, 84 : 16, 92 : 8, 96 : 4, and 98 : 2.
FTIR spectra of the blend films recorded with the spectrometer "Bruker IFS-48"
(Germany) at resolution 2 cm-1 the number of the scans about 70. Computer analysis of final
spectra performed with the interior programs in the range 500 – 3500 см–1. A Perkin-Elmer
differential scanning calorimeter (Model DSC7) calibrated with indium was applied for the
study of thermal behavior of PHB-PA blends as well as for neat polymers (PHB and PA)
separately. Specimens of about 5mg were encapsulated in aluminium pans and heated/ cooled
at constant rate 10oC/min. The range of heating includstemperature interval from room
temperature to 182oC. The fusion enthalpies ∆HPHB for PHB and ∆HPA for PA were measured
to calculate the crystallinity degrees αPHB and αPA using the following equations
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Copyright © 2011. Nova Science Publishers, Inc. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under The Characterization of Novel Biodegradable Blends… 107
αPHB = ∆HPHB/∆HoPHB(1/wPHB) 100% A
αPA = ∆HPA/∆HoPA(1/wPHA) 100% B
where wi (i=PHB or PA) is weight fraction of each component in the blend and ∆HoPHB or
∆HoPA fully crystalline PHB (87cal/g) or PA(54 cal/g) [9].

General approach in framework of Flory Huggins theory.
The analysis of water solubilities in accessible intercrystalline area for about 50 polymers
with different chemical structures (hydrophilicity) portrays that classification of such
polymers can be performed on the base of combination between the modified Flory-Huggins
equation (at aw = 1) and expression for solubility parameter in framework of the regular
solution model [10] (eqs 1 and 2, respectively)
ln ϕ w + ϕ p + χ wpϕ p2 = 0 (1)
χWP = Vw
RT (δW − δ P )
2 2
(2)
Inserting expression for χWP in equation 1 we immediately result the following final
equation
ln ϕ w + ϕ p + Vw
RT (δW − δ P )ϕ p = 0
2 2 2
(3)
Here the ϕw, ϕp are the volume fractions of water and a polymer respectively, and δi is the
solubility parameters of water and a polymer. χWP - Flory interaction parameter, Vw -
molar volume of water, R and T are gas constant and absolute temperature (oK) respectively.
The plot of Flory-Huggins equation (at water activity, aw = 1) in coordinates (lnϕw + ϕp)
vs. (δW2 − δ P2 ) ϕp2 ≡ Z is generally nonlinear and can be approximated by two intersectional
lines in intervals: Z ≤ 600 J/cm3 for the hydrophilic polymers (PVA, cellulose, chitosan and
the like) and Z ≥ 800 J/cm3 for the hydrophobic polymers (LDPE, HDPE, polypropylene,
polystyrene, rubbers and the like), see Figure1. The points located in the vicinity of the
intersection point of the above lines, at 600 < Z < 800 J/cm3, belong to the moderately
hydrophilic polymers [11].
In the Figure1 the water equilibrium sorption in the above systems of coordinates is
presented. Two polymers (PHB and PHBV) from the family of polyhydroxyalkanoates with
Hildebrand solubility parameters δp = 19,8 and 19,4 J1/2/cm 3/2 (Pa1/2) respectively [12] are
situated in the vicinity of the intersection point. The data collected about for 55 polymers with
different hydrophilicity which have been collected from our work [13]. V
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Figure 1. The pattern of water solubility in polymers with different hydrophilicity [11] in framework of
Flory-Huggins equations.
ariation of second polymer polarity in its blend/composite with the PHB (PHBV)
regulates composite morphologies and, hence, both water and drug transport as well as
thermophysical and mechanical behavior of polymer systems. Here we initiate our
consideration with description of an utmost situation where the PHB has been combined with
typical hydrophobic polymer - polyethylene (PELD).
Analyzing the microphotos obtained in our preliminary paper [14] we can distinctly
discern the porous space between continuous medium of the major phase of PELD and band-
like fibrils of PHB. These materials have microscopically complex structure with random
distribution of pore sizes, ranging from a few microns to tens of microns. In packaging or
pharmaceutical practice, in order to regulate the water permeability is slightly effected by
external force arousing during a film preparation or exploitation. Thus, controlling optimal
values of the composite parameters such as porosity, permeability and hydrophilicity are
important issues in PHB-PE research.
TRANSPORT BEHAVIOR OF WATER IN BLEND OF PHB WITH

HYDROPHOBIC POLYMER (PELD)
The total water permeability of the LDPE/PHB blends (PW) can be described by the
following equation:
PW = αSPE FPE PWPE + αSPHB FPHB PWPHB + αSInt PWH (4)
where PWPE , PWPHB, and PWH are the water permeabilities in phases of LDPE, PHB, and
through the interphase respectively; αSPE, αSPHB, and αSint are the fractions of the film cross
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section possessed by the phase of each component and interphase; FPE and FPHB are function
characterizing the effect of polymeric segments’ orientation on the water permeability in
phases of LDPE and PHB respectively. αSint = 1 - αSPE - αSPHB. In according with scanning
electron microscopy results [14], the porous structure in the interphase is formed and, hence,
parameter PWInt is equal to the hydraulic permeability [15]. Here the porous medium is
modeled as a continuum, composite material and its structure is characterized with a minimal
set of properties, namely the porosity (αSInt), the hydraulic permeability (PWH), which might
be functions of position (architecture) and structural elemen orientation (anisotropy) FPE,
FPHB. Further, φk, φπ, φν are the local volume fractions of cells, hydrated EPS and water in
the biofilm. From the local volume balance follows that
α SPE + α SPHB + αSint = 1 (5)
The final term on the right hand side of Eq. (4) reflects the hydraulic movement of water
through porous area and usually referred to as Darcy term [16]:
1 dμ
JWDa = − K Da (6)
α S ρ w dx
where JWDa is the water flow into a pore-containing area (m3 [water] m−2 [pore cross-
sectional surface area] s−1), K Da is hydraulic Darcy constant (m s−1) and dμ/dx is a water
potential gradient (m s−2) expressed through the water activity or the pressure of water vapor.
The expression for water permeabilities through PELD and PHB matrices has a classical form
dCW
JWi = − PWi (7)
dx
where i - index used for PHB or PELD and dCW is gradient of water concentration. The
dx
Figure 2 shows the total course of water permeability (fluxes) through the blend films as
function of PHB content.
The sharp permeability jump from the matrices having the anisotropical orientation of the
PHB bands in LDPE to matrices where the PHB fibrils formed the isotropic network is
illustrated by corresponding photos [14] reflecting the two different types of morphology.
At the relatively low PHB concentrations (4-8 % wt), the water flux resistance is
maximal and exceeds the resistance of the initial LDPE film, see Figure 3. Then, the
resistance is decreased with the increase of PHB concentration. It is significant that the same
manners have both the IR polarization ratio. Note that in this case mechanical tensile strength
dependence on the PHB concentration with minimum is situated at the same PHB/PE
fraction, about 4 - 8% (here not presented, see [14]).
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Fig.2. Water permeability through the blend films prepared on the base of the different polymer
fractions (shown on the top). Simultaneously the photo of anisotropic (a) and isotropic (b)
morphologies of the blends. The lines show the correspondence between kinetics and TEM data.
0 4 8 12 16 20 24 28 32
Rec ipro c al wate r perme ability *10 ,c m *h*mm Hg /g *c m
8 2,6
2,4
6
2
2,2
FTIR Dichro is m (1230 cm )
-1
-9
2,0
4
1,8
2 1,6
1,4
0
0 4 8 12 16 31 32
Content of the PHB, %wt.
Fig.3. Comparison of reciprocal permeability of water (■), FTIR dichroism (♦), as functions of PHB
content in PHB-LDPE composite films.
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It is apparent from the above data that transport behavior of water in the blended films is
substantially affected by the orientation of polymer segments (Fi) in LDPE continuum phase
and by the defects/pores formed in interphase areas (αSInt PWInt in Eq.1) if one suggests that
tensile strength was dominantly determined by defects (pores) of the heterogeneous matrix.
Analysis of extreme points for “transport coefficient - blend content” relationships
combined with the morphology features (controlled by FTIR, XRD, SEM and AFM) and
thermophysical testing (DSC, TGA) enable us to elucidate the impact of crystallinity and
second component nature (macromolecular polarity) upon mechanism of both controlled
release and (bio)degradation.
PHASE TRANSITIONS IN THE BLEND OF PHB WITH MODERATELY

HYDROPHILIC POLYMER (PA)
On the elaboration of binary polymer composition where both components have
moderate hydrophilicity (macromolecule polarity) we have selected poly(3-hydroxybutyrate)
[PHB] and copolymer of polyamides PA54C characterized in [17] and hereafter designated
by PA acronym. The one of important reasons for such selection was the proximity of their
melting points 175,7oC (PHB) and 168,3oC (PA) and as consequence the processing of their
blends through the melt became much more efficacious. The other reason is the elasticity of
PA at low crystallinity and hence we would need that addition of PA to PHB could improve
viscous-elasticity of the neat PHB.
The assay of repeated cycles ‘melting-crystallization’ provided by DSC for PHB-PA
composition testifies a PHB crystallinity decrease as the result of their blending. The
crystallinity degree were calculated through enthalpy melting on measuring endothermic peak
areas as shown in Experimental part. Under blending with moderately hydrophilic polymer
(PA), the crystallinity decline resembles qualitatively the course of decrease in crystallinity
for the system PHB-PVA that is at blending with hydrophilic polymer [18]. It is important
that the location of melting point for PHB on DSC curves displaced to low temperature area
from the value 175,7 оС for neat PHB to 168,5oC for PHB in the blend at 87,5% PA.
Recently on the base of FTIR spectroscopy data[17] we have shown that in the blend
films of PHB-PA there is the system of hydrogen bonds which are formed between carbonyl
group of PHB and amide one of PA. Taking into account the accessibility of interacting
groups in PHB and PA, the maximal interaction estimated as the shift of location for band
maximum of carbonyl group happens at mole ratio PHB/PA = 1:1. With provision for FTIR
data we can suggest that in a chilled-down polymer composition the impact of the second
component (PA) upon immobilization of PHB kinetic segments causes the decrease in their
mobility and, hence, brings the drop of PHB segment fraction involved into crystallization.
The next step of blend crystallinity transfer study embraces the analysis of cooling
thermograms from the melts PHB-PA. For all compositions (besides the blend with ratio
PHB/PA = 1:9) there are two peaks with appropriate resolution on the temperature scale.
Each peak belongs to the successive crystallization of individual components in the blend. It
is interesting that the low-temperature maximum reflects the crystallization of the PHB
melted at ~175oC while the high-temperature peak does the crystallization of the PA melted at
lower temperature about 165oC. Consequently, the supercooling degree (designated as the
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difference in melting point and crystallization point) is much higher for the high-crystalline
PHB relative to the PA.
For overcooled melts of the PHB blends the addition of second component gradually
decreases the temperature of crystallization as result of a solid crystalline phase formation in
PA. The solidification of PA (its crystalline part) produces steric and kinetic hindrances
effecting the PHB crystallization. Along with that, as we said above, the blending PHB and
PA decreases the melting point of the former. Generally, the locations of endothermic and
exothermic peaks moved on the temperature scale with such manner that the supercooling
degree keeps nearly constant. In a number of works [e.g. 18] it has been shown that both the
rate of crystallinity and the rate of heterogeneous nucleation increase with the value of
supercooling degree (ΔТСМ = TM - Tc). Therefore, it is quit possible to assume that the
formation of crystalline phase in PHB must perform with constant rate and the rate does not
depend on the PHB-PA composition.
Enhancing or inhibiting in segmental mobility for the blended components reflecting the
melting or crystallization respectively can be discovered by the FTIR spectra obtained as the
step-like series of temperatures. The Fig 4 and 5 portray a set of spectra recorded for heated
and cooled samples of PHB-PA system.
Here we shown that stretching vibration bands of carbonyl group pertaining ester entity
of PHB are very sensitive to “defrosting” in mobility of polymer molecules. Such jump of
segment mobility is the result of PHB crystal fusion. A low-frequency shoulder of
multicomposed band of >C=O group vibration (at1724 cm-1)disappears in the vicinity of
melting temperature of PHB in the PHB/PA (1:1) blend and for the blend melt above 172oC
there is the only diffuse band with the maximum at 1740cm-1. The extended maximum in this
area most likely reflects the existence of wide distribution of mobile conformers to be
responsible for the vibration of the ester groups in the melt. We emphasize that temperature
conforming to mobility deceleration (FTIR data) is in good agreement with melting point
(DSC data) for PHB in the blend.
Figure 4. FTIR-imaging for melting in the blend PHA-PA in the area of C=O group vibration.
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The parallel temperature series has been performed under cooling of the melt blend Fig 5.
The successive record of the FTIR spectra at different temperatures demonstrate clearly the
transfer from the liquid state to crystalline state. In the vicinity of 65oC this process is
characterized by the sharp appearance of low-frequency mode mentioned above and related
with immobilized carbonyl gropes. Under blend cooling we observe also the coincidence this
temperature with temperature interval of phase transition, measured by DSC procedure.
Summarizing the section devoted to PHB blend with moderately hydrophilic polymer
(PA) we have just shown that phase transition as thermo-induced process when each polymer
component has the proper structure evolution and both components interact each other. The
displacements of endothemal peak (Tm) and exothermal peak (Tc) on the temperature scale
as function of blend composition give also evidences of intermolecular interactions between
the polymers forming the novel blend composition.
Figure 5. FTIR-imaging for crystallization in the blend PHA-PA in the area of C=O group vibration.
Mechanism of thermophysical behavior can help us to design a novel therapeutic system

for controlled drug delivery.
CONCLUSION
We propose a common simplified (relative to e.g. 3D Hansen model [19]) approach for
preliminary selection of the pair of polymer components for the production of potentially
partly-miscible blends. The approach is based on modified equation Flory –Huggins and used
for equilibrium water sorption in polymers with different macromolecule polarity
(hydrophilicity). As sample of an immiscible pair forming the blend we studied the
PHB/PELD composition. The morphological features of PHB/PE blend demonstrate the self-
reinforced matrix where the minor component (PHB) forms the like-band fibrils embedded in
the PELD matrix. Above 16%PHB, the blend system undergoes the morphology transfer
from oriented PHB structure to isotropic one where the PHB fibrils transform into a network.
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The distinction between two morphologies reflects the different values of water permeability
through the blend films.
To elucidate the role of hydrophilicity of second component presenting in the PHB
blends, we studied the PHB/PA blends where PA is the polyamide resin composed of
statistical copolymer of hexamethyleneadipinate and ε-caprolactam in ratio 1:1. The complex
of techniques including DCS and FTIR-imaging (for T-scale) demonstrates the interaction
between PHB and PA in the temperature ranges of crystallization and melting. The general
approach based on Flory-Huggins equation is presented as the way to choice the pairs of
compatible or partly compatible polymers. Blending PHB with PA could be a simple and
effective method to design new matrices for drug delivery in medicine, while the same
procedure applied for PHB-PELD system with better resistance again hydrolysis and lower
price than initial PHB could be used as novel bioerodible packaging materials.
ACKNOWLEDGMENTS
This work was financially supported by the Russian State Contract of Federal Agency of
Sciences and Innovations №02.512.12.2004 from 10.06.2008 and by special grant from
Presidium of the Russian Academy of Sciences 2009 “Academic sciences to medicine”. The
authors would like also to thank the Biomer Co (Krailing, Germany) and personally Dr.
U.Hanggi for its valuable supplying with PHB.
REFERENCES
[1] Chen, Guo-Qiang. Chem. Soc. Rev., 38, 2434–2446 (2009). A microbial
polyhydroxyalkanoates (PHA) based bio- and materials industry.
[2] Siracusa, V., Rocculi, P., Romani, S., Rosa, M. Dalla. Trends in Food Science and
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packaging: a review.
[3] Mooney B.P. Biochem. J. 418, 219–232 (2009)The second green revolution?
Production of plant-based biodegradable plastics
[4] Gross, R.A., Kalra, B. Science, 297 (5582), 803-807 (2002) Biodegradable polymers
for the environment.
[5] Zhong, Z.W., Song, B., Huang, C.X. Materials and Manufacturing Processes 24 (5), pp.
519-523 2009. Environmental impacts of three polyhydroxyalkanoate manufacturing
processes.
[6] Akiyama, M., Tsuge, T., Doi, Y. Polymer Degradation and Stability, 80 (1), pp. 183-
194 (2003). Environmental life cycle comparison of polyhydroxyalkanoates produced
from renewable carbon resources by bacterial fermentation.
[7] Chiellini E., Corti A., D’Antone S., Solaro R. Prog. Polym. Sci. 28 963–1014(2003).
Biodegradation of poly (vinyl alcohol) based materials.
[8] Gabathuler R. Neurobiology of Disease 37 48–57 (2010). Approaches to transport
therapeutic drugs across the blood–brain barrier to treat brain diseases.
[9] Gonzalez-Montiel A., Keskkula H., Paul D.R. J.Pol.Sci. B: Polym.Phys. 33 (1995) 1751
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[10] Ying Hu, Robert H. Hurt. Carbon 39 887–896 (2001). Thermodynamics of

carbonaceous mesophase II. General theory for nonideal solutions.
[11] A.L.Iordanskii. Impact of Structure and Morphology upon Water Transport in Polymers
with Moderate Hydrophilicity. From Traditional to Novel Environmentally Friendly
Polymers. In: Water Transport in Synthetic Polymers.(Eds A.L.Iordanskii,
O.V.Startsev, and G.E.Zaikov.) Nova Science Publishers, Inc. New York. 2004 . Ch.1,
pp 1-14 .
[12] Terada M., Marchessault R.H. International Journal of Biological Macromolecules 25
207–215 (1999). Determination of solubility parameters for poly(3-hydroxyalkanoates).
[13] Iordanskii A.L., Rudakova T.E., and Zaikov G.E.. Interaction of Polymers with
Bioactive and Corrosive Media. . Ser. New Concepts in Polymer Science. VSP Science
Press. Utrecht –Tokyo Japan. 1994., 298p.
[14] Ol’khov1 A. A., Vlasov C. V., Shibryaeva L. S., Litvinov I. A., Tarasova N. A.,
Kosenko R. Yu., and. Iordanskii A. L. Polymer Science, Ser. A, Vol. 42, No. 4, pp.
447–452 (2000).Structural Features of LDPE–Poly(3-hydroxybutyrate) Blends.
[15] 15. Williams, C.G., Macpherson, J.V., Unwin, P.R., Parkinson, C. Analytical Sciences
24 (4), 437-442 (2008).Laser scanning confocal microscopy coupled with hydraulic
permeability measurements for elucidating fluid flow across porous materials:
Application to human dentine.
[16] Furmaniak S., Terzyk A.P., Gauden P.A., Rychlicki G. Journal of Food Engineering 79
718–723 (2007). Applicability of the generalised D’Arcy and Watt model to description
of water sorption on pineapple and other foodstuffs.
[17] Pankova Yu.N. Novel polymer compositions on the base of PHB and polyamides.
Moscow Fine thechology Academy. M. 2007. Thesises PHD.
[18] A.A.Olkhov, S.V.Vlasov, A.L.Iordanskii, G.E.Zaikov, and V.M.M.Lobo.
J.Appl.Polymer. Sci. v.90, 1471-1476 (2003) Water transport, structure features and
mechanical behavior of biodegradable PHB/PVA blends.
[19] Hansen Solubility Parameters: A User's Handbook 2nd Edition by Charles M. Hansen,
John Durkee, Charles M. Hansen, Georgio Kontogeorgis Barnes and Noble Lyndhurst,
NJ 2007 . ISBN-13: 9780849372483
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Chapter 14
MACROKINETIC MECHANISM OF BIODEGRADATION

OF POLYMER SAMPLES BASED ON CROSS-LINKED
DEXTRANS
G.E. Zaikov1 and K.Z. Gumargalieva*

N.M. Emanuel Institute of Biochemical Physics,
Russian Academy of Sciences, Moscow, Russia
*N.N. Semenov Institute of Chemical Physics,
Russian Academy of Sciences
Moscow, Russia
ABSTRACT
The contributors collected information about macrokinetic mechanism of

biodegradation of polymer samples based on cross-linked dextrans. The kinetics of
medicine absorption, degradation, and evolution is studied in the model media most
closely resembling living organisms and in blood plasma.
Keywords: biodegradation, dextranes, kinetics, mechanism, cross-linked polymers.
1. INTRODUCTION
It is shown that crosslinked dextrans can serve as a basis for constructing a peculiar kind
of drug-storing vehicular facilities comprising a physiologically active grafted polymer with
medicines attached to it with labile chemical bonds. The kinetics of medicine absorption,
degradation, and evolution is studied in the model media most closely resembling living
1 Chembio@sky.chph.ras.ru, N.M. Emanuel Institute of Biochemical Physics,Russian Academy of Sciences4

Kosygin str., Moscow 119334, Russia.
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Copyright © 2011. Nova Science Publishers, Inc. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under 118 G. E. Zaikov and K. Z. Gumargalieva
organisms and in blood plasma. It is reliably established that polymeric derivatives of a broad
spectrum of antibiotics (of isoniazid and kanamycin series) can be used as durable polymeric
medicines whose long life in organisms is associated with biological absorption of medicines
and polymer matrices and depends on the conditions of their modification and the medium in
which they were implanted.
Applicability and efficiency of polymeric medicines depend not only on their therapeutic
properties but also on biological compatibility of the medicine-carrying polymeric matrix and
the medicine itself with living tissues, and on whether the products of its biodegradation are
toxic or not. Dextran and its derivatives are biocompatible compounds prone to
biodegradation, when exposed to hydrolytic enzymes (such as dextranase and acid α⎯α-
glucosidase) contained in living organisms [l - 4]. The products of their biodegradation are
non-toxic, partake in metabolism, cause no allergic reaction, and pose no other threats to
living organisms. Despite a great many works on this subject, we failed to find any references
to model experiments giving a comprehensive idea about degradation of the polymer-
medicine complexes and macrokinetic parameters of this process.
A series of runs undertaken was intended first, to synthesize macrocomplexes of cross-
linked dextrans (sephadexes) with medicines, in particular, with antibiotics effectively curing
infected cavities of soft tissues, and second, to explore the macrokinetic mechanism of their
degradation.
2. MATERIALS AND TECHNIQUES

Polymeric medicines were synthesized as physiologically active grafted polymers to
which medicines were attached with labile chemical bonds. Polymeric carriers were made of
functional derivatives of cross-linked dextrans representing strongly swelling hydrogels.
Sephadex U-150 (supplied by LKB Inc.) was chemically modified to include reactive
functional groups - aldehyde groups - via oxidation by periodate or carboxy groups via
interaction with monochloroacetic acid (the schemes of the appropriate reactions numbered
(1) and (2) are given below; see also Figs. 1 and 2).
CH2 CH2
O O
O O
OH + 2HIO4
OH
HO
HO OH
O
CH2 CH2
O O
O O
OH HO + HCOOH
HO O HO
O
O + 2HIO3 + H
2 O
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Copyright © 2011. Nova Science Publishers, Inc. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under Macrokinetic Mechanism of Biodegradation of Polymer Samples… 119
CH2 CH2
O
O O
O HC
OH
O HC
O O
C H 2N H 2 C H 2O H H 2N N HC O
O OH
O
I OH
OH
HO O
HO O N H2 II
HO N
N H2 IAH
kanamycin (isonicotinic acid hydrazine)
N H2
CH2 CH2 CH2 CH2

O O O O
O O O O
OH HC OH HC
IV III
N HC N HC
O O
N NH N
NH
Scheme 1.
Aldehyde sephadex (AS) arises by the reaction

CH 2
CH 2 O
O O
O + 2 HIO 4
OH
OH
HO
HO OH
O
(1)
CH 2 CH 2
O O
O O
OH HO + HCOOH
HO O HO
O
O + 2HIO 3+ H O
2
Carboxymethylsephadex is produced by the reaction
C H2 C H2
O O O
O O
OH + Cl C H2 C OH
OH
HO
HO OH
O
(2)
C H2
C H2 O
O O
O + HCl
OH OH
OH O C H2C O O H
Figure 1. (a) Modification of sephadex by periodic acid; (b) immobilization of kanamycin and isoniazid
on aldehyde sephadex.
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Medicines “grafted” onto polymeric supports were well-known antitubercular remedies,

kanamycin and isoniazid (IAH). As indicated in our earlier paper, the species reactive to
polymers, irrespective of stability of the latter, are water, salts (phosphates, sulfates,
bicarbonates), and enzymes; their combination successively models the tissue fluid: 0.1 M
phosphate buffer solution (pH 7.4); 0.1 M citrate-phosphate buffer solution (pH 4.0); aqueous
solution of α-amylase (enzyme) and native blood plasma [5 - 8].
CH2
CH2 O
O O
O O
OH + Cl CH2 C
OH
OH
OH
O
CH2
a
CH2 O
O O
O + HCl
OH OH
OCH2COOH
O
CH2NH2 CH2OH H2N NHC O

OOH
O
OH
OH
HO HO O
O NH2
HO N
NH2
kanamycin IAH
NH2
CH2 CH2 CH2 CH2

O O O O
O O O O
OH OH
O O O O
CH2 CH2
C C
+_
O_ H3 ~ HNH3N O
+
b O N~ O
Scheme 2.
Degradation of polymeric carriers and medicinal polymers was followed by variation of

their relative mass in water, aqueous buffer solutions, and blood plasma at 37°C. At certain
intervals, insoluble portions of the polymer were filtered out and dried to a constant weight.
Weight loss was calculated as m t m 0 , where mt is the instantaneous mass of the polymer
sample, and m0 is its initial mass.
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CH2
CH 2 O
O O
O O
OH + Cl CH 2 C
OH
OH
O OH
CH2
a
CH 2 O
O O
O + HCl
OH
OH
O OCH 2COOH
CH2NH 2 CH2OH H 2N NHC O

OOH
O
OH
OH
HO HO O
O NH 2
HO N
NH 2
kanamycin IAH
NH 2
CH2 CH 2 CH 2 CH2
O O O O
O O O O
OH OH
O O O O
CH 2 CH2
C C
H3 + _
O_ ~ HNH 3N O
+~
b O N O
Figure 2. (a) Modification of sephadex by monochloroacetic acid; (b) immobilization of kanamycin and
isoniazid oil carboxymethylsephadex.
The activation energy was calculated as a slope of the logarithmic temperature

dependence of the rate constant for the medicine release
RT
E= log k ,
τ
where E is the activation energy (J⋅mol-1); k is the rate constant for medicine release (s-1); τ is
time (s); R is the absolute gas constant, R = 8.314 J⋅mol-1K-1; T is temperature (K).
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Copyright © 2011. Nova Science Publishers, Inc. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under 1222 G E. Zaikov and
G. a K. Z. Gum
margalieva
Fiigure 3. Dissolu
ution of aldehydde sephadex in various
v media at
a 37°C: (1) watter; (2) 0.1 M phosphate
p
buuffer solution with
w pH 7.4; (3) 0.1 M phosphaate buffer solution with pH 8.2.
Fiigure 4. Time histories

h of the rate
r of (a) isoniaazid and (b) kannamycin releasee (curves 1 - 3) and of the
reelative weight of the AS-mediccine complex (ccurves l’ -3’, 4) in different media at 37°C: (1,, 1’) water
annd aqueous solu ution of α-amyllase (0.1 mg/ml)); (2, 2’) 0.1 M citrate-phosphaate buffer solutiion with pH
4..0; (3, 3’) 0.1 M phosphate bufffer solution witth pH 7.4; (4) blood
b plasma.
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−1
Figure 5. Logarithmic time histories of ⎛ m t ⎞ ⎛ m t ⎞ for degradation of polymeric complexes of (a)
⎜ ⎟ ⎜ ⎟
⎝ m0 ⎠ 0 ⎝ m0 ⎠ t
kanamycin and (b) isoniazid with AS in aqueous solutions with different pH: (1) 3.4; (2) 4.0; (3) 7.4.
3. EXPERIMENTAL RESULTS AND DISCUSSION

Initial polymer (modified AS containing 30 mol.% of aldehyde groups) placed in water or
buffer solutions gradually dissolved, and the rate of its “bioabsorption” increased with pH of
the medium (Figure 3). This is presumably associated with the presence of hydrophilic
aldehyde groups in its structure and rupture of some cross links in the course of sephadex
oxidation.
The kinetics of medicine ((a) isoniazid and (b) kanamycin) release and absorption of
medicinal polymer AS carrying the medicines in different media displayed in Figure 4
suggests that hydrolytic decomposition of the medicines in the tested model systems occurs
concurrent with biodegradation of the polymeric matrix and that the process follows the same
basic pattern for both medicines.
The two concurrent processes decelerate with time and are complete in 2 - 6 days. Water
(curves 1 and 1′) proved to be most efficient in biodegradation of both polymeric medicines.
AS-isoniazid and AS-kanamycin completely dissolve releasing the medicines into the
solution in 72 h and 48 h, respectively. As the polymeric medicines dissolved in water, pH of
the medium changed from 6.5 to 3.4, which presumably indicated formation of water-soluble
fragments of the acid nature [9, 10]. It turned out that 0.1 M citrate-phosphate (pH = 4.0) and
neutral 0.1 M phosphate (pH = 7.4) buffer solutions catalyze degradation of the chosen
medicinal polymers only slightly if at all (curves 2’ and 3’).
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Copyright © 2011. Nova Science Publishers, Inc. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under 1224 G E. Zaikov and
G. a K. Z. Gum
margalieva
Fiigure 6. Time histories

h of the rate
r of (a) isoniaazid and (b) kannamycin releasee (curves 1 - 3) and of the
reelative weight of the AS-mediccine complex (ccurves l’ - 3’) att different amouunts of the mediicine (mg)
peer 1 g of AS (water, 37°C): (1, 1’) 125; (2, 2’)) 250; (3, 3’) 5000.
T
Table 1. Kineetic parameters of degradaation of mediccinal polymerrs in aqueouss solutions
with
h different pH
H
pH of the
t medium k, 1005×s-1 k, 106×s-1
Kanaamycin Isooniazid
7.4 1.0 5.11
4.0 1.5 7.22
3.4 2.0 11.7
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Table 2. Kinetic parameters for abstraction of kanamycin and isoniazid from the
polymeric matrix
T, °C k, 105×s-1 E, kJ/mol
Kanamycin Isoniazid Kanamycin Isoniazid
25 0.9 0.7
37 1.9 1.2 34.4 47.6
40 2.6 1.6
Figure 7. Time histories of the rate of (a) isoniazid and (b) kanamycin release (curves 1 - 3) and of the
relative weight of the AS-medicine complex (curves l’ - 3’) at different temperatures in water: (1, 1’)
25; (2, 2’) 37; (3, 3’) 40°C.
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⎛ m∞ ⎞
Figure 8. Logarithmic time histories of ⎜ ⎟ for abstraction of isoniazid from AS at different
⎝ mt ⎠
temperatures: (1) 25; (2) 37; (3) 40°C.
Investigation into degradation of medicinal polymers in the presence of α-amylase has

revealed that this hydrolytic enzyme exerts almost the same effect as water (curve 1’). The
reason perhaps lies in the fact that dextran matrices are susceptible to dextranase rather than
to α-amylase [1].
To bring the experimental conditions closer to those realized in living organisms, we
studied behavior of medicinal polymers in blood plasma. The rate of biodegradation in blood
plasma assumed a value intermediate between its values in water and buffer solutions (curve
4). Experiments on degradation of medicinal polymers in media with different pH (7.4, 4.0,
and 3.4) enabled us to calculate the kinetic parameters of this process (Figure 5, Table 1). As
seen from Table 1, the degradation rate of polymeric derivatives of kanamycin and isoniazid
increases with decreasing pH of the medium and peaks at pH 3.4.
We also studied the effect of other factors (the medicine content and temperature) on the
degradation rate of medicinal polymers.
As the medicine content of AS changed, so did the rates of polymer degradation and
medicine abstraction (Figure 6a, b). For example, polymer-isoniazid complex containing 125
mg medicine per 1 g carrier decomposed by 55% in 24 h, while polymeric kanamycin, by
75% (Figure 6, curves 1 and 1’); as the medicine concentration in the polymer increases, so
do the rates of degradation and medicine release (curves 2, 2’, 3, and 3’), i.e., the amount of
medicine bound to the polymeric carrier can be adjusted to attain the wanted supply of
physiologically active species to the recipient.
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Figure 9. Arrhenius plot of the rate constant for abstraction of isoniazid from AS.
⎛ m∞ ⎞
Figure 10. Logarithmic time histories of ⎜ ⎟ for abstraction of kanamycin from AS at different
⎝ mt ⎠
temperatures: (1) 25; (2) 37; (3) 40°C.
The effect of temperature on the rates of degradation of medicinal polymers and medicine
release in water was studied in a thermostat at three different temperatures, 25, 37, and 40°C
(Figure 7a, b). As seen from Figure 7, degradation of medicinal polymers (curves l’ - 3’) and
medicine release (curves 1 - 3) accelerate with increasing temperature. The kinetic parameters
of hydrolytic abstraction of medicines from the polymeric matrix were calculated from the
temperature dependence of its rate (Figs. 8 - 11., Table 2).
Rate constants and activation energies listed in Table 2 suggest that in hydrazone, the
banding energy is higher than in aldimine. This tendency was observed in every run:
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regardless of the experimental conditions, kanamycin was always released faster than
isoniazid. As noted in [11], medicine may escape from a disintegrating polymeric matrix
together with a fragment of the carrier bound to it.
Thus, medicinal polymers on the AS basis are apt to decompose in near-physiological
media, so that degradation of the polymeric matrix occurs con current with medicine release
in the solution. These two processes gradually decelerate and are complete by 80 - 90% in 2 -
3 days. It is reliably established that liberation of active species into the model medium
depends on the nature of chemical bonds between the polymer and medicine and on the rate
of polymer degradation.
Carboxymethylsephadex (CMS) was chosen for an ionogenic polymeric carrier.
Medicine was immobilized on the carrier by electrovalent interactions between functional
groups of the polymer and medicine which finally led to formation of polymer-medicine
complexes (Figure 2b).
As noted by some authors [12], interaction of medicines with polyelectrolytes alters
specificity, raises stability, reduces toxicity, and extends the useful life.
In a liquid biological medium, such polymeric complexes dissociate to the initial polymer
(if the latter is not prone to degradation) and medicine under the action of competing or
displacing counterions.
Experiments on biodegradation of CMS and polymeric complexes on its basis in analogs
of biological media revealed some characteristic features of these polymers. In contrast to AS,
CMS resisted biodegradation in both phos phate buffer solution (pH 7.4) and Ringer-Lock
solution (pH 6.5) (Figure12, curves 1 and 2). This is presumably because chemical
modification of sephadex to produce its carboxy derivative leaves the carbohydrate skeleton
and cross links unscathed, while modification to AS destroys them. Slow degradation of CMS
was observed in blood plasma (curve 3). Blood plasma probably contains biologically active
species which split the polymeric chain of CMS into biologically absorbable fragments.
Complexes of kanamycin and isoniazid with CMS in model biological media (phosphate
buffer, Ringer-Lock solution) decompose by 10 - 20% in 4 - 5 days, releasing 30 - 40% of
free medicines. In blood plasma, these polymeric complexes of medicines decompose by 80 -
90% in 5 days.
Figure 11. Arrhenius plot of the rate constant for kanamycin abstraction from AS.
Thus, it turned out that complexes of CMS with kanamycin and isoniazid gradually
release medicines without damaging the initial structure of the polymeric carrier in all the
studied media except in blood plasma where the polymer matrix undergoes biodegradation.
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Copyright © 2011. Nova Science Publishers, Inc. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under Macrokinetic
M M
Mechanism of Biodegradatio
B on of Polymer Samples… 129
Hence, it would
w be expeected that in liiving organism
ms, polymericc derivatives of
o isoniazid
annd kanamycin n will functionn for long ass “drug storess” slowly suppplying medicines to the
orrganisms.
Fiigure 12. Time histories of the relative mass of

o carboxy-methhylsephadex in various media ata 37°C: (1)
0..1 M phosphate buffer solutionn with pH 7.4; (2) Ringer-Lockk solution with pH
p 6.5; (3) bloood plasma.
REFFERENCESS
[11] R. Ammo on, Enzymologgia, 1963, 25, 245.
[22] M.E. Preoobrazhenskaya, A.L. Minakkova, Carbohyydrate Res., 19974, 38, 268.
[33] M.E. Preeobrazhenskayya, Uspekhi Biologicheskkoi Khimii (A Advances in Biological
Chemistry
ry), Ed. B.N. Stepanenko,
S N
Nauka, Moscow
w, 1975, 25, 2445. (Rus)
[44] V.B. Kozziner, N.A. Feedorov, Mekhaanizm Deistviy iya Poliglitsina (Mechanism m of Action
of Polygly
lycine), Meditssina, Moscow, 1974, p. 191. (Rus)
[55] Appl. Cheem. 28th Macrromol. Symp. Amhers.
A Masss., 1982, 390.
[66] K.Z. Gumargalieva, Yu.V. Mooiseev, and T.T. Dallrrova, Promyyshlennost’
Meditsinsskogo Stekla i Plasticheskikkh Mass (Com mmercial Prodduction of Meddical Glass
and Plasttics), TsBNTI Med. Prom., Moscow, 1981, No.2, 2. (R Rus)
[77] K.Z. Gum margalieva, G..E. Zaikov, Yuu.V. Moiseev,, Usp. Khim., 1994, 63(10), 845. (Rus)
[88] Yu.V. Moiseev,
M G.E. Zaikov,
Z Chem
mical Resistannce of Polymeers in Aggresssive Media,
Plenum Publ.,
P New Yoork, 1987.
[99] M. Singh h, D. Vasadevaan, Biomateriaals, 1982, 3(l), 18.
[110] M. Singhh, D. Vasadevaan, J. Biomed. Mater. Res., 1981, 15(5), 655.

6
[111] V.P. Torcchilin, L.S. Boobkova, V.N. Smirnov, E.I. Chazov, Biooorg. Khim., 1976, No. l,
116. (Russ)
[112] G.V. Sammsonov, L.V. Dmitrienko,
D ett al., Vysokom
mol. Soedin., 19971, 13B(4), 286.
2 (Rus)
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Chapter 15
THERMAL DEGRADATION AND FLAMMABILITY OF

THE POLYETHYLENE/CLAY NANOCOMPOSITE
PREPARED BY MELT INTERCALATION
G. E. Zaikov*1, I. L. Dubnikova2, N.G. Shilkina2, S. M. Lomakin1,

R. Kozlowski†3, Gyeong-Man Kim4
and G. H. Michler‡4
1NM Emanuel Institute of Biochemical Physics of Russian Academy of Sciences,
Moscow, Russia,
2NN Semenov Institute of Chemical Physics of Russian Academy of Sciences, Moscow,
Russia,
3Institute of Natural Fibres, Poznan, Poland,
4Martin-Luther-Universität Halle-Wittenberg, Merseburg, Germany
ABSTRACT
Studies of thermal and fire-resistant properties of the polyethylene/organically
modified montmorillonite (PE/MMT) nanocomposites prepared by means of melt
intercalation are discussed. The sets of the data acquired with the aid of non-isothermal
TGA experiments have been treated by the model kinetic analysis. The extra acceleration
of thermal-oxidative degradation of the nanocomposite which has been observed at the
first stage of the overall process has been analyzed and is explained by the catalytic effect
of the clay nanoparticles. The results of cone calorimetric tests lead to the conclusion that
char formation plays a key role in the mechanism of flame retardation for
nanocomposites.
*
Correspondence to: G. E. Zaikov, N.M. Emanuel Institute of Biochemical Physics of Russian Academy of
Sciences, Moscow, Russia, Kosygin 4, 119934, chembio@chph.ras.ru.
†
Institute of Natural Fibres, Poznan, ul. Wojska Polskiego 71 b, Poland,
‡
Martin-Luther-Universität Halle-Wittenberg, Geusaer Straße, D-06217 Merseburg, Germany
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Keywords: Intercalation polymerization; kinetics; layered clay; nanocomposite;

oxidation; polyethylene; thermal degradation, combustion.
INTRODUCTION
The properties and thermal degradation of model polyethylene (PE) are reasonably well
known [1-12]. It is generally accepted that pristine PE has relatively low thermal stability and
flame resistance. The approach to the enhancement of thermal stability and fire resistance
based on the use of polymer nanocomposites has been extensively developed in the last years
[13–18].
Intercalation in polymer melts is widely used as a simple method for the synthesis of
corresponding materials [18]. In these experimental studies, it was found that PE
nanocomposites based on layered silicates exhibit lower flammability as compared with the
parent polymer, which can be achieved by introducing a small amount of an inorganic silicate
ingredient [13–16].
It is believed that, in the course of high temperature pyrolysis and/or combustion, clay
nanoparticles are capable of promoting formation of protective clay-reinforced carbonaceous
char which is responsible for the reduced mass loss rates, and hence the lower flammability.
Alongside with an enhancement of flame resistance of such nanocomposites the rise of
thermal stability observed during TGA experiments. Generally, TGA cannot be used to
elucidate a complex mechanism of polymer thermal degradation. Nevertheless, dynamic TGA
has been frequently used to study the overall thermal degradation kinetics of polymers
because it gives reliable information on the kinetic parameters, such as preexponential factor,
the activation energy, and the overall reaction order [20-22]. The thermal degradation kinetics
of polyethylene has been studied by many investigators. Various suggestions for the kinetic
parameters for polymer degradation have been reported [8–10, 20-22]. Although some
attempts have been made to understand the complex nature of decomposition of a polymer,
involving numerous reactions, some authors have found it sufficient to consider a global first
order kinetic expression to represent the overall decomposition rate [8].
In this work we applied the model kinetic analysis of PE and PE/MMT thermal-oxidative
degradation in order to predict an increase of flame resistance for PE nanocomposite, i.e. the
reduction of the mass loss rate and the rate of heat release.
EXPERIMENTAL
1. Materials
Polyethylene (PE), Basel Lupolen, was used to prepare PE nanocomposites in the

combinations with polar compatibilizer, maleic anhydride-modified oligomer (MAPE)
Polybond 3109, provided by Crompton. A Cloisite 20A (purchased from Southern Clay
Products, Inc.) has been used as the organically modified montmorillonite (MMT) to prepare
PE-MMT and PE-MAPE-MMT nanocomposites throughout this study. The content of an
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organic cation-exchange modifier, N+2CH32HT (HT=hydrogenated tallow, C18≈65%;

C16≈30%; C14≈5%; anion: Cl-), in the MMT was of 38 % by weight.
2. Preparation of Nanocomposites
PE/MAPE/MMT nanocomposites were prepared by the melt mixing of the components

in a double-rotor laboratory (Brabender) mixer in two steps. PE and maleic anhydride-
modified oligomer (MAPE - Polybond 3109 by Crompton co.) were blended/mixed using a
laboratory Brabender mixing chamber in two steps. In the first step, the two polymers PE and
MAPE were blended in a 4 : 1 ratio for 2 min; after that, an MMT powder was added in an
amount of 3 and 7 wt %. The mixing of components at the second step lasted for 10 min at a
temperature of 190°C and rotor speeds of 60 rpm. Samples designed for cone calorimeter
testing in the form of 70x70x3 mm plates with a mass of 14.0±0.1 g were prepared by
molding at 190°.
3. Investigation Techniques
Transmission Electron Microscopy (TEM).

The filler dispersion in the composites was studied by the TEM technique with a Philips
EM-301 electron microscope (the Netherlands) at an accelerating voltage of 80 kV. Thin
sections of film samples for TEM examination were prepared with an LKB Ultratome III®
ultramicrotome.
Small-Angle X-Ray Scattering (SAXS).

SAXS analysis of nanocomposite layered structure was performed in the reflection mode
over the angular range of on film samples at room temperature using a DRON-2 X-ray
Diffractometer (CuKα radiation) with modified collimation. Diffraction patterns were
collected in reflection-mode geometry from 2° to 10°2θ. Interlayer distances in MMT were
determined from the angular positions of base reflections (d001) of MMT in the diffraction
patterns of composites. The degree of polymer intercalation was determined from a change in
the interlayer distance in MMT.
Thermogravimetric Analysis (TGA).

A Perkin-Elmer TGA-7 instrument calibrated by Curie points of several metal standards
has been employed for non-isothermal thermogravimetric analysis. The measurements were
carried out at a desired heating rate (in the range of 2.5 – 10 K/min) in air. A kinetic analysis
of the thermal degradation of composites was performed with the use of the NETZSCH-
Gerätebau Thermokinetics software. The algorithm of the kinetic analysis program was based
on the calculation of regression by the fifth-order Runge-Kutta method using the dedicated
Prince-Dormand formula for automatic optimization of the number of significant digits [23,
24].
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Combustibility Characteristics (Cone Calorimeter)

Ignitability tests were performed according to the standard procedures ASTM 1354-92
and ISO/DIS 13927 using a cone calorimeter [25].

Investigation of Nanocomposite Structure
Small-angle X-ray scattering (SAXS) has been used to evaluate the degree of
intercalation of the organoclay particles in the polymer matrix. SAXS diffraction patterns for
SAXS patterns for the original Cloisite 20A, PE-7% Cloisite 20A, PE-MAPE-7% Cloisite
20A and MAPE-7% Cloisite 20A are displayed in Figure1.
Figure1. SAXS patterns for the original Cloisite 20A (1), PE-7% Cloisite 20A (2), PE-MAPE-7%
Cloisite 20A (3) and MAPE-7% Cloisite 20A (4)
The Cloisite 20A itself has a single peak at around 3.7o with d-space of 2.4 nm (Figure1
curve 1). The shift of the clay basal spacing d001 from 3.7° to 2.7° in PE-MAPE-7% Cloisite
20A (Figure1 curve 3) sample suggests the intercalated nanocomposite sample have higher d-
space (3.3 nm) than that in the original clay (2.4 nm), it may have some exfoliated structures,
and considering the smearing of peak in nanocomposite sample, the nanocomposite structure
have not been well exfoliated. Figure1 also shows the shift of the base reflection toward
smaller angles for PE-7% Cloisite 20A sample from 3.7° to 2.9° (curve 2), which indicates an
increase in the interplanar distance in the silicate structure of the PE-7% Cloisite 20A
nanocomposite from 2.4 to 3.07 nm by intercalation.
TEM technique has been used to evaluate the degree of exfoliation of the organoclay
particles in the polymer matrix. Figs. 2-4 show the influence of polar compatibilizer (MAPE)
on the exfoliation degree of the MMT in the nanocomposites.
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Figure2. TEM micrographs of MAPE-7%Cloisite 20A - maleic anhydride-modified PE oligomer

(Polybond 3109) at different magnification showing mainly exfoliated nanocomposite.
Figure3. TEM micrographs of PE-MAPE-7%Cloisite 20A at different magnification showing discrete

(hybrid) structure of nanocomposite consisting of intercalated tactoids and exfoliated monolayers.
Figure4. TEM micrographs of PE-7%Cloisite 20A at different magnifications (for the most part
intercalated nanocomposite).
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It is seen that the full exfoliation of the MMT particles to the monolayers takes place
under the action of maleic anhydride-modified PE compatibilizer in the MAPE-MMT
nanocomposite (Figure2), whereas in the PE-MAPE-MMT nanocomposite the hybrid
structure of consisting of intercalated tactoids and exfoliated MMT monolayers has been
formed (Figure3). Finally, the pure PE-MMT composition has the intercalated structure of
nanocomposite (Figure4).
Study of Thermal-Oxidative Degradation of PE-MAPE-MMT

Nanocomposite
It is acknowledged that thermal stability of polymer nanocomposites is higher than that of

pristine polymers, and this gain is explained by the presence of anisotropic clay layers
hindering diffusion of volatile products through the nanocomposite material.
The radical mechanism of thermal degradation of PE has been widely discussed in a
framework of random scission type reactions [1-10]. It is known that PE decomposition
products comprise a wide range of alkanes, alkenes and dienes. The polymer matrix
transformations, usually observed at lower temperatures and involving molecular weight
alteration without formation of volatile products, are principally due to the scission of weak
links, e. g. oxygen bridges, incorporated into the main chain as impurities. The kinetics of
thermal degradation of PE is frequently described by a first-order model of mass conversion
of the sample [10,21]. A broad variation in Arrhenius parameters can be found in literature, i.
e., activation energy (E) ranging from 160 to 320 kJ/mol and pre-exponential factor (A)
variations in the range of 1011 and 1021 s-1 [7-10] are not unusual. It is believed that the broad
range of E values reported may be explained by the polymers molecular mass variations, by
use of various additives, and by different experimental conditions [10] employed by different
authors.
Thermal-oxidative degradation of PE and PE nanocomposites has been extensively
studied over the past decades [26-28, 14-17]. It has been reported that the main oxidation
products of PE are aldehydes, ketons, carboxylic acids, esters and lactones [26, 27].
According to [26], β-scission plays an important role in thermal oxidation of UHMWPE.
Notably, the feasibility of intra-molecular hydrogen abstraction by the peroxy radicals for
polyethylene has been questioned in frames of a thermal oxidation mechanism proposed by
Gugumus [27, 28]. A mechanism describing oxidation of organic molecules by virtue of
complex chain reactions has been proposed earlier by Benson [29].
In the present work, the processes of thermal degradation of PE and PE-MAPE-MMT
nanocomposite with MMT content of 7 wt. % have been investigated by TGA in an air at the
heating rates of 2.5, 5 and 10 K/min. According to the dynamic TGA data, the polymer
thermal-oxidative degradation starts at about 300°C and then, through a complex radical
chain process, the material totally destructs and completely volatilizes in the range of 450-
500oC (Figure 4).
The diverse behavior of PE and PE-MAPE-MMT (Figs.5 and 6) shows that the influence
of MMT nanoparticles on the thermal-oxidation process resulted in higher thermal-oxidative
stability of hybrid PE-MAPE-MMT nanocomposite. It can be seen a regular increase in the
temperature values of the maximum mass loss rates (about 50oC) for the PE-MAPE-MMT as
compared to pristine PE (Figure 6).
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Figure5. TGA curves for PE (1 – 2.5K/min, 2 - 5K/min, 1 - 10K/min,) and PE-MAPE-MMT (4 –

2.5K/min, 5 - 5K/min, 6 - 10K/min).
Figure 6. DTG curves for PE (1 – 2.5K/min, 2 - 5K/min, 1 - 10K/min,) and PE-MAPE-MMT (4 –

2.5K/min, 5 - 5K/min, 6 - 10K/min).
It seems reasonable to suggest that thermally stable crosslinked carbonized layer on the
nanocomposite surface is formed during the thermal-oxidative degradation and starts to
hinder the diffusion transport of both the volatile degradation products (out of the polymer
melt into the gas phase) and the oxygen (from the gas phase into the polymer). The above set
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of events results in actual increase of the nanocomposite thermal stability in the temperature
range of 350-500°C, where normally a general degradation of the main part of PE takes place.
Kinetic Analysis of PE-MAPE-MMT Thermal Oxidative Degradation
Kinetic studies of material degradation have long history, and there exists a long list of
data analysis techniques employed for the purpose. Often, TGA is the method of choice for
acquiring experimental data for subsequent kinetic calculations, and namely this technique
was employed here.
It is commonly accepted that the degradation of materials follows the base equation (1)
[23]
dc/dt = - F(t,T co cf) (1)
where: t - time, T - temperature, co - initial concentration of the reactant, and cf - concentration

of the final product. The right-hand part of the equation F(t,T,co,cf) can be represented by the
two separable functions, k(T) and f(co,cf):
F(t,T,co,cf) = k[T(t)·f(co,cf)] (2)
Arrhenius equation (4) will be assumed to be valid for the following:
k(T) = A·exp(-E/RT) (3)
Therefore,
dc/dt= - A·exp(-E/RT)·f(co,cf ) (4)
All feasible reactions can be subdivided onto classic homogeneous reactions and typical
solid state reactions, which are listed in Table 1 [23]. The analytical output must provide good
fit to measurements with different temperature profiles by means of a common kinetic model.
Kinetic analysis of thermal oxidative degradation of PE and PE-MAPE-MMT at the
heating rates of 2.5, 5 and 10K/min. (Figure7 a, b) has been accomplished by using the
interactive model based nonlinear fitting approach in accordance with a formalism we
proposed earlier [30].
In order to assess the activation energy for development of a reasonable model for kinetic
analysis of pristine PE and PE-MAPE-MMT thermal degradation processes, a few

evaluations by model-free Friedman analysis have been done as the starting point [31].
Further, nonlinear model fitting procedure for PE and PE-n-MMT TGA-curves has led to the
following triple-stage model scheme of successive reactions, wherein a general nth-order (Fn)
reaction was used for all steps of the overall process of thermal oxidative degradation (Table
1) (Figure7 a, b):
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Table 1. Reaction types and corresponding reaction equations, dc/dt= - A·exp(-

E/RT)·f(co,cf )
Name f(co,cf ) Reaction type

F1 c first-order reaction
F2 c2 second-order reaction
Fn cn nth-order reaction
R2 2 · c1/2 two-dimensional phase boundary

R3 3 · c2/3 reaction
three-dimensional phase boundary
D1 0.5/(1 - c) reaction
D2 -1/ln(c)
D3 1.5 · e1/3(c-1/3 - 1) one-dimensional diffusion
D4 1.5/(c-1/3 - 1) two-dimensional diffusion
three-dimensional diffusion (Jander's
B1 co · cf type)
Bna con · cfa three-dimensional diffusion
(Ginstling-Brounstein type)
C1-X c · (1+Kcat · X)
simple Prout-Tompkins equation
expanded Prout-Tompkins equation
Cn-X cn · (1+Kcat · X) (na)
first-order reaction with

A2 2 · c · (-ln(c))1/2 autocatalysis through the reactants,
A3 3 · c · (-ln(c))2/3 X. X = cf.
An N · c · (-ln(c))(n-1)/n
nth-order reaction with autocatalysis
through the reactants, X
two-dimensional nucleation
three-dimensional nucleation
n-dimensional nucleation/nucleus
growth according to Avrami/Erofeev
(5)
As data in Table 2 for the first stage of thermal oxidative degradation reaction show, the
activation energies values for PE and PE-MAPE-MMT amount to 65.5 and 87.5 kJ/mol, thus
indicating that the degradation of these samples is initiated by the similar oxygen induced
reactions. At the same time, the values of activation energy found at the second and third
stages of thermal-oxidative degradation for PE-n-MMT (266.2 kJ/mol and 279.6 kJ/mol) are
higher than those for PE (238.5 and 250.2 kJ/mol) (Tab.2). This difference may be attributed
to a shift of the PE-n-MMT degradation process to a diffusion-limited mode owing to
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emergence in the system of a carbonized cross-linked material. It is known [11] that the
contribution of radical recombination reactions, which lead to the intermolecular crosslinking,
increases under the oxygen deficiency conditions. Such conditions are realized at thermal
oxidative degradation of the PE nanocomposites due to the labyrinth effect of the silicate
layers towards the diffusing gas.
Figure7. Nonlinear kinetic modeling of PE (a) and PE-MAPE-MMT (b) thermal-oxidative degradation
in air. Comparison between experimental TGA data (dots) and the model results (firm lines) at several
heating rates.
The formation of chemical crosslinking during the thermal-oxidative degradation of the

PE nanocomposites is a necessary condition of PE carbonization process.
This fact infers that the last stage of the PE-n-MMT degradation process is governed
mainly by random scission of C-C bonds, rather than by an oxygen catalyzed reactions. On
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the other hand, these results are also consistent with the barrier model mechanism, which
suggests that inorganic clay layers can play a role of barriers retarding the diffusion of oxygen
from gas phase into the nanocomposite.
Flammability Characteristics of PE and PE-MAPE-MMT Nanocomposites
The flammability characteristics of pristine PE and PE-MAPE-MMT with 3 and 7% by

weight Cloisite 20A nanocomposites were examined with a cone calorimeter at the incident
heat flux of 35 kW/cm2 for the samples having a standard surface area of 70 × 70 mm and
identical masses of 12.0 ± 0.2 g.
Table 2. Results of the multiple-curve kinetic analyses for thermal-oxidative
degradation of PE and PE-MAPE-MMT in accordance with the reaction model (5)
Material Parameter Value Corr. Coeff.
logA1, s-1 3.7

E1, kJ/mol 65.5
n1 1.2
logA2, s-1 15.5
E2, kJ/mol 238.5 0.9989
PE
n2 0.6
logA3, s-1 16.9
E3, kJ/mol 250.2
n3 1.7
logA1, s-1 5.2

E1, kJ/mol 87.5
n1 1.3
PE-MAPE-MMT logA2, s-1 16.5
E2, kJ/mol 266.2 0.9992
n2 0.8
logA3, s-1 17.2
E3, kJ/mol 279.6
n3 0.9
Figures 8, 9 and 10 depict the plots of the basic ignitability characteristics: heat release
rate, mass loss rate, and specific heat of combustion, versus time for PE, as well as for the
PE–MAPE–7 wt % MMT and PE–MAPE–3 wt % MMT nanocomposites.
From Figure8, it is seen that the maximum heat release rate for pristine PE is 2005
kW/m2, whereas that for the PE-MAPE-MMT-3% wt. nanocomposite and the PE-MAPE-
MMT-7% wt. nanocomposite is 789 and 728 kW/m2, respectively; thus, the peak heat release
rate decreases by 40%. A similar trend is observed in Figure9, which illustrates the
dependence of the mass low rate on the combustion time; Figure11 shows the time
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dependence for the specific heat of combustion, which is practically identical for all of the
three samples.
Figure8. Rate of heat release vs. time for PE (1), PE-MAPE-MMT-3% wt. (2) and PE-MAPE-MMT-
7% wt. (3) obtained by cone calorimeter at the incident heat flux of 35 kW/cm2.
Figure9. Mass loss rate vs. time for PE (1), PE-MAPE-MMT-3% wt. (2) and PE-MAPE-MMT-7% wt.
(3) obtained by cone calorimeter at the incident heat flux of 35 kW/cm2.
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Figure10. Heat of combustion vs. time for PE (●), PE-MAPE-MMT-3% wt. (○) and PE-MAPE-MMT-
7% wt. (▲) obtained by cone calorimeter at the incident heat flux of 35 kW/cm2.
This resemblance confirms that the silicate agent does not inhibit the gas-phase
combustion process and, thus, does not affect the heat of combustion of the samples; the
effect of twofold reduction in the maximum rate of heat release may be explained in terms of
formation of a protective char layer on the burning polymer surface. The value characterizing
the average amount of released carbon monoxide remains practically unchanged over the
entire set of test samples; however, a small increase in the maximum CO yield for
nanocomposite samples at the end of combustion time intervals indicates the crossover of
active combustion to the oxygen-deficient smoldering phase (Figure11).
Figure11. CO yield vs. time for PE (1), PE-MAPE-MMT-3% wt. (2) and PE-MAPE-MMT-7% wt. (3)
obtained by cone calorimeter at the incident heat flux of 35 kW/cm2.
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It is noteworthy that despite effective charring, the maximum level of smoke formation
during the combustion of PE nanocomposites does not exceed the level of pristine PE, and its
total yield is practically the same in all cases (Figure11).
The obtained results validate the conclusion that char formation plays a key role in the
mechanism of flame retardation for nanocomposites. The sample surface coated with a
composition of silicate particles and the heat-resistant organic ingredient of char is a very
effective barrier on the way of flame propagation over the surface. The ideal structure of the
protective layer containing silicate particles and organic char must be a densely crosslinked
network structure and must possess a considerable mechanical strength sufficient for the
protective layer to remain intact during the burning up of the polymer from the surface.
CONCLUSION
Dynamic TGA experiments show substantial increase in thermal oxidative stability of the
PE-MAPE-MMT nanocomposite as compared to pristine PE.
Collective action of chemical cross-linking and catalytic dehydration promoted by MMT
presents a necessary and sufficient condition of solid phase carbonization reactions, which is
observed in the process of thermal-oxidative degradation and combustion of PE-MAPE-MMT
nanocomposites. Carbonized layer formation leads to appreciable increase of thermal stability
of PE-MAPE-MMT nanocomposite, owing to a hindrance of the mass transfer in the
nanocomposite. This fact explains an increase of thermal-oxidative stability in the PE-MAPE-
MMT nanocomposite as well as its fire-proof properties.
Design data of the isothermal oxidative degradation at 600oC provided by the model
kinetic analysis reveal substantial reduction of the mass loss rate of PE-MAPE-MMT
nanocomposites as compared to pristine PE. These results are in close agreement with the
experimental cone calorimeter tests performed at an incident heat flux of 35 kW/cm2.
REFERENCES
[1] Lacey DJ; Dudler V.V. Polym. Degrad. Stab. 1996, 51, 1011.
[2] Paabo M; Levin BC Fire Mater 1987, 11, 55.
[3] Lattimer RP J. Anal. Appl. Pyrolysis 1995, 31, 203–226.
[4] Kuroki T; Sawaguchi T; Niikuni S; Ikemura T Macromolecules 1982, 15, 1460–1462.
[5] Kiran E; Gillham JK J Anal Appl Pyrolysis 1976, 20, 2045–2068.
[6] Blazso M J. Anal. Appl. Pyrolysis 1993, 25, 25–35.
[7] Hornung U; Hornung A; Bockhorn H Chem. Ing. Tech. 1998, 70, 145–148.
[8] Hornung U; Hornung A; Bockhorn H Chem. Eng. Tech. 1998, 21, 332–337.
[9] 9 Bockhorn H; Hornung A; Horung U J. Anal. Appl. Pyrolysis 1998, 46, 1–13.
[10] Bockhorn HA; Hornung A; Hornung U; Schawaller D Journal of Analytical and
Applied Pyrolysis 1999, 48, 2, 93.
[11] Grassie N; Gerald S Polymer Degradation and Stabilization; Cambridge University
Press: Cambridge - New York – Melbourne – Sydney, 1988, 222.
[12] C. Breen, P.M. Last, S. Taylor, Komadel P., Thermochim. Acta 363 (2000) 93-04
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[13] Zanetti M., Lomakin S.M., Camino G., Macromol Mater Eng. 2000, 279, 1-9.
[14] Alexandre M; Dubois P Mater Sci. Eng. R 2000, 28, 1–63.
[15] Giannelis EP Adv. Mater. 1996, 8, 29-35.
[16] Gilman J.W., Kashiwagi T., Nyden M., Brown J.T., Jackson C.L., Lomakin S.M.,
Gianellis E.P., Manias E In: Chemistry and Technology of Polymer Additives; Al-
Maliaka S, Golovoy A, Wilkie CA, Eds.; Blackwell Scientific: London, 1998; 249–265.
[17] Zanetti M., Bracco P., Costa L., Polym. Degrad Stab. 85 (2004) 657-665.
[18] Ray S.S., Okamoto M., Prog. Polym. Sci. 28 (2003) 1539–1641.
[19] Kojima Y., Usuki A., Kawasumi M., Okada A., Fukushima Y., Kurauchi T., Kamigaito
O., J. Mater. Res. 8 (1993) 1185.
[20] C. Breen, P.M. Last, S. Taylor, Komadel P., Thermochim. Acta 363 (2000) 93-04.
[21] Gao Z., Amasaki I., Kaneko T., Nakada M., Polym. Degrad. Stab. 81(2003) 125-130.
[22] Jin Woo Park J., Oh S., Lee H., Kim H., Yoo K., Polym. Degrad. Stab. 67 (2000) 535-
540.
[23] Opfermann J, J. Thermal Anal. Cal., 60 (2000) 641.
[24] D. Marquardt. J. Appl. Math. 11 (1963) 431.
[25] Babrauskas V. Fire and Materials 19 (1995) 243.
[26] Lacoste L; Carlsson DJ J. Polym. Sci. Part A Polym. Chem. 1992, 30, 493-500.
[27] Gugumus F Polym. Degrad. Stab. 2002, 76, 2, 329.
[28] Gugumus F Polym. Degrad. Stab. 2002, 77, 1, 147.
[29] Benson SW Thermochemical Kinetics; Wiley:New York, 1976, 114.
[30] Lomakin S.M., Dubnikova I.L., Berezina S.M., Zaikov G.E., Polym. International 54
(2005) 7, 999-1006.
[31] Friedman HL J. Polym. Sci. C 6 (1965), 1, 175.
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Chapter 16
MECHANISM OF THE REACTION FOR FORMATION OF

GLYCOSIDE BONDS OF SUGAR CARBAMIDES
J. A. Djamanbaev*, J. A. Abdurashitova, G. E. Zaikov†, and

V.A. Afanasjev
Institute of Chemistry and Chemical Technology,
Kyrgyz National Academy of Sciences,
Bishkek, Kyrgyzstan;
N. M. Emanuel Institute of Biochemical Physics,
Russian Academy of sciences,
Moscow, Russia
ABSTRACT
The reactional ability of the glycoside center with the purpose of elaboration of the
effective methods of introduction of the urea rests and its derivatives in the first position
of the carbohydrate ring have been presented in this work. It was shown that the
protoning of N-glycoside in the conditions of acid catalysis leads to the growth of the
effective, positive charge on C1 and it increases its reactional ability with reference to
attacking nucleophiles, that was confirmed by the quantum-chemical calculations.
Keywords: monosaccharides, glycosides, glycosylureas.

The reactional ability of the first carbon atom of monosaccharides and glycosides have
been examined in works [1, 2]. It is well-known, that reactional ability of glycoside center C1
in the processes of nucleophilic connection and replacements is defined mainly by the size of
positive charge on C1. The calculations of electronic charges carried out by the method of
*
720071, Kyrgyzstan, Bishkek, 267 Chui Prospect, e-mail: Djamanbaev-J@mail.ru.
†
119334, Russia, Moscow, 4 Kosydin Str.e-mail: Chembio@sky.chph.ras.ru.
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Copyright © 2011. Nova Science Publishers, Inc. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under 148 J. A. Djamanbaev, J. A. Abdurashitova, G. E. Zaikov et al.
inductive parameters Del-Re [3] and modern quantum-chemical methods of calculation of

electronic structure [HyperChemPro7, MNDO] show, that among all carbon atoms of a
carbohydrate molecule the greatest effective positive charge really possesses C1. Effective
charges on atoms and lengths of bonds of the urea’s carbohydrate derivatives received by
method MNDO, are presented in figure 1.
(a)
0,197
-0,312 H
0,947
O
0,014 0,024
H 1,388
H
1,122 1,123
0,010 0,191
0,176
H
H 0,151
1,132 1,589 -0,334
1,005 H
0,204 1,402 O
0,125 -0,424 -0,298
H 1,393 0,112 0,013 1,007
1,403
N N
0,947 O 1,586 H 1,470
1,130 0,435 1,422
-0,313 1,132 1,413
1,585 C 1,005
-0,309 H 0,080
O 0,003 1,233
0,948 0,108 1,593 0,282 H
1,389 1,584 0,150
H 1,389 1,135 O
0,191 1,129 -0,388
O 0,947 H
H -0,298 0,061
0,005 H
0,188
(b)
0,196
-0,312 H
0,947
O
0,014 0,025
H 1,387
H
1,122 1,123
0,010 0,191
H 0,171 0,171
1,132 1,580 -0,336 H H -0,001
0,204 1,402 O H
0,125 1,007 1,003
H 1,393 0,112 0,012 -0,425 1,115
-0,377
0,947 O 1,586 H 1,403 N N
-0,313 1,130 0,466 0,196
1,584 1,132
1,470 1,421 1,410 1,464 C 1,115
-0,309 H 0,080 C
O 0,001 H
0,948 0,108 1,589 0,278 1,112
1,584 1,233 0,019
1,389
H 1,389 1,135
0,191 1,129 O H
O 0,947 H -0,393 -0,015
H -0,298 0,054
0,004 H
0,187
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Copyright © 2011. Nova Science Publishers, Inc. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under Mechanism of the Reaction for Formation of Glycoside Bonds… 149
(c)
0,066 0,064
H H
0,196
H -0,042 -0,054
-0,312
0,947
O 0,070 0,062
-0,063
0,014 H -0,057 H
0,025
H 1,387
H
1,122 1,123 0,033 -0,046
0,010 0,191
H H
1,132 1,580 -0,336 0,176 0,068
0,191 1,402 O H
0,125 0,112
H 1,393 0,012 1,007
1,586 1,403
0,947 O H -0,414
1,130
-0,310 1,584 1,132 N 1,410 N -0,307
-0,309 H 0,076 1,470 0,455
O 0,001 1,421
0,948 0,108 1,589 0,290 C 1,003
1,389 1,584 H
H 1,389 1,135 1,233 0,161
0,191 1,129
O 0,947 H O
H -0,301 0,068
0,004 H -0,383
0,187
Figure 1. Charges on atoms and lengths of bonds in molecules of derivatives glycosylurea received by
optimization of the geometrical parameters by quantum-chemical method MNDO: a) glycosylurea; b)
glycosylmetylurea; c) glycosylphenylurea.
Nevertheless, in the reactions of formation of glycosyl bonds takes always place the acid
catalysis which is connected with effects of protoning of heteroatoms, directly connected with
the glycoside center, for example:
O C1 OH + H3O+ O C1 OH2 + H2O (a)
H H
O C1 OH + H3O+ O C1 OH + H2O (b)
H H H
Regardless of, on what of oxygen atoms there takes place a protoning, connection of a
proton considerably raises owing to inductive effect the size of a positive charge on С1 and
due to it increases its reactional ability with the reference to nucleophilic agents. This point of
view on the nature of activating action of acids is the most widespread. There are also another
representations connected with studying of reactions of carbonyl group [4-6]. It is believed,
for example, that protoning is necessary not at the stage of connection nucleophile, but at the
stage of elimination of a water molecule from the intermediate compound, having the
structure of aminoalcohol. It means that reactional ability of C1 and nucleophility of attacking
nucleophile are great enough to proceed the first stage without acid activation of the glycosid
center. This representation is fair for such strong agents as aliphatic and many aromatic
amines with high enough values of a basicity parameter (pKa). As for urea and its derivatives
(as well as amids in general) they have low nucleophility and basicity and therefore enter the
reactions of connection on С1 with great difficulty. The lowered reactional ability of the
amino group in urea is explained by the strong delocalization of electronic density or
imposing of structures of type (A) and (B):
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H2N C O H2N C O
R R
(A) (B)
0,183 0,183
H H
0,992 0,992
1,393 0,497 1,393
N C N -0,426
-0,426
0,994 0,994
1,235
H O
0,201 -0,415 H
0,201
(а)
-0,002
0,201 H
H
1,114
0,995
-0,427 0,500 -0,446 0,233 1,114 -0,002

1,402
N C N C H
1,394 1,455
0,992
1,233
0,998 1,114
H O H
0,183 -0,407 H
0,179
-0,011
(b)
0,062
0,092 H
H 1,091
1,089
0,203
H -0,086
-0,032
0,995 1,408
1,417 1,403
-0,427 0,503 -0,360 0,062
1,411
N C N 0,137 -0,090 H
1,396 1,417 1,090
0,992
1,230 1,406
1,003 1,426 1,402
O -0,030
H H -0,121
0,185 -0,391 0,178

1,091 1,091
H
H
0,057
0,059
(c)
Figure 2. The effective atomic charges and lengths of bonds in the molecules of derivatives of urea
received by optimization of geometrical parameters by quantum-chemical method MNDO: a) urea; b)
metylurea; c) phenylurea.
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The structure (B) is actually interfaced acid and as the results of potensiometric titrations
show, amides of carbonyl acids are more weak acids, than bases [4]. As basicity and
nucleophility are the values, mutually connected with each other, the decrease of basicity
leads to the decrease of nucleophilic reactional ability of amino group of urea. The effective
atomic charges and lengths of bonds in molecules of derivatives of the urea received by
optimization of geometrical parameters by semi-empirical, quantum-chemical method
MNDO are shown in figure 2.
What approaches are possible for activation of urea and its derivatives and simplification
of reactions of formation N-glycosylureas?
The variant at which the molecule of urea is deformed is theoretically possible and gets
such space arrangement at which n-orbital of nitrogen atom are not blocked with π-orbitals of
C=O group. In this case the basicity and nucleophility of amino group should increase
sharply. It is known, for example, the cyclic lactam in which uncoupledcoupled electrons of
nitrogen atom are not blocked with π- electrons of carbonyl group [4]. As the result of it is the
increase in basicity parameter at five orders in comparison with usual (not cyclic) lactams.
However, it is hardly possible to deform a molecule of urea and to deduce π-orbitals from the
interface with n-orbitals in conditions of coordination catalysis.
On account of stated one can believe, that attempts to activate the carbamide fragments
with using of homogeneous acid or coordination catalysis is the work of the future. In this
connection searching of ways for increasing the nucleophilic reactional ability of glycoside
center of sugars is actual.
Because of the weak protoning of glycoside and cyclic oxygen atoms usual acids
catalysis of proton type appears to be very poorly effective – it is necessary to use the
concentrated solutions of acids. However, in the field of Gamete acidity (H0) the secondary
reactions of sugar start to develop. It is necessary to take into consideration also that in
solutions of the concentrated acids there is a protoning of urea and its derivatives. Thus, as the
calculations of the electrostatic field of urea (method PPDP/2) have shown [5-6] mainly it
should be protoning of carbonyl oxygen, therefore communication C-O is weakened and
communication С-N is strengthened, but the essential change for nucleophility of the amino
group does not occur. These peculiarities in the behavior of reagents in sour environments
limit synthetic opportunities of acid catalysis and demand to search for new ways of
activation.
For development of the effective methods of synthesis of carbohydrate derivatives of urea
we have addressed to N-glycosides, which, as the kinetic studies showed, possess much
greater reactional ability to the nucleophilic agents [1]. From the point of view of electronic
representations the replacement of glycoside hydrocsyl HC1-OH on N-aglycon should not
increase the electrophilic reactional ability of С1. Indeed, as it was shown by the carried out
calculations of σ-electronic charges by the method of inductive parameters Del-Re, during the
formation of N-glycosid bond it occurs an appreciable increase in the effective positive
charge on С1, therefore the electrophilic reactional ability of the glycoside center should
increase too.
It should be considered, however, one important circumstance – high protono-acseptornic
ability of nitrogen atom in comparison with the atom of oxygen. Protoning of this center in N-
glycosides in conditions of acid catalysis will lead to the growth of an effective positive
charge on С1 and to the increase of its reactional ability in relation to attacking nucleophils.
These reasons specified a real opportunity for the development of effective methods of
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synthesis of glycosides with little basicity on the basis of N-glycosides in which N-aglycon
has high enough basicity [7-9].
Let's explain above-mentioned on an example of the simple scheme for acid catalysis
reactions of nucleophilic replacement at С1 [1, 2]. The presented mechanism includes two
basic stages of reaction – protoning of initial glycosid on the atom of nitrogen of N-glycosid
bond (a) and as the result of it interaction of the protoning form of glycosid with attacking
nucleophyl (b) the replacement of initial N-aglycon on a new aglycon take place (the scheme
1 ).
CH2OH CH2OH
O O
Ka
OH NH R + H OH NH2 R (a)
OH OH
OH OH
CH2OH CH2OH
O O
a
OH NH2 R + HB OH B + NH2R + H (b)
OH OH
OH OH
Scheme 1.
Having taken advantage of a method of stationary concentration, it is easy to receive the

final expressions for the observed speed of the reaction (1) and for the observed action
constant (2) [10].
νobser.= а [-HC1NH2+R]⋅[HB] (1)
kobser..= а [H+] / ka (2)
According to last expression, the less the constant of dissociation Ка of the protoning
form of glycoside (i.e. the more basicity initial the N-aglycon, expressed in the size pKa), the
lower acidity of solution the reaction (b) of replacements initial N-aglycon on a new aglycon
will proceed.
Therefore, knowing the size of a parameter of basicity pKa of initial N-glycoside it is
possible to estimate approximately that area of values pH in which the reaction of
replacement will proceed with good speeds for practice.
EXPERIMENTAL RESULS, DISCUSSION AND CONCLUSION

As a result of searching of mechanism of catalysis the reaction for formation of glycoside
bonds was elaborated the method of synthesis of glycosides with varies aglycons.
Methods of investigations: paper chromatography, element analysis, IR, PMR-
spectrocopy.
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Preparation of Derivatives of Urea for Example N-Glucoside Urea
To a mixture of 2 g N-glucoside of metanitroanilin, 15 ml of methanol is added the

solution, containing 1,8 g urea, 12 ml methanol and 0,25 ml a concentrated hydrochloric acid
and heated for 10 minutes. The reside is recrystallized from methanol. The product yield is
72%. M.p. 205-2060C, [α]20D=-20,50 (c 0,68; water), Rf=0,11 system: butanol: acetic
acid:water (4:1:%). Found, % N-11,50; % C-34,94; % H-6,60.
Thus, on the base of kinetic investigations of the reaction of glycoside center was offered
the effective method of synthesis of the carbohydrate derivatives of urea with using
glucosylarylfmines.
REFERENCES
[1] V. A. Afanasjev. The mechanisms for activation of the molecules of carbohydrates in
the condition of the acid-basicity catalysis.-Frunze.: Ilim,1974, p.137.
[2] Bochkov A. F., Afanasjev V. A., Zaikov G. E. Formation and splitting of glycosid
bonds. M.: Sciences, 1978.
[3] Del Re G. R. A simple MO LCAO method for c alculating the charge distribution in
saturated organic molecules // J. Chem. Soc.-1958.-p.4031-4040.
[4] Arnett M. The quantitative comparison of the weak organic bases // The new problems
of the physical chemistry.-M.: Peace, 1967.-p. 195-341.
[5] Panteleev Yu. A., Lipovsky A.A. The calculations of the electronic structure of the
molecule of urea and its protonic kations. I. The definition of the protoning place. The
role of the electrostatic interaction // J. of structure chemistry.-1976.-T. 17.-N 1.-p. 4-8.
[6] Panteleev Yu. A., Lipovsky A.A. The calculations of the electronic structure of the
molecule of urea and its protonic kations. II. The change in the structure of the
molecule of urea by protoning // J. of structure chemistry.-1976.-T. 17.-N 1.-p. 9-14.
[7] Afanasjev V. A., Djamanbaev J. A. The synthesis of glycosylurea on the basis of N-
glycosyd m-nitroanilin as a glycosilic agent // The news of Academy of Sciences of
Kyrgyz SSR.-1973.-N 2.-p. 64-65.
[8] Afanasjev V. A., Djamanbaev J. A. The effective method of obtaining N-glycosids of
urea // The chemistry of nature compounds.-1974.-N 2.-p.176-178.
[9] J. A. Djamanbaev, J. A. Abdurashitova, G. E. Zaikov. Sugar carbamides. Organic and
physical chemistry using chemical kinetics. Prospects and development, Ed. By Yu. G.
Medvedevskich, A. Valente, R.A. Howell, G. E. Zaikov. Nova Science. Publishers.
New York.-2008.-p. 291.
[10] Afanasjev V. A. Structure and relational ability of N-glycosides.-Frunze.: Ilim, 1976,

p.83.
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Chapter 17
HEADSPACE ANALYSIS OF AROMA COMPOUNDS

USING POROUS ADSORBENTS
T.A. Misharina*
N.M. Emanuel Institute of Biochemical Physics,
Russian Academy of Sciences,
Moscow, Russia
ABSTRACT
A novel procedure is developed for the quantitative determination of volatile
compounds in the vapour phase over samples. Substances were extracted and
preconcentrated from the headspace on porous polymer adsorbents under the conditions
of thermodynamic equilibrium, followed by back extraction from the adsorbent using
organic solvents. The final monitoring was performed by capillary gas chromatography
with an internal standard. The influence of adsorption time and the concentration of
substances in an aqueous solution on the degree of extraction were also studied; linear
correlations between the quantities of substances in the gas and aqueous phases were
found. The method was used for the determination of volatile substances in the gas phase
over liquid and solid matrixes of different composition.
Keywords: adsorbents, porous, headspace analysis, quantitative determination, volatile

compounds, compositions.
INTRODUCTION
The composition and concentration of volatile organic substances (odorants) in the gas
phase over foods determine their aroma. Odorants release from the bulk of food matrix and
*
4 Kosygin str., Moscow, 119334 Russia, tmish@rambler.ru.
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Copyright © 2011. Nova Science Publishers, Inc. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under 156 T. A. Misharina
transfer into the gas phase according to their volatility. The odorant release is affected by their
structure, by the presence and type of functional groups within, the concentration of the
odorants in initial material, as well as the composition and physicochemical state of the food
matrix. Moreover, in the odorant release, the important input is contributed by their
interactions with food biopolymers and lipids [1, 2]. Ordinarily, the composition of volatile
substances in food has a rather complicated profile, e.g., the number of substances can reach
several hundred, therein the total concentration of individual species does not exceed 0.01%,
and the range of concentrations for the volatile substances can be several orders of magnitude
[3]. The complexity of such objects substantially restricts the line of acceptable analytical
methods for sample preparation and the final detection of volatile substances.
To determine volatile substances in the vapour phase over the product, static or dynamic
methods of analysis are used [4, 5]. The dynamic technique includes the extraction of volatile
odorants with a flow of an inert gas followed by their trapping by porous adsorbents. Then,
the substances are thermally desorbed into the initial section of a GC column or eluted with
organic solvents. Since the process does not appear to be in equilibrium, there is no chance to
estimate the real ratio of the odorants forming the aroma of the product [4–6].
In the static procedure, the composition of volatile substances in the gas phase is
determined in a closed container under the condition of thermodynamic equilibrium. Such
approach allows the analysis of the true aroma of product. In the most common case, 1– 10
mL of vapors are injected into a GC column; the composition is determined by the areas of
chromatographic peaks then. However, the method is characterized by several significant
restrictions, e.g., low sensitivity and reproducibility of determination, especially in the case of
capillary gas chromatography, because this method detects only substances present in
concentrations sufficient for the detector. Meanwhile, many key substances, which are
responsible for the aroma of products, are present in amounts too low for registration without
additional preconcentration. Moreover, the method does not allow the use of internal
standards and required the calibration of all procedures [5–8]. Recently, a method of solid
phase micro extraction is used, in which volatile substances from the headspace are collected
by special tools on a layer of a liquid or a solid polymer (or mixtures of polymers), then the
concentrate is thermally desorbed directly into the injection unit of a chromatograph and
analyzed [7–10]. The technique also confines the utilization of an internal standard, which
makes the obtaining of reliable quantitative results rather difficult. The thermal desorption
from a polymer matrix requires a certain amount of time (a minute approximately), which
leads to the drop of the quality of the chromatographic separation itself [11]. The comparison
of some sorption methods for the isolation of volatile substances has revealed an essential
spread among the data on the qualitative and quantitative composition of odorants in the same
specimen of cheese [12], cured ham [13], and whisky [14]. As a rule, the method of solid
phase extraction has given undersized results.

Meanwhile, the porous and hydrophobic polymer adsorbents with highly developed
surfaces possess high sorption activity and capacity in relation to a wide spectrum of organic
substances, including volatile ones. The retention of substances by this type of adsorbents is
determined by the physical adsorption on the surface and in the pores and capillaries due to
van der Waals and electrostatic forces. The binding is rather reversible, and the substances
retained can be released easily by thermal desorption or back extraction with a solvent [4–7,
15]. These polymers are usually used in cartridges for the dynamic vapor analysis. I used the
adsorbents in the mode of static headspace analysis. Herein, I report a novel version of the
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Copyright © 2011. Nova Science Publishers, Inc. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under Headspace Analysis of Aroma Compounds Using Porous Adsorbents 157
solid phase extraction of volatile substances from the headspace over samples and its
application to the analysis of model systems and real foods.
EXPERIMENTAL
Model mixtures of odorants. We used two model mixtures of odorants prepared by
dissolving individual substances 20–200 μL each in 2 mL of ethanol (Mixture 1) or essential
oils of oregano and nutmeg to which individual odorants of carvone, camphor, caryophyllene,
and eugenol were added (Mixture 2). According to the GC data, all materials contained not
less than 98% of the main component. To control the qualitative composition of mixtures, 10
μL of each mixture was diluted in 100 μL of ethanol, then 1 μL of a 10% n-dodecane solution
was added as an internal standard. The resulting mixture was analyzed by capillary gas
chromatography. The composition of the mixtures, the concentration of the odorants (relative
to the n-dodecane), and their basic parameters are presented in the table.
Table. Characteristics of odorants and their concentrations in model mixtures

(relatively to n-dodecane)
Compound Mixtu-re Relative MW, Hydrobocity Retentio

no content in 10 g/mol (log P n index
μL of a model октанол/вода ) on DB-1
mixture [16]
Esters
Ethyl butyrate 1 210 116 1.70 784
Amyl acetate 1 216 130 2.15 880
Hexyl acetate 1 236 144 2.83 996
Geranyl acetate 1 97 196 4.04 1364
Terpene hydrocarbons
α-Pinene 2 569 136 4.16 932
Limonene 1 490 136 4.38 1025
γ-Terpinene 2 310 136 4.36 1050
Caryophyllene 2 516 204 - 1420
Alcohols and aldehyde
2-Hexenal 1 240 98 1.58 832
Hexanol 1 250 102 2.03 852
Heptanol 1 254 116 2.45 954
Octanol 1 210 130 - 1055
Linalool 1 655 154 3.50 1085
Ketones and phenols

Camphor 2 151 152 2.74 1125
Carvone 2 610 150 2.75 1218
Thymol 2 783 150 3.30 1278
Eugenol 2 945 164 2.99 1330
Myristicin 2 120 192 - 1492
Porous adsorbents. We used three porous adsorbents (Supelko, USA): Tenax GC (40–60
mesh), representing the polymer of n-2,6-diphenylene oxide with a specific surface area of
18.6 m2/g and average pore size of 72 nm; Porapack R (60–80 mesh) was based on poly-N-
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vinylpyrrolidone and had specific surface area of 550–570 m2/g. Chromosorb 105 (60– 80
mesh) was a polyaromatic polymer with a specific surface area of 600–700 m2/g and average
pore size of 50 nm [5]. Prior to use, all adsorbents were washed with ethanol, ether, and
acetone and kept in a flow of helium for 24 h at 250°С in a thermostat.
Extraction of volatile substances. To extract volatile substances from the gas phase, a 0.5
mL Erlenmeyer flask was sequentially charged with 10 mL of distilled water, 10 μL of model
mixture 1 or 2, then closed with a glass stopper and kept at ambient temperature (22– 23°С)
for 2 h. A chemical glass with a diameter of 1.8 mm and height of 20 mm was charged with
100 mg of one of the porous adsorbents specified and positioned on the bottom of the flask
with a model solution. Then, the flask was corked up again and kept for 3 h to compare the
effectiveness of adsorbents and evaluate the odorant concentration in aqueous solutions in
relation to the degree of extraction. Kinetic curves were built using a set of nine samples (10
mL each); the exposure time for the polymer in the gas phase over aqueous solutions was 30
min, 1, 2, 3, 4, 5, 18, 24, and 48 hours. Then the glass was extracted from the flask, and the
adsorbent was transferred into a glass test tube. Diethyl ether (1 mL) and 5 μL of 1%
ethanolic solution of n-dodecane were added to the polymer. The mixture was shaken for 10
min followed by the decantation of the liquid into a clean test tube. Extraction was repeated
without the addition of n-dodecane. The extracts were combined and, if necessary, evaporated
using a 35-cm -long Vigreux column at 40°С to get the residual volume 0.2–0.4 mL. A
special check was performed that showed that the procedure guaranteed the quantitative
extraction of the odorants. Each experiment was repeated 3–5 times.
Gas chromatographic analysis. The extracts were analyzed on an HP 5730 chromatograph
(Hewlett Packard, USA) furnished with a fused silica capillary column DB-1 (50 m x 0.32
mm, immobile phase width df = 0.25 5 μm) operated at a temperature from 60 to 250°С with
the gradient rate 8°C/min. The rate of carrier gas helium was 1 mL/min, the temperature of
the injector unit and flame-ionization detector was 250°С. The volume of the sample was 2 5
μL. The chromatograms were registered by the Ecochrom (State Registration no. 16616-97,
Russia) system for the collection and processing of chromatography data. The relative
concentration of the components in the initial model solutions and samples was calculated
from the comparison of peaks referring to the components and the internal standard by simple
adjustment, and expressed in units, equivalent to the number of μg of n-dodecane. The
efficiency of extraction (%) was determined as the ratio of the odorant quantity found in the
gas phase to the quantity introduced into the aqueous solution. The procedure made
unnecessary the determination of the sensitivity coefficients of the detector to compounds of
various structures, since these coefficients were cancelled in the calculation. The processing
and averaging of the data obtained were performed using the ANOVA software at the value p
< 0.05. The plotting, construction of linear correlations and their processing were realized
using the Origin 7.5 software.

The traditional static analysis of the gas phase is based on the equilibrium distribution of
substances between a liquid or solid and the gas phases in a closed space and the
determination of the concentration of volatile substances in vapors. All general methods for
the determination of volatile substances in vapors, their theoretical and practical aspects,
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benefits, and drawbacks are considered in detail in the reviews [4, 5]. The actual version
included the adsorption of volatile substances from the gas phase by porous adsorbents under
batch conditions; the quantity of the adsorbent could be changed to fit the desired task under
consideration. Upon exposure, the concentration of species in vapors reduced gradually, and
new portions from them transferred from aqueous into the gas phase according to their
distribution coefficients. Finally, the entire process resulted in the preconcentration of volatile
substances on a porous adsorbent, which allowed for the improvement of the accuracy,
reproducibility and effectiveness of the parameters of the following GC determination of the
contents of the odorants, released from the products to the gas phase over them. The retained
substances were eluted by diethyl ether in the presence of an internal standard; therefore, the
sample could be further preconcentrated, analyzed by a number of GS and GS–MS methods
under various conditions and processed quantitatively. To sum up, the major advantages of
the technique reported was represented by its simplicity, the lack of the need for special
equipment, and the possibility of using an internal standard to quantify the entire
determination.
The study of odorant adsorption from vapors over their aqueous solution revealed a
correlation between the efficiency of extraction and the structure of the analyte and the
adsorbent nature. Figure 1 presents the degree of extraction of a model mixture of odorants
relating to various classes of organic compounds from vapors over their aqueous solution
using three porous adsorbents upon exposure for 3 h. Porapack R and Chromosorb 105
appeared to have an identical sorption activity, while the activity of Tenax appeared to be
almost two times lower.
Figure 1. Recovery of odorants from the gas phase over an aqueous solution using three porous
adsorbents (3 h). 1, hexyl acetate; 2, geranyl acetate; 3, limonene; 4, caryophyllene; 5, heptanol; 6,
eugenol; 7, camphor.
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Since the concentration of volatile species over all adsorbents was identical, the effect
apparently corresponded to the lower affinity of Tenax toward nonpolar odorants in
comparison to Porapack R and Chromosorb. The lower sorption activity of Tenax filled traps
was observed before under the conditions of dynamic headspace analysis [7].
Lower esters (see Table) demonstrated a similar degree of extraction, which was 42–56%
for Porapack R; geranyl acetate was extracted to 17% only. After exposure over Porapack R
and Chromosorb for 3 h, only 48–66% of monoterpene hydrocarbons (pinene, limonene and
terpinene) and 12–13% of sesquiterepene caryophyllene were isolated. All adsorbents showed
a low extraction degree for polar substances: alcohols, ketones, aldehyde, and phenols that
were likely determined by the lower volatility of the polar odorants from aqueous solutions.
Thus, in comparing the adsorption properties for the three adsorbents, Tenax demonstrated
the lowest activity and was excluded from further investigation. Chromosorb 105 and
Porapack R showed similar adsorption properties (Figure 1); to study in detail the behavior of
odorants under the conditions of static headspace analysis, Porapack R was chosen.
Figure 2 presents relative kinetic curves (those adjusted to the initial concentration of
each odorant in the model solution), which illustrate the relation of exposure time to the
extraction degree of components by Porapack R. As can be seen, the longer the exposure
time, the bigger the quantity of substances was trapped; however, the specific rate of
accumulation depended on the structure of substances and their hydrophobic properties.
Generally, the extraction of components from the gas phase over their (or another food
species) aqueous solution appeared to be a two step process: the transition of odorants from
water into the gas phase followed their adsorption on a polymer matrix. The overall process is
called extraction, it depends on two sets of distribution coefficients of the odorants: between
the gas and aqueous phases and between the gas phase and the adsorbent surface. The
distribution coefficients reflect the sum of the interactions between the odorants and the
matrix, and the affinity of the volatile species to the adsorbents. The time of settlement of the
sorption equilibrium is determined by the hydrophobic properties, molecular weight, and
diffusion parameters of odorants in the medium [17, 18]. The equilibrium retention by an
adsorbent is a quick process, since diffusion in gas proceeds much faster than in liquids.
Under such conditions, the rate-limiting step is the transition of odorants from liquid into the
gas phase. Therefore, the obtained relations of the degree of extraction of substances to the
exposure time (kinetic curves) could be used for calculating the kinetic parameters for the
release of odorants from aqueous solutions or another matrix. The rate of the evolution is
determined by the slope of the kinetic curves in their linear segments. Finally, the rate
constant of transfer is calculated based on the rate of release and the initial concentration of
the substances in the sample. These parameters are crucially important for the evaluation of
stability of product aroma and the identification of components responsible for the formation
of the entire aroma.

The maximum degree of extraction was observed for nonpolar esters with low molecular
weights: ethyl butyrate, amyl and hexyl acetates as well as for hydrocarbons pinene,
limonene, and terpinene (Figs. 2a and 2b). In three hours, Porapack R extracted around one
half of the substances from an aqueous solution; a fairly good quality extraction was achieved
in 18–24 h. The less volatile nonpolar substances of the same class, geranyl acetate and
caryophyllene, were 46–47% extracted after exposure for 48 h.
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In the series of esters, the growth of molecular weight was accompanied by the
enhancement of hydrophobic properties (see Table); however, volatility in this series reduced,
which resulted in the decrease of the extraction degree of the odorants. Within the series of
monoterpene hydrocarbons with equal molecular weights, hydrophobicity increased in the
following order: pinene < terpinene < limonene. The same order was found to determine their
degree of extraction from aqueous solutions (Figure 2b).
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Figure 2. Time dependence of extraction degree by Porapack R from vapors over an aqueous solution.
1, ethyl butyrate; 2, hexyl acetate; 3, geranyl acetate; 4, limonene; 5, pinene; 6, caryophyllene; 7, 2-
hexenal; 8, octanol; 9, linalool; 10, hexanol; 11, myristicin; 12, carvone, camphor; 13, thymol, eugenol.
Analogous behavior was registered for alcohols as well: hexanol, heptanol, and octanol.
Despite the growth of molecular weight, the enhanced hydrophobic properties led to a higher
degree of extraction; however, the absolute value was only 5–7% in 3 h, and did not exceed
30–39% in 48 h (Figure 2c). The determined degree of extraction for linalool appeared lower
than that for octanol, its behavior copied heptanol’s behavior. 2-Hexenal tended to be
extracted easier than alcohols, in 20 h more than one half of the substance was transferred
from aqueous solution into the gas phase (Figure 2c). Figure 2d presents kinetic curves for
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carvone, thymol, and myristicin. The substitution of the hydroxyl group in myristicin by
nonpolar groups increased its extraction degree from aqueous solution fivefold in comparison
to thymol. The kinetics and extraction degree for camphor and eugenol had the same values
as those for carvone and thymol, respectively. The assumption that the poor extraction of
alcohols was determined by their low concentration in the gas phase over the aqueous
solution and did not indicate the low true affinity of the adsorbent to this class of organics
was proved by the data obtained for the same mixture in an empty flask with no solvent.
Figure 3 presents a comparison of the degrees of extraction for equal quantities of odorant
mixtures from an aqueous solution and with no solvent in 3 h. The extraction of alcohols and
aldehydes by Porapack R from vapors over solvent-free mixtures exceeded the value over an
aqueous solution by 10–15 times and, for nonpolar odorants, by 1.5–2 times (Figure 3).
Apparently the difference reflected the interaction of odorants with water, resulting in the
lower concentration of them in the gas phase. Hence, the interaction of nonpolar compounds,
hydrocarbons and esters, with water appeared much weaker in contrast to alcohols and the
aldehydes. The difference between the odorant сomposition over an aqueous solution and the
same solution in the presence of some food polymer, e.g., protein or polysaccharide, or
emulsion, provided the grounds for the evaluation of the interaction of the odorant with food
polymers and the determination of distribution coefficients between various phases [2,19–24].
Figure 3. Comparison of extraction extent of odorants by Porapack R from vapors over a solvent-free
mixture and its aqueous solution (3 h). 1, ethyl butyrate; 2, amyl acetate; 3, hexyl acetate; 4, 2-hexenal;
5, hexanol; 6, heptanol; 7, octanol; 8, linalool; 9, limonene.
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Figure 4a illustrates the relation of the odorant quantity introduced into the initial
aqueous solution to that trapped by Porapack R from the gas phase over 3 h. The obtained
relations were found to be linear in the concentration range checked (from 90 to 8000 μg).
The linear behavior of the relations revealed the constant character of the degree of extraction
for each odorant; it was independent of concentration. Therefore, both processes of the
transition of odorants from the aqueous phase into vapors and the following accumulation on
a porous adsorbent were clearly thermodynamically equilibrium.
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Figure 4. Effect of odorant concentration in the aqueous phase on their content the gas phase. 1, ethyl
butyrate; 2, hexyl acetate; 3, geranyl acetate; 4, limonene; 5, pinene; 6, caryophyllene; 7, 2-hexenal; 8,
octanol; 9, linalool; 10, hexanol; 11, myristicin; 12, carvone, camphor; 13, thymol, eugenol.
Such behavior allowed the use of the method proposed in flavor chemistry; for instance,
to determine the kinetic and thermodynamic parameters of the release of odorants, to reveal
substances that specify the aroma of food, and estimate the interaction of volatile organics
with polymer components of food matrixes, etc. In combination with the method of phase
ratios, one can simply and reliably measure the distribution constants of odorants between the
gas phase and the food substance or another object [24–27]. As a practical example, Figure 5
presents the estimated time dependence of odorant release from some liquid solvents and dry
supporters for the selection of a matrix that would provide the desirable presence of essential
oil components in vapors. The amount of the essential oil mixture and concentration of each
individual component, the volumes of the gas phases were kept similar or identical, and all
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other conditions were kept equal. As expected, the nature of solvent and matrix substantially
influenced the odorant composition in vapors. Thus, hydrocarbons vaporized easily from
propylene glycol, less easily from triacetin and maltodextrin, and were retained very well by
vegetable oil. Alcohols and phenols were found to leave maltodextrin most easily, in contrast
to the liquid matrixes tested.
Figure 5. Concentration of odorants in the gas phase over solutions and dry disperse samples containing
equal quantities of essential oils (24 h, ambient temperature). 1, pinene; 2, limonene; 3, linalool; 4,
thymol; 5, carvacrol; 6, eugenol.
The retention of phenols by triacetin and starch was close to each other. The ratio of
substances in the initial mixture of essential oils due to their transfer to the gas phase was
reproduced best in the case of maltodextrin matrix used dry. This material was chosen to
maintain the predetermined concentration of volatile species in chambers for tests on
laboratory animals.
In summary, a new version of the quantitative determination of volatile organics in the
gas phase over samples using porous adsorbents was developed. The method proposed is
simple, and allows for the application of internal standards and the analysis of complex
mixtures by chromatography and other techniques. The quantities of substances in the vapor
and aqueous solution were found to correlate linearly, which revealed the thermodynamic
equilibrium behavior of extraction and preconcentration on porous adsorbents. Therefore, the
extraction degree of odorants was independent of their concentration in the initial solution.
Extended exposure time was shown to favor an increase in the degree of extraction, while the
specific rate of accumulation was affected by the structure of the substance, its hydrophobic
properties, and the nature of the matrix. The method was proved to be applicable to various
tasks in flavor chemistry.
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REFERENCES
[1] Wilson, C.E. and Brown, W.E., J. Sens. Stud., 1997, vol. 21, p. 69.
[2] Seurve, A.M., Diaz, M.A., and Voilley, A., J. Agric. Food Chem., 2000, vol. 48, no. 9,
p. 4296.
[3] Golovnya, R.V. and Misharina, T.A., Zhurn. anal. khim., 1981, vol. 36, no. 7, p. 1390.
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R.L. and Cadwallader, K.R., New York: Academic Plenum, 2001.
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Int., 2006, vol. 22, no. 1, p. 51.
[6] Zhu, J.Y. and Chai, X.-C., Curr. Anal. Chem., 2005, vol. 1, no. 1, p. 79.
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Montedoro, G.F., J. Chromatogr. A, 2004, vol. 1054, no. 1, p. 17.
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[11] Vichi, S., Castellote, A.I., Pizzale, L., Conte, L.S., Buxaderas, S., and Lopez-Tamames,
E., J. Chromatogr. A, 2003, vol. 983, no. 1, p. 19.
[12] Bellesia, F., Pinetti, U.M., Rinaldi, R., Caglioti, L., and Palyi, G., Food Chem., 2003,
vol. 83, no. 1, p. 55.
[13] Ruiz, J., Cava, R., Ventanas, J., and Jensen, M.T., J. Agric. Food Chem., 1998, vol. 46,
no. 11, p. 4688.
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Chromatogr. A, 2003, vol. 985, nos. 1. 2, p. 221.
[15] Tienpont, B., David, F., Bicchi, C., and Sandra, P., J. Microcolumn Sep., 2000, vol. 12,
no. 11, p. 577.
[16] Griffit, S., Wyllie, S.G., and Markham, J., J. Chromatogr. A, 1999, vol. 894, no. 2, p.
221.
[17] Zhu, P.-L., Liu, C.-L., and Liu, M.-C., J. Chromatogr. A, 2003, vol. 988, no. 1, p. 25.
[18] Zhang, Z. and Pawliszyn, J., Anal. Chem., 1993, vol. 65, no. 14, p. 1843.
[19] Engels, W.J.M., Dekker, R., Jong, C., Neeter, R., and Visser, S., Int. Dairy J., 1997,
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Chapter 18
THE INFLUENCE OF ACID–BASE INTERACTION ON

THE SOLUBILITY OF DIISOPROPYLBENZENES
HYDROPEROXIDES
R. G. Makitra*1, G. G. Midyana,1 L. I. Bazylayk1,

O. Ya. Palchykova†2 and G. E.Zaikov‡3
1 Physical Chemistry of Combustible Minerals Department
L. M. Lytvynenko Institute of Physical–Organic Chemistry and Coal Chemistry,National
Academy of Sciences of Ukraine, Lviv, Ukraine
2 Institute of Geology and Geochemistry of Combustible Minerals
National Academy of Sciences of Ukraine, Lviv, Ukraine
3 N. Emmanuel Institute of Biochemical Physics
Russian Academy of Sciences, Moscow, Russia
ABSTRACT
Tthe data concerning to the solubility of p– and m–diisopropylbenzenes
dihydroperoxides can be connected with the properties of the solvents via multi–
parametric equations, besides the determining factor of the latest is the basicity upon
Palm in a case of p–diisopropylbenzene dihydroperoxide. In a case of m–
diisopropylbenzene dihydroperoxide only one factor, namely solvents self–association is
the determining factor with increasing of which the solubility (in moles) is linearly
decreased.
Keywords: dihydroperoxides, solubility, correlation analysis.
*
National Academy of Sciences of Ukraine, 3a Naukova Str., 79053, Lviv, Ukraine, e–mail: hop_vfh@ukr.net.
†
e–mail: hop_vfh@ukr.net.
‡
N. Emmanuel Institute of Biochemical Physics,Russian Academy of Sciences, 4 Kosygin Str., 117977, Moscow,
Russia, e–mail: chembio@sky.chph.ras.ru.
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Copyright © 2011. Nova Science Publishers, Inc. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under 170 R. G. Makitra, G. G. Midyana, L. I. Bazylay et al.
AIM AND BACKGROUND

Hydroperoxides of diisopropylbenzenes have a much wide application not only as the
initiators of polymerization reactions, but also they are used as the intermediates in the
synthesis of hydroquinone and resorcin [1]. That is why taking into account their very low
solubility in water very importantly is to determine their solubility into organic solvents and
to define the optimal medium for the realization of these syntheses, and also to study the
dependences between the solubility and the nature of solvents.
INTRODUCTION
In Ref. [2, 3] it was determined the solubility of dihydroperoxides of m– and p–
diisopropylbenzenes in a series of solvents at 20, 40 and 60 0C and it was shown, that
depending on their nature it can be varied via the limits of two orders: namely, it can be
increased at the solvents polarity increasing and, especially, at their ability to be by acceptors
of the hydrogen bond. The latest is clear, especially taking into account the acidic character of
the hydroperoxides, which able to form the salts with the bases [2]. It was shown also, that
into homolytic series of the solvents (esters, ketones, and especially alcohols) a solubility of
the hydroperoxides is decreased with the solvent molecular weight increasing that is the
length of their alkyl chain increasing. However, the quantitative dependences between the
solubility of dihydroperoxides and some characteristics of the solvents were not determined in
the Ref. [2, 3]; that is why such analysis is done by us in the presented work.
First of all, it was advisable the attempt to determine the possible influence of the solvents
basicity on the solubility.
Taking into account, that the interaction between molecules R–О–OH…Solvent proceeds
into the active solvents, it were represented in Table 1 the values for the solubilities of the
dihydroperoxides of m– and p–diisopropylbenzenes in grams of peroxide dissolved into 1
mole of the solvent (SM), calculated by us on the basis of data Ref. [2], where the solubilities
presented in weight %.
It was shown on the Figure 1 the ratio between the solubility of p–diisopropylbenzene
dihydroperoxide at 20 0C (SM) and the solvents basicity (B) upon Palm (displacement of the
stripe corresponding to OH–group of phenol in IR–spectrum in the presence of presented
solvent). As we can see from Figure 1, the solubility of the dihydroperoxide is essentially
higher in more basic solvents; at the same time, any proportionality between B and lgSM (all
the more SM) is not observed. Obviously, this caused by fact that also others physical–
chemical characteristics of the solvents have the influence on the value SM.
It is known, that for taking into account the medium influence on the behavior of diluted
substrates (for example, in chemical kinetics) advisable is the application of multi–parametric
equations, which take into account the solvation ant others factors [4, 5]. Such approach was
effective also for the generalization and interpretation of data concerning to the solubility of
substances. In Ref. [6] it was shown, that the data on the fullerene C60 solubility into 84
solvents can be generalized with the use of five–parametric equation:
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Copyright © 2011. Nova Science Publishers, Inc. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under The Influence of Acid–Base Interaction… 171
METHODS OF CALCULATIONS
Table 1. Solubility of the Diisopropylbenzenes Dihydroperoxides
p– m–diisopropylbenzene
diisopropylbenzene
№ Solvent
I II III IV V
0 0
20 C 40 C 60 0C 20 0C 40 0C
1 Heptane
– – – 0,1100 –
2 Benzene 0,1560 0,9250 1,2220 43,32 95,87
3 Toluene 0,0740 – 0,5562 22,60 126,20
4 Chloroform 0,5870 2,8297 5,1800 137,85 287,91
5 ССl4 0,0307 0,3625 0,7810 6,027 10,554
6 Chlorobenzene 0,0969 0,2591 0,4860 – –
7 Dichloroethane 0,0418 1,9280 5,0364 111,22 169,29
8 Ethanol 7,500 11,882 32,680 77,940 86,700
9 Butanol 7,600 8,9741 16,990 105,3 119,4
10 isoamyl alcohol 3,150 6,840 16,98 64,37 72,13
11 Octyl alcohol 2,9840 11,003 15,198 – –
12 Cyclohexanol 7,8749 – 38,889 – –
13 Glycerin – – – 22,426 –
14 Diethyl ether 0,9550 23,625 – 197,06 –
15 Diisopropyl
1,6590 – – 158,20 199,78
ether
16 Acetone 22,590 – – – –
17 Methylethyl-
12,910 20,541 36,08 216,0 248,0
ketone
18 Methylisobutyl
6,383 15,742 22,550 208,6 244,8
ketone
19 Acetophenone 7,6690 13,041 – – –
20 Ethyl acetate 6,1680 9,8872 14,850 126,12 104,71
21 Butyl acetate 5,0390 8,5480 15,221 – –
22 Nitrobenzene 0,8680 1,4562 – – –
23 Water 0,0108 0,0216 – 0,4615 0,9874
n2 − 1 ε −1
lgSм = a0 + a1 + a2 + a3B + a4Ет + a5δ2 (1)
n +2
2
2ε + 1
in which n is the light refractive index of solvents, ε is their dielectric permeability; В is

the basicity upon Palm; Ет is the electrophilicity upon Reinhardt; δН is the solubility
Hildebrand’s parameter [5].
First two terms characterize the ability of the solvents to the non–specific solvation of
substrates; two others terms characterize the ability of the solvents to the specific solvation;
the term δН is proportional to the cohesion energy of the liquid medium and, as a rule, strikes
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the energy expense for the molecule penetration into the structure of liquid. The following
analysis of the obtained equation in accordance with the recommendations of Ref. [7] showed,
that the valuation of the fullerene solubility is determined only by two factors, namely by
polarization of liquids, which assists to the solubility, and by cohesion, which decreases it.
Figure 1. Dependence of the p–diisopropylbenzene dihydropeoxide solubility lgSм on basicity of

solvents В. (The numbers of points on graph correspond to numbers of solvents in Table 1).
RESULTS AND DISSCUSIONS

It is necessary to note, that the similar obtaining of the connection between the valuation
of solubility for a series of compounds, for example, diphenylsulphone, hexachlorobenzene,
1–nitronaphthalene and ect., and physical–chemical characteristics of the solvents by means
of multiparametric equations was done in works of W. E. Acree and coworkers [8–10], but in
these works it were used other digital scales in comparison with the Ref. [6].
That is why it was advisable the attempt to treat the data of Ref. [2, 3] concerning to the
solubility of diisopropylbenzene dihydroperoxides. The generalization was carried out with
the use of eq. (1) added by the six term, namely by molar volume of the solvents VМ. The
characteristics of the solvents were taken from Ref. [11, 12], the mathematical treatment was
done accordingly to Ref. [7]. The correlation of obtained equations was considered by enough
when the value of multiple correlation coefficient R was more than 0,95.
In a case of p–diisopropylbenzene dihydroperoxide the data concerning to the solubility
in 21 solvents at 20 0C (the column I in Table 1) are generalized by six–parametric equation
with R = 0,892, and after the exclusion from the consideration the most disagreed data for the
dichloroethane and diethyl ether it was obtained for the 19 solvents the six–parametric eq. (2)
with sufficiently high value R:
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lgSМ = –0,655 – (3,077 ± 2,935)f(n2) + (5,934 ± 1,394)f(ε) + (0,0045 ± 0,0015)B +

(0,0053 ± 0,0234)EТ – (0,0020 ± 0,0003)δ2 – (0,0072 ± 0,0039)VМ
(2)
R = 0,958; mean–root–square error s ± 0,281.
An analysis of the equation shows, that accordingly to the dihydroperoxide’s acid

character, increasing the basicity and polarity of the solvents leads to the substrate solubility
increasing and, respectively the solvents’ self–association degree and the molar volume
decrease the substrate solubility.
The values of the paired correlation coefficients between lgS and separate parameters of
the equation rі, which are equal to 0,286; 0,541; 0,696; 0,068; 0,433 and 0,334 respectively
don’t give the possibility quantitatively to estimate their influence on the solubility; it can be
only assumed the maximal significance of the solvents basicity, but not the proportionality
with this factor, that is agreed with the Figure 1. That is why in accordance with the Ref. [7] it
has been done the alternating exclusion of the separate terms of eq. (2) with every time
determination of R for obtained equations with the less number of terms.
At this, if R is decreased incidentally, the excluded term of the equation is considered by
not significant. Thus, it was determined the practical insignificance of the terms with f(n2) (R
without it is equal to 0,955), ЕТ (R = 0,958) and lesser significance VМ (R = 0,950). Finally,
a dependence of the hydroperoxide solubility on the properties of the solvent can be
satisfactory described by four–parametric eq. (3):
lgSМ = –1,140 + (5,691 ± 1,122)f(ε) + (0,0056 ± 0,0011)B – (0,0019 ± 0,0002)δ2 –

(0,009 ± 0,004)VМ
(3)
R = 0,955; s ± 0,290.
Some worse, although adequate as to the Student’s criterion, will be the generalization
with the use of three–parametric equation – after the exclusion from the consideration of term
with VМ R is decreased till 0,937.
In accordance with the above presented thinking, the solubility of hydroperoxide is
increased at the ability of the solvents to the formation of hydrogen bond with acid group
OOH (the influence of the basicity and polarity increasing) and is decreased with the self–
association of liquids, that is with the energy expense increasing needed for the penetration of
exterior molecule of the hydroperoxide in their structure.
In Table 2 there are experimental and calculated accordingly to eq. (3) values of lgSМ
and also their divergences ΔlgSМ.
On Figure 2 it is presented the ratio between the experimental and calculated accordingly
to eq. (3) values of lgSМ. As we can see, between these values is kept the satisfactory linear
ratio. The divergence of the lgSМ calculated values from the experimental ones for 16
solvents among 19 is less than the root–mean–square error s ± 0,290; the data only for 3
solvents (namely, isopropyl ether, ethyl acetate and butyl acetate) are deflected from the
error’s corridor, bur even for these solvents such deviations is less than the values ± 2s.
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Evidently, the deviations for the excluded from the calculations diethyl ether and
dichloroethane are essentially more.
Also the data concerning to solubility of p–dihydroperoxide at higher temperatures (40
0C and 60 0С) are satisfactory generalized by six–parametric equation, although they
determined for less number of solvents. For 40 0C (the column II in Table 1) the data for 17
solvents are generalized by six–parametric equation with R = 0,965 and by as same as in eq.
(2) signs at its separate terms. The same terms are insignificant: f(n2), ЕТ and VМ and the
generalization of data can be satisfactory realized by three–parametric eq. (4):
lgSМ = –0,324 + (1,887 ± 0,978)f(ε) + (0,0054 ±0,0008)B – (0,0014 ± 0,0001)δ2

(4)
R = 0,956; s ± 0,242.
The value of the pair coefficient r between lgSМ and B, which is equal to 0,628 is some
less than in a case of 20 0C (r = 0,689), maybe, as a result of weakening the donor–acceptor
(hydrogen) bond at the temperature increasing.
For solubility’s data at 60 0С (the column III, Table 1) it was obtained the equation with
value R = 0,954 and pair correlation coefficient with the basicity r = 0,864. However, in spite
of this fact, for obtaining of the adequate generalization it is necessary to take into account the
factor of the solvent’ electrophilicity, and in the same time, the influence of the polarity is
insignificant.
lgSМ = 0,341 + (0,0059 ±0,0011)B + (0,108 ± 0,028)EТ – (0,0067 ± 0,0015)δ2 – (0,014

± 0,003)VМ
(5)
R = 0,954; s ± 0,204.
Figure 2. The ratio between the calculated and experimental values lgSм for p–diisopropylbenzene
dihydroperoxide.
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The following exclusion of the EТ factor decreases of R till 0,903, and the exclusion of
δ2 or VМ destroys the correlation: R falls below 0,9; probably, at 60 0C the character of the
solvation processes is changed.
Table 2. Ratio Between the Calculated and Experimental Values of lgSМ

for p– and m–Diisopropylbenzene Hydroperoxides Solubility at 20 0С In Different
Solvents
p–diisopropylbenzene m–diisopropylbenzene
№ Solvent
lgScalc
lgSexp. lgScalc. ΔlgS lgSexp. ΔlgS
.
1 –– –– –– –0,9586 – 0,1877
Heptane
0,7709
2 Benzene –0,8069 –1,0362 –0,2293 1,6367 1,4593 –0,1774
3 Toluene –1,1308 –1,0510 0,0798 1,3541 1,4075 0,0534
4 Chloroform –0,2314 –0,4300 –0,1986 2,1394 1,5818 –0,5576
5 TetraChloro- –1,5129 –1,3272 0,1857 0,7801 1,0149 0,2348
methane
6 1,2– 2,0462 2,1708 0,1246 –1,3788 0,0604 1,4392
Dichloroethan
e
7 Chlorobenzene –1,0137 –0,4258 0,5879 –– –– ––
8 Ethanol 0,8751 1,0390 0,1639 1,8918 1,6083 –0,2835
9 n–Butanol 0,8808 0,8962 0,0154 2,0224 1,5801 –0,4423
10 Iso–Amil 0,4983 0,7485 0,2502 1,8087 1,5156 –0,2931
alcihol
11 n–Octanol 0,4748 0,3573 –0,1175 –– –– ––
12 Cyclohexanol 0,8962 0,8585 –0,0377 –– –– ––
13 Gliceryn –– –– –– 1,3508 1,7636 0,4128
14 Diethyl ether –0,0200 0,9617 0,9817 2,2946 2,4363 0,1417
15 Isopropyl ether 0,2198 0,7008 0,4810 2,1992 2,0707 –0,1285
16 Acetone 1,3539 1,1651 –0,1888 –– –– ––
17 Methylethyl- 1,1109 1,1480 0,0371 2,3345 2,7770 0,4425
ketone
18 2–Hexanone 0,8050 0,8774 0,0724 2,3193 2,5426 0,2233
19 0,8847 0,6543 –0,2304 –– –– ––
Acetophenone
20 Ethylacetate 0,7901 0,4293 –0,3608 2,1008 1,9598 –0,1410
21 n–Butylacetate 0,7023 0,0374 –0,6649 –– –– ––
22 Nitrobenzene –0,0615 0,1172 0,1787 –– –– ––
23 Water –1,9666 –1,9901 –0,0235 –0,3358 – 0,2025
0,1333
Complicated character of the solvation processes at the p–diisopropylbenzene

dihydroperoxide solution is confirmed by the solution heat determination. Under the graphs
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lgSМ – 1/Т construction it is observed both positive (hydrocarbons, halogen derivatives) and
negative (alcohols) deviations from the rectilineal dependence (Figure 3). Evidently, this is
connected with the change of nature and activity of the hydroperoxide and solvent interaction.
Practically, the rectilineal dependences between lgSМ and 1/Т are observed for such donors
of the electrons (acceptors of the hydrogen bonds) as ketones and esters, although they are not
strongly reciprocally parallel. However, the values of the solution enthalpies calculated on the
basis of slope angle of these dependences are little differed between themselves and ΔНsol. =
(2,7 ± 0,1) kilocalorie for the dilution of p–dihydroproxide into 1 mole of solvent.
Figure 3. Dependence of the p–diisopropylbenzene dihydropeoxide solubility lgSм on 1/Т.
Under the absence of the solvation effects the enthalpy of the dilution should be equal to
the enthalpy of the dihydroperoxide melting. The most inert among the additional solvents
would be the ССl4, but since the values of lgSМ at 20 0С are sharply deviated downward, then
the value ΔНdis. ≅ ΔНmelt. was calculated only based on the data for two temperatures: 40 0С
and 60 0С; this value is equal to 4,00 kilocalorie; this is higher, than the ΔНmelt. calculating
based on the data for donors of electrons.
Essentially other dependences were observed for the solubility of other isomer, namely
m–diisopropylbenzene dihydroperoxide (Table 1). The solubilities in the presented case
independently on the solvent nature (excepting the hydrophilic water and glycerin and also
ССl4) are differed insignificantly, only in 1,5 – 2 times, and are not enough increased with the
temperature. At the same time, in comparison with the p–isomers, for polar solvents their
values are increased insignificantly, but for non–polar hydrocarbons and halogen derivatives
– practically on order. Generalization of the data upon solubility at 20 0С for 16 solvents leads
to the equation with R = 0.969. However, the pair correlation coefficient with the basicity in
such a case is comparatively very low, r = 0,470 and practically is equal to r with δ2 or n2 –
respectively 0,455 and 0,452. Also, in spite of the high value of R, to exclude from the
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consideration here it is permissible only one parameter, namely δ2; the following exclusion of
any parameter leads to the correlation destruction.
lgSМ = 0,026 + (18,919 ± 3,415)f(n2) + (11,842 ± 1,605)f(ε) + (0,0059 ± 0,0012)B –

(0,166 ± 0,019)EТ – (0,0160 ± 0,0044)VМ
(6)
R = 0,952; s ± 0,297.
As we can see, as same as in a case of the p–isomer, the ability of the solvent to the non–
specific solvation and to the formation of hydrogen bond increase of the dihydroperoxide
solubility; however, not cohesion decreases the solubility, but the electrophilicity one and the
increasing of its volume. In Table 2 there are also calculated accordingly to eq. (6) values of
lgScalc. and their deviations from the experimental values lgSМ. In this case too the deviations
values are within the errors corridor s ± 0,297 with the exception of three solvents
(chloroform, butanol, glycerin).
On the contrary, the values of lgSМ for m–dihydroperoxide up to 40 0C are determined by
only one parameter, namely cohesion energy density.
After exclusion of data for ССl4 the values of solubility for 12 solvents are satisfactory
described by one–parametric equation (7):
lgSМ = 2,611 – (0,0011 ± 0,0001)δ2 (7)
R = 0,969; s ± 0,161.
CONCLUSIONS
Evidently, in a case of this dihydroperoxide its ability to the solvation interactions is
sharply decreased with a temperature. Authors of Ref. [2, 3] explain of such peculiarities by
fact, that the m–isomer gives the intermolecular hydrogen bonds with the formation of
oxygen–containing cyclic structures, which are less able to the solvation (especially the
donors of the hydrogen bond) and that is why it melted under the temperature essential lower
than in a case of the p–isomer: the melting temperature is equal to 63,4–64, 4 0C and 151,0–
152,5 0С respectively.
REFERENCES
[1] Kharlampovych G. D., Churkin Yu. V. Phenols // М.: “Khimiya” (1974), 376 p. (in
Russian)
[2] Kostyuk N. G., Lezhniova I. M., Sinovych I. D. Solubility of the Hydroperoxides of m–
and p–Diisopropylbenzenes // Nieftiekhimiya (1970), v. 10, № 1, p. 73–75 (in Russian).
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[3] Fedorova V. V., Chernyshova L. N., Kasparova I. A. About Solubility of Di– and
Oxyhydroperoxide of p–diisopropylbenzene // Izviestiya VUZov. – Khimiya I
Khimicheskaya Technologiya (1967), v. 10, № 10, p. 1181–1182 (in Russian).
[4] Koppel I. A., Palm V. A. The Influence of the Solvent on Organic Reactіvity – in
“Advances in Linear Free Energy Relationships // Eds. N. B. Chapman, A. J. Shorter;
London: – New York: Plenum Press (1972), p. p. 203–280.
[5] Makitra R. G., Turovsky A. A., Zaikov G. E. Correlation Analysis in Chemistry of
Solutions // Utrecht – Boston. VSP (2004), 320 p.
[6] Makitra R. G., Prystansky R. E., Flyunt R. I. The Influence of Solvents Properties on
Solubility of Fullerene С60 // Zhurnal Organich. Khim. (2003), v. 73, № 8, p. p. 1244–
1245 (in Russian).
[7] Recommendations for Reporting the Results of Correlation Analysis in Chemistry
Using Regression Analysis // Quant. Struct. Act. Relat. (1985), v. 4, № 1, p. 29.
[8] De Fina K. M., Van Tiffany T., Fletchev K. A., Acree W. E. Jr. Solubility of Diphenyl
Sulfone in Organic Nonelectrolyte Solvents. Comparison of Observed vs. Predicted
Values Based Upon Mobile Order Theory // Canad. J. Chem. (2000), vol. 78, № 4, p. p.
449–453.
[9] De Fina K. M., Van Tiffany T., Fletcher K. A., Acree W. E. Jr. Solubility of
Hexachlorobenzene in Organic Nonelectrolyte Solvents. Comparison of Observed vs.
Predicted Values Based Upon Mobile Order Theory // Canad. J. Chem. (2000), vol. 78,
№ 4, p. p. 459–463.
[10] Hoover K. R., Acree W. E. Jr., Abraham M. H. Correlation of the Solubility Behavior
of Crystalline 1–Nitronaphtalene in Organic Solvents with the Abraham Solvation
Parameter Model // J. Solut. Chem. (2005), vol. 31, № 10, p. p. 1121–1133.
[11] Makitra R. G., Pyrig Ya. N., Kivelyuk R. G. The Important Characteristics of the
Solvents Applied into LFE Equations // Deponent VINITI / М.: (1986), № 628В – 86.
34С.
[12] Abboud J. L. M., Notario R. Critical Compilation of Scales of Solvent Parameters. Part
I. Pure, Non–Hydrogen Bond Donor Solvents // Pure Appl. Chem. (1999), v. 71, № 4, p.
645.
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Chapter 19
REGULATION OF THE CATALASE FERMENT

ACTIVITY BY BIOSURFACTANTS
A. A. Turovsky1*, R. O. Khvorostetsky†2 L. I. Bazylyak,

A. R. Kytsya2, A. N. Shulga1, O. V. Karpenko1 and G. E.Zaikov‡‡3
1
Chemistry and Biotechnology of Combustible Minerals Division; Physical Chemistry of
Combustible Minerals Department; Institute of Physical–Organic Chemistry and Coal
Chemistry named after L. M. Lytvynenko; National Academy of Science of Ukraine
Lviv, Ukraine;
2
Chemistry of Oxidizing Processes Division; Physical Chemistry of Combustible
Minerals Department; Institute of Physical–Organic Chemistry and Coal Chemistry
named after L. M. Lytvynenko; National Academy of Science of Ukraine, Lviv, Ukraine;
3
Kinetics of Chemical and Biological Processes Division; Institute of Biochemical
Physics named after N. N. Emanuel; Russian Academy of Sciences, Moscow, Russia
ABSTRACT
Iit has been studied the dynamics of the catalase synthesis by Bacillus Sp. ShR–05
strain depending on the cultivation conditions. It was determined that the biosurfactants
of rhamnolipid nature can be able increase the catalase activity in 4 times. It was
investigated the influence of supernatant of the Pseudomonas Sp. PS–17 culture broth
containing the rhamnolipids on the ferment activity. The action of rhamnolipids on the
catalase activity is discovered in a wide diapason of pH (6,0 – 10,0) and temperatures (20
– 80 0C) that gives the perspective of their practical using.
Keywords: fermentative catalysis, catalase, kinetics, bioSAS
*
National Academy of Science of Ukraine, 3а Naukova Str., Lviv–60, 79053, UKRAINE; e–mail:
biotech@ukr.net.
†
e–mail: hop_vfh@ukr.net.
‡‡
4 Kosygin Str., Moscow, 119991, RUSSIA; e–mail: chembio@sky.chph.ras.ru.
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Copyright © 2011. Nova Science Publishers, Inc. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under 180 A. A. Turovsky, R. O. Khvorostetsky, L. I. Bazylyak et al.
I. INTRODUCTION
Regulation of the ferments activity is the subject of a great interest among scientists from
the point of view both of fundamental and applied microbiology and biochemistry.
Development of high–effective complex enzymatic preparations is the actual task of the
modern biotechnology. Among potential regulators of enzymatic activity the surface–active
substances (SAS) call a special attention, since they are characterized with unique physical–
chemical properties. Thus, in references, for example, there are data as to stimulative action
of the separate synthetic SAS on the activity of the horse–radish peroxidase [1−3]. At the
same time, biogenic SAS (or biosurfactants or bioSAS) of the high activity are characterized
by a series of advantages in comparison with the synthetic SAS, in particular: they are non–
toxic, biodegradable, they are characterized by high efficiency in a wide range of the
temperatures and рН [4−8]. Today the biosurfactants have a much wide application in
different fields of industry (for example, food industry, medicine, cosmetic industry, for
detergent means production) and also in agriculture [9, 10]. It was shown, that the
biosurfactants can be applied in bioengineering as cryoprotectors, solubilizers of proteins and
regulators of biomembranes functionalization [11–13]. However, in references practically
there are not data as to biosurfactants action on the ferments activity. That is why the aim of
the presented work was to study the influence of the bioSAS on activity of catalase ferment,
which was synthesized by the Bacillus Sp. ShR–05.
II. EXPERIMENTAL PART

The Bacillus Sp. ShR–05 strain has been cultivated by deep method for 3 days and nights at 37
0
C into Erlenmeyer flasks by volume 750 ml containing the 150 ml of the nutrient medium by
following composition, g/mole:
NH4NO3 – 4,0;
KH2PO4 – 1,2;
K2HPO4·3H2O – 2,0;
MgSO4·7H2O – 0,1;
CaCl2·2H2O – 8·10–4;
FeSO4·7H2O – 5·10–6;
Natrium citrate – 4,0;
Yeast extract – 1,0;
Sucrose – 20,0;
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Copyright © 2011. Nova Science Publishers, Inc. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under Regulation of the Catalase Enzyme Activity… 181
Distillated water – up to 1 l.
The Pseudomonas Sp. PS–17 strain has been cultivated by deep method for 3 days and nights at
37 0C into Erlenmeyer flasks by volume 750 ml containing the 150 ml of the nutrient medium with
the use of circular walking beam at 150–180 revos [14].
Extraction of the lipids from supernatant of culture broth was carried out in accordance with the
Blaya–Dayer’s method with the use of chloroform–methanol mixture (2 : 1) [15].
Qualitative analysis has been carried out by thin–layer chromatography method on the Silufol
plates (Kavalier, Czechia).
The concentration of rhamnolipids was determined accordingly to method [15].
The value of catalase activity was expressed in mCat/l [16], and the activity itself was
determined by spectrophotometrically with the use of spectrophotometer of UV–visible
diapason Uvmini–1240 (P/N 206–89175–92; P/N 206–89175–38; Shimadzu Corp., Kyoto,
Japan) at the wave length λ = 410 nm. Catalase has been purified via the following stages: і)
centrifugation of culture broth of bacteria by Bacillus Sp. ShR−05 strain; іі) precipitation of
protein from supernathant with acetone and ііі) ion exchange chromatography. In order to
carry out the ion exchange chromatography the 50 mg of ferment preparation were
re−dissolved in 5 ml of distilled water and after that were drifted on column (1,5 × 25 sm)
with DEAE−Toyopearl 650 M (Toyo Soda MFG, Co. Japan). Washing out of proteins was
carried out using the following buffers: (і) 20 mM tris−HCl, pH 7,0; (іі) 10 mM Na−acetate
buffer, pH 5,5; (ііі) 1 M NaCl in Na− acetate buffer, рН 5,5.
III. RESULTS AND DISCUSSIONS

Producer–strain of catalase has been isolated from the wastewater of sugar–refinery in
Vinnitsa region and was determined as Bacillus Sp. ShR–05. This strain is distinguished by the
high propagation rate both under aeration conditions and under stationary conditions and is
characterized by the ability to the synthesis of extracellular ferment (catalase) with the maximal
activity 17 mCat/l.
It has been studied the dynamics of catalase biosynthesis under cultivation of the Bacillus
Sp. ShR–05 producer–strain on the nutrient medium containing the glucose as the only one
carbon source under the aeration conditions (cultivation using the rocker) and under the
organic aeration (stationary conditions). It was determined, that the synthesis of catalase
depends on the aeration conditions (see Figure 1).
Thus, under cultivation of the Bacillus Sp. ShR–05 strain under aeration conditions it was
synthesized in 8 times more catalase, than under stationary conditions. On the second day and
night of the investigated strain cultivation under stationary conditions and on the fourth day
and night under aeration conditions it is observed the decrease of a catalase activity against a
background of the total protein increasing into supernatant. Probably, this is connected with
the start of the bacterial cells sporulation process of producent and also with the outcome of
the proteolitic ferments hydrolyzing the proteins including also ferments into culture broth.
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Account: ns063387
18
0,60
Concentration of enzyme, mg/ml

16 0,55
0,50
Activity of Catalase, mKat/l

14
0,45
12 0,40
10 0,35
0,30
8
0,25
6 0,20
4 0,15
0,10
2
0,05
0 0,00
1 2 3 4 7
Tim e, days & nights
Figure 1. Dynamics of the catalase biosynthesis by Bacillus Sp. ShR–05 strain under conditions of
organic aeration (stationary) – and under aeration conditions – .The concentration of total protein into
supernatant of the strain under stationary conditions – ● and under aeration – ▲.
With the aim of carrying out more precise investigations it have been done the
eliminating and purification of catalase from the supernathant of culture broth of the Bacillus
Sp. ShR−05 strain.
Characteristics of separate stages of the ferment eliminating and also the efficiency of
catalase purification are represented in Table 1 and on Figure 2. Obtained in
above−mentioned purification way catalase was used for carrying out the following experimental
investigations with the use of bioSAS.
It was investigated the influence of rhamnolipids (in solutions by different
concentrations) on the catalase activity. It has been shown, that the surface–active
rhamnolipids synthesized by the Pseudomonas Sp. PS–17 strain in concentrations from 0,075
mg/ml to 0,2 mg/ml increases the catalase activity in 4–4,5 times (Figure 3).
Table 1. Characteristic of separate stages of the ferment eliminating and also the
efficiency of catalase purification
Specific Multip Yield

General General
Stage of Volume,
activity, licity upon

protein, activity,
purification ml mCat purific activity,
mg mCat/l
/l·mg ation %
Supernathant 250 400 79 0,16 (1) (100)
Acetone 80 48 47 0,84 5,3 60
DEAE−
Toyopearl 60 1,62 5,5 6 36 6
650 M
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1 ,0
Concentration of enzyme, mg/ml

8

0 ,8
6
0 ,6
4 0 ,4
2 0 ,2
0 ,0
0
0 10 20 30 40 50 60 70
N u m b e r o f f r ic r io n
Figure 2. Ion exchange chromatography of catalase on DEAE−Toyopearl 650 M. ○ is the catalase

activity and ● is the concentration of protein.
It was studied the rhamnolipids action on the processes of fermentative catalysis under
different values of pH. During the previous experiments it was shown, that the optimum of
pH for catalase synthesized by Bacillus Sp. ShR−05 strain is in a range of pH 7 – 10. The
addition of the rhamnolipids at values of pH 4,0 – 5,0 has not the considerable influence on
the catalase activity (Figure 4).
30
25
20
15
10
0
0 ,0 0 0 ,0 5 0 ,1 0 0 ,1 5 0 ,2 0
C o n c e n tr a tio n o f S A S , m g /m l
Figure 3. An influence of the rhamnolipids on catalase activity.
Activating action of the investigated bioSAS was discovered at values of pH 6,0 – 10,0.
An increase of the catalase activity was observed at the rhamnolipids addition in
concentrations from 0,075 to 0,2 mg/ml. Thus, the rhamnolipids by concentration of 0,1
mg/ml increase the catalase activity in 4 times.
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Account: ns063387
25
20

15
10
4 5 6 7 8 9 10
pH
Figure 4. An influence of the rhamnolipids on catalase activity under different values of pH. The
concentration of rhamnolipids is as follow: ● – 0; ○ – 0,01; ▼ – 0,025; ∇ – 0,075; □ – 0,1; Δ – 0,125; ■
– 0,15; ▲ – 0,2 mg/ml.
It was investigated the bioSAS action on the catalase activity under different
temperatures. During the previous experiments it was shown, that the catalase activity a great
extent depends on the reactive medium temperature (Figure 5). It was studied the
rhamnolipids influence on catalase activity under the temperatures from 20 to 80 0C. Obtained
experimental data show, that the activating action of bioSAS on catalase is kept under
different temperatures (Figure 5).
34
32
30
28
26
24
22
20
18
16
14
12
10
8
20 30 40 50 60 70 80
0
t, C
Figure 5. An influence of the rhamnolipids on catalase activity under different temperatures. The
concentration of rhamnolipids is as follow: ● – 0; ○ – 0,01; ▼ – 0,025; ∇ – 0,075; □ – 0,1; Δ – 0,125; ■
– 0,15; ▲ – 0,2 mg/ml.
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Account: ns063387
It was studied the action of the supernatant of culture broth on the ferment activity in a
range of temperatures (20 – 80 0C) and pH (4,0 – 10,0) (Figure 6, 7). It was shown, that the
supernatant with the concentration of rhamnolipids from 0,01 to0,1 mg/ml increases the
catalase activity in 1,5 – 2,0 times whereas the purified rhamnolipids under the same
concentrations increase the catalase activity in 2,5 – 4,0 times. Decreasing the ferment
activity at the supernatant using with respect to the variant of purified rhamnolipids can be
explain by the presence of pyocyanin into culture broth; such compound is the inhibitor of the
ferments activity [17].
15
10
4 5 6 7 8 9 10
pH
Figure 6. An influence of the supernatant of culture broth Pseudomonas Sp. PS–17 on catalase activity
under different values pH. The concentration of rhamnolipids is as follow: ● – 0; ○ – 0,01; ▼ – 0,025;
∇ – 0,075; □ – 0,1 mg/ml.
It is necessary to notify, that the optimum of the rhamnolipids concentration needed for
the increase of the catalase activity under different values of pH and temperatures is in the
ranges of their micelle forming critical concentration (MFCC) – 0,1 mg/ml. These results are
in good agreement with the results of the references obtained as a result of the carried out
experiments with the use of the synthetic SAS. Thus, authors of [1] inform, that at the
concentrations of SAS (cetyltrimethylammonium bromide – CTAB, chlorides of
alkyltrimethylammonium – ATMACh, Twin–20), neared to the MFCC, the peroxidase of the
horse–radish good interacts with the substrate; this is repulsed on the ferment activity
increasing. Surface–active substances depending on concentration specifically interact with
the ferment and changes of its conformation or chemical mechanism of interaction between
ferment, substrate and the product of reaction [1–3]. Essential is the fact that under high
concentrations of SAS its molecules can sterically prevent to the interaction of substrate with
the ferment inhibiting the oxidation process. Probably, the investigated by us biogenic SAS
has the same action on catalase.
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20

18
16
14
12
10
20 30 40 50 60 70 80
0
t, C
Figure 7. An influence of the supernatant of culture broth Pseudomonas Sp. PS–17 on catalase activity
under different temperatures. The concentration of rhamnolipids is as follow: ● – 0; ○ – 0,01; ▼ –
0,025; ∇ – 0,075; □ – 0,1 mg/ml.
So, on a basis of the experimental data it was shown, that the bioSAS by rhamnolipid
nature in concentrations from 0,075 mg/ml to 0,2 mg/ml can increase the catalase activity in 4
times in a range of pH 6,0 – 10,0 under the temperatures from 20 to 80 0C. Obtained results
permit to apply the bioSAS in experimental practices and in different fields of industry as
regulators of ferments activity. Discovered regularities of the bioSAS influence on catalase
activity have a great sense, since permit to wide the possibilities of practical application of the
presented ferment and to create the modern complex enzyme compounds effective in a wide
range of the temperatures and pH.
REFERENCES
[1] Mietielitsa D. I. Modelling of the Oxidizing–Reduction Ferments // Minsk: «Nauka I
tekhnika», 1984, 293 p. (in Russian).
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Biophys. Acta”, 1975, v. 415 (1), p. p. 29−79
[3] Nelson C. A. The Binding of Detergents to Proteins: I. The Maximum Amount Of
Dodecyl Sulfate Bound To Proteins And The Resistance To Binding Of Several
Proteins // “J. Biol. Chem.”, 1971, v. 246 (2), p. p. 3895−3901

[4] Bognolo G. Biosurfactants as emulsifying agents for hydrocarbons Colloids //
“Physical Chemistry and Engineering”, 1999, v. 152, p. p. 41−52
[5] Eliora Z., R. and E. Rosenberg Natural roles of biosurfactants : Minireview // “Env.
Microbiology”, 2001, v. 3 (4), p. p. 229−236
[6] Bezborodov A. M. // «Biotechnologiya produktov mikrobnogo sinteza» / М.:
«Agropromizdat», 1991, 235 p. (in Russian).
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[7] Karpenko E. V., Martynyuk N. B., Shulga A. N. Surface–active biopreparation // Patent of

Ukraine № 71222, bull. № 12, 2004 (in Ukrainian)
[8] Karpenko E. V., Vildanova R. I., Shcheglova N. S. Change in the Composition of a
Bacterial Association Degrading Aromatic Compounds during Oil Sludge
Detoxification in a Continuous-Flow Microbial Reactor // “Appl. Biochem. and
Microbiology”, 2006, v. 42, p. p. 156−159
[9] Banat I. M., Makkar R. S., Cameotra S. S. Potential commercial applications of
microbial surfactants // «Appl. Microbiol. Biotechnol.», 2000, v. 53, p. p. 495–508.
[10] Desai J. D., Banat I. M. Microbial production of surfactants and their commercial
potential // «Microbiology and Molecular Biology Reviews», 1997, v. 61, № 1, p. p. 47–
64
[11] Ishigami Y. // «Characterization of biosurfactants» / New York Edn., 1997, p. p. 197–
226.
[12] Vasileva–Tonkova E., Galabova D., Karpenko O., Shulga A. Biosurfactant–
rhamnolipid effects on yeast cells // «Letters in Applied Microbiology», 2001, v. 33, p.
p. 280–284.
[13] Sotirova A., Galabova D., Vasileva–Tonkova E., Shulga A., Karpenko O. Effects of
biosurfactant–rhamnolipid on bacterial growth and protein release // «Ecological
Engineering and Environmental Protection», 2003, v. 1.
[14] Shulga A. N., Karpenko E. V., Elyseev S. A., Vildanova−Martsishyn R. I. Strain
Pseudomonas Sp. PS–17 – producer of the extracellular bioSAS and biopolymer //
Patent of Ukraine № 10467 A, 1996, bull. № 4, 3 p. (in Ukrainian).
[15] Ado S., Saito M. Chromatography lipid, biomedical research and chemical diagnostic
// «Elsevier».: Amsterdames, 1987, p. p. 266–310.
[16] Korolyuk M. A., Ivanova L. I., Mayorova I. G., Tokaryev V. E. Technique of the
Catalase Activity Determination // «Laboratornoye dielo», 1988, iss. 1, p. p. 16−19 (in
Russian).
[17] Yunxia Q., O’Malley, Krzysztof J. Reszka, George T. Rasmussen, Maher Y. Abdalla,
Gerene M. Denning and Bradley E. Britigan The Pseudomonas secretory product
pyocyanin inhibits catalase activity in human lung epithelial cells // «Am. J. Physiol.
Lung. Cell Mol. Physiol.», 2003, v. 285, p. p. 1077 –1086.
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In: Polymer and Composites ISBN 978-1-61728-038-2

EPOXY POLYMERS AS NATURAL NANOCOMPOSITES:

G.M. Magomedov*1, Z.M. Amirshikhova1, G.V. Kozlov1,

Keywords: Epoxy polymer, nanostructures, mechanical properties, solid-state extrusion,

AIM AND SCOPE

calculated according to the formula [7]:

The stress-strain characteristics were studied in conditions of uniaxial compression on a

RESULTS AND DISCUSSION

At temperature increase or mechanical stress application nonstable clusters are

mechanical devitrification and, as consequence, glassy polymers rubber-like behaviour on

EPOXY POLYMERS AS NATURAL NANOCOMPOSITES:

G.M. Magomedov1, Z.M. Amirshikhova1, G.V. Kozlov1,

Keywords: Epoxy polymer, structure, nanoclusters, yield stress, elasticity modulus.

AIM AND SCOPE

where NA is Avogadro number.

RESULTS AND DISCUSSION

where b is Burgers vector, ρd is linear defects density, ν is Poisson’s ratio.

where Tg and T are glass transition and testing temperatures, accordingly.

In table 1 the comparison of the obtained experimentally σY and calculated according to

(average discrepancy of σY and makes up 6.6 %, that is comparable with mechanical

Table 1. The structural and mechanical characteristics of epoxy polymers

Epoxy Kst νs×10-26, ϕcl E, GPa σY, MPa σYt ,

THE CHARACTERIZATION OF NOVEL

Yu.N. Pankova1, A.N. Shchegolikhin2, A.L. Iordanskii*1,

pairs of compatible or partly compatible polymers. Blending PHB with PA could be a

Keywords: polyhydroxybutyrate, biodegradation, blends, properties, kinetics, diffusion.

αPHB = ∆HPHB/∆HoPHB(1/wPHB) 100% A

αPA = ∆HPA/∆HoPA(1/wPHA) 100% B

RESULTS AND DISCUSSION

TRANSPORT BEHAVIOR OF WATER IN BLEND OF PHB WITH

PW = αSPE FPE PWPE + αSPHB FPHB PWPHB + αSInt PWH (4)

α SPE + α SPHB + αSint = 1 (5)

PHASE TRANSITIONS IN THE BLEND OF PHB WITH MODERATELY

Mechanism of thermophysical behavior can help us to design a novel therapeutic system

[10] Ying Hu, Robert H. Hurt. Carbon 39 887–896 (2001). Thermodynamics of

MACROKINETIC MECHANISM OF BIODEGRADATION

G.E. Zaikov1 and K.Z. Gumargalieva*

The contributors collected information about macrokinetic mechanism of

Keywords: biodegradation, dextranes, kinetics, mechanism, cross-linked polymers.

1 Chembio@sky.chph.ras.ru, N.M. Emanuel Institute of Biochemical Physics,Russian Academy of Sciences4

2. MATERIALS AND TECHNIQUES

CH2 CH2 CH2 CH2

Aldehyde sephadex (AS) arises by the reaction

Carboxymethylsephadex is produced by the reaction

Medicines “grafted” onto polymeric supports were well-known antitubercular remedies,

CH2NH2 CH2OH H2N NHC O

CH2 CH2 CH2 CH2

Degradation of polymeric carriers and medicinal polymers was followed by variation of

CH2NH 2 CH2OH H 2N NHC O

The activation energy was calculated as a slope of the logarithmic temperature

dependence of the rate constant for the medicine release

Fiigure 4. Time histories

3. EXPERIMENTAL RESULTS AND DISCUSSION

Fiigure 6. Time histories

Investigation into degradation of medicinal polymers in the presence of α-amylase has

Fiigure 12. Time histories of the relative mass of

[110] M. Singhh, D. Vasadevaan, J. Biomed. Mater. Res., 1981, 15(5), 655.

THERMAL DEGRADATION AND FLAMMABILITY OF

G. E. Zaikov*1, I. L. Dubnikova2, N.G. Shilkina2, S. M. Lomakin1,

Keywords: Intercalation polymerization; kinetics; layered clay; nanocomposite;

Polyethylene (PE), Basel Lupolen, was used to prepare PE nanocomposites in the

organic cation-exchange modifier, N+2CH32HT (HT=hydrogenated tallow, C18≈65%;

PE/MAPE/MMT nanocomposites were prepared by the melt mixing of the components