Supramolecular catalytic system triton X-100-polyethyleneimine-La(III) for hydrolysis of phosphonic acid esters

Article abstract of DOI:10.1134/S0023158411010101

The self-organization of systems based on the nonionic surfactant Triton X-100, polyethyleneimine, and lanthanum ions has been investigated. The micellar solutions of Triton-X-100 alone and the Triton-X-100-polyethyleneimine binary systems inhibit the hyd

Full text of DOI:10.1134/S0023158411010101

ISSN 0023ꢀ1584, Kinetics and Catalysis, 2011, Vol. 52, No. 1, pp. 55–61. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © Yu.R. Kudryashova, F.G. Valeeva, A.R. Ibragimova, L.Ya. Zakharova, A.I. Konovalov, 2011, published in Kinetika i Kataliz, 2011, Vol. 52, No. 1,
pp. 56 62.
⎯
Supramolecular Catalytic System
Triton Xꢀ100–Polyethyleneimine–La(III)
for Hydrolysis of Phosphonic Acid Esters
Yu. R. Kudryashova, F. G. Valeeva, A. R. Ibragimova, L. Ya. Zakharova, and A. I. Konovalov
Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center,
Russian Academy of Sciences, Kazan, 420088 Tatarstan, Russia
eꢀmail: lucia@iopc.ru
Received April 22, 2009
Abstract—The selfꢀorganization of systems based on the nonionic surfactant Triton Xꢀ100, polyethyleneꢀ
imine, and lanthanum ions has been investigated. The micellar solutions of TritonꢀXꢀ100 alone and the Triꢀ
tonꢀXꢀ100–polyethyleneimine binary systems inhibit the hydrolysis of phosphonic acid esters. The Tritonꢀ
Xꢀ100–polyethyleneimine–La(III) ternary system with a certain component ratio exerts a considerable catꢀ
alytic effect, raising the rate of the reaction by more than three orders of magnitude relative to the rate of the
alkaline hydrolysis of the phosphonates.
DOI: 10.1134/S0023158411010101
A promising area of presentꢀday catalysis science is 3–6 orders of magnitude relative to the rate of the
design of supramolecular systems that, due to their alkaline hydrolysis of the same substrates.
biomimetic character, can ensure high catalytic activꢀ
Continuing those works, we have designed a new
ity and selectivity under mild conditions [1–3]. In our
catalytic system based on the nonionic surfactant
earlier works [4–6], we suggested an approach to the
polyethylene glycol(10) mono(4ꢀisooctylphenyl)
design of multicomponent catalytic systems capable of
ether (Triton Xꢀ100). As distinct from the nonionic
executing a combined catalytic action, including
surfactant С ЕО10, which is inactive in the hydrolysis
micellar, macromolecular, and homogeneous catalyꢀ
sis. Surfactants of various natures, polymers, and
metal ions were used as the components of these sysꢀ
tems. In particular, we investigated catalytic systems
based on polyethyleneimine (PEI) and a lanthanum
12
of phosphorus acid esters, the aqueous solutions of
Triton Xꢀ100 slow down the hydrolysis of the subꢀ
strates. Therefore, by varying the nature and concenꢀ
trations of components, it is possible to formulate
salt, modified with the anionic surfactant sodium compositions ranging in activity from inhibition to
dodecyl sulfate [4], geminal pyrimidineꢀcontaining catalysis. For this purpose, we studied, in succession,
surfactants [5], and the nonionic surfactant decaethylꢀ the catalytic effects of the singleꢀcomponent system
ene glycol monodecyl ether (С ЕО10) [6]. These sysꢀ Triton Xꢀ100, the binary system Triton Xꢀ100–PEI,
12
tems afforded a considerable catalytic effect, raising and the ternary system Triton Xꢀ100–PEI–La(III) on
the rate of the hydrolysis of phosphorus acid esters by phosphorus acid ester hydrolysis:
O
O
ClCH2
RO
ClCH2
RO
P O
NO + H O
P OH + HO
NO2
2
2
1, 2
R = С Н (
2
1
) or С Н (2)
5
6
13
In addition, the micellization properties of these sysꢀ fore, the stability of these substrates is a topical issue.
tems were studied by surface tension measurements The hydrolysis of phosphorus acid esters in water in
and dynamic light scattering.
Phosphoryl group transfer is among the most tems has been studied in detail [1–3, 9], so it is a conꢀ
important biochemical reactions [7]. The esters of venient test reaction. The hydrolysis of ꢀnitrophenyl
phosphorus acids are biologically active compounds esters occurs through P–OAr bond breaking, yielding
widely used as pesticides, medicines, etc. [8]. Thereꢀ ꢀnitrophenol.
the absence of a surfactant and in simple micellar sysꢀ
p
p
55

56
KUDRYASHOVA et al.
Particle sizes were determined by the dynamic light
γ
, mN/m
5
scattering method on a Photocor Complex photon
correlation spectrometer (Milton Roy, United States)
6
6
5
5
4
4
1
2
3
4
5
equipped with a 25ꢀmW He–Ne laser ( = 633 nm).
λ
о
The scattering angle was 90 , and the pulse counting
time was 500 s. Before measurements, the samples
were filtered through Millipore membrane filters with
0
5
0
5
0
a pore diameter of 0.45 m to remove dust. The autoꢀ
µ
correlation functions of scattered light intensity flucꢀ
tuations were measured with a PhotoCorꢀM 72ꢀchanꢀ
nel correlator and were analyzed using the cumulant
method and the DynaLS program, which allowed the
aggregate size distribution to be estimated.
The kinetic data obtained for the PEI solutions
were fitted to Eq. (1), an analogue of the Michaelis–
Menten equation, which is widely used in enzyme and
micellar catalysis [1] and assumes the formation of a
substrate–micelle catalytic complex:
k + k K C
w
cat
S
kapp
=
,
(1)
1
+ KSC
where kapp is the apparent pseudoꢀfirstꢀorder rate conꢀ
stant; kw and kcat are the firstꢀorder rate constants of
the reaction in water and in the catalytic complex
medium, respectively; KS is the reduced substrate–
3
5
0
micelle binding constant; and
centration minus the critical micelle concentration
CMC).
С is the surfactant conꢀ
3
1
E−
5
1E−4
1E
−
3
0.01
(
[
Surfactant], mol/l
Fig. 1. Surface tension (
γ
) isotherms for the systems (
1)
RESULTS AND DISCUSSION
Triton Xꢀ100–H O, ( ) Triton Xꢀ100–PEI–H O, (
2
3
) Triꢀ
2
2
ton Xꢀ100–PEI–La(III)–H O,
(
4)
Triton Xꢀ100–
5) Triton Xꢀ100–
SelfꢀOrganization
2
DMF–H O (10 vol % DMF), and (
2
DMF–H O (30 vol % DMF). [PEI] = 0.05 mol/l;
According to the literature [11], the mutual affinity
2
3
[
La(NO ) ] = 0.008 mol/l;
T
=
25°C
.
of the components in nonionic surfactant–polymer
systems is much weaker than that in ionic surfactant–
polymer systems. Figure 1 shows the surface tension
isotherms from which we derived the CMC values for
the Triton Xꢀ100 solution, the binary system Triton
Xꢀ100–PEI, and the ternary system Triton Xꢀ100–
PEI–La(III). The introduction of the polymer into
the solution does not decrease the CMC, which
remains equal to 0.00021 mol/l. The absence of a
polymer effect on the micellization behavior of a surꢀ
factant is conventionally considered to be evidence of
weak mutual affinity in the surfactant–polymer pair.
The introduction of metal ions into the system exerts
only a slight effect on the CMC (Fig. 1).
Addition of solvents that disturb the structure of
water diminish the hydrophobic effect [12–14], which
plays the key role in the formation of normal phase
micelles. We studied the effect of the aprotic solvent
dimethylformamide (DMF) on the micellization
properties of the surfactant. A comparison of surface
tension isotherms for Triton Xꢀ100 solutions containꢀ
ing different DMF concentrations (Fig. 1) demonꢀ
strates that the addition of 10 and 30 vol % DMF
3
EXPERIMENTAL
and were synthesized using a stanꢀ
Compounds
1
2
dard procedure [10]. The components of the catalytic
system were Triton Xꢀ100 (Sigma), branched PEI
molecular weight of 50000, 50% solution, Aldrich),
(
La(NO ) · 6H O (Aldrich). The PEI molar concenꢀ
3
3
2
trations specified below refer to the monomer unit.
The hydrolysis kinetics was studied spectrophotoꢀ
metrically on a Specord Mꢀ400 spectrophotometer
under pseudoꢀfirstꢀorder conditions by measuring the
absorbance of the
rate constants (kapp) were determined using the relaꢀ
tionship ln(A∞ ) = –k t + const, where and A∞
are the absorbances of the solution at the point in time
and after the completion of the reaction, respectively.
pꢀnitrophenolate anion. Apparent
–
A
А
app
t
These calculations were carried out by the weighted
least squares method. The arithmetic mean values of
three measurements differing by no more than 5%
were involved in the calculations.
Surface tension was measured at 25°С by the Du sharply raises the Triton Xꢀ100 CMC from 0.00021 to
Nouy ring detachment method. 0.00090 and 0.0048 mol/l, respectively.
KINETICS AND CATALYSIS Vol. 52
No. 1
2011

SUPRAMOLECULAR CATALYTIC SYSTEM TRITON
57
Proportion of particles, %
R,
nm
R, nm
1
10
00
90
160
1
35
30
25
20
15
10
5
8
7
6
0
0
0
1
1
40
50
120
00
40
30
20
2
1
10
0
8
6
4
0
0
0
−10
0
0.01 0.02 0.03 0.04
Surfactant], mol/l
[
2
20
0
0
0.002 0.004 0.006 0.008 0.010
La(III)], mol/l
[
1
Fig. 3. Average hydrodynamic radius of the particles in the
PEI–La(III) system as a function of the lanthanum ion
concentration at 25°С and [PEI] = 0.05 mol/l.
0
0.01
0.02
0.03
0.04
[Surfactant], mol/l
likely due to the immobilization of micellar aggregates
accompanied by some unfolding of the polymer coil.
The small aggregates are apparently free Triton Xꢀ100
micelles not bound to a macromolecule. As the surfacꢀ
tant concentration is increased, the number of free
micelles increases, resulting in a decrease in effective
aggregate size in the binary system. This is in agreeꢀ
ment with theory [11], according to which coaggregaꢀ
Fig. 2. Average hydrodynamic radius of the particles (
the ( ) Triton Xꢀ100 solution and ( ) Triton Xꢀ100–PEI
system as a function of the surfactant concentration at
5°C and [PEI] = 0.05 mol/l. Inset: Proportion of partiꢀ
cles with a radius of ( 50 and ( ) 4–6 nm as a function
of the surfactant concentration in the Triton Xꢀ100–PEI
system.
R) in
1
2
2
1)
±
5
2
The formation of aggregates in systems based on tion via the immobilization of surfactant aggregates on
the polymer matrix occurs in surfactant–polymer sysꢀ
tems at low surfactant concentrations. Upon the satuꢀ
ration of the macromolecules with micelles, ordinary
micelles unbound to the polymer form in the solution.
Triton Xꢀ100 was proved by dynamic light scattering
Figs. 2, 3). The average hydrodynamic radius of the
(
aggregates in the Triton Xꢀ100 solutions is 4 nm. The
Triton Xꢀ100–PEI system was also investigated by
dynamic light scattering. The concentration depenꢀ
dences of the effective hydrodynamic radius of the
aggregates measured by the cumulant method (autoꢀ
correlation function expansion in two cumulants) are
plotted in Fig. 2. The inset in Fig. 2 shows the particle
size distribution obtained using the DynaLS program.
In the Triton Xꢀ100–PEI system, the effective aggreꢀ
gate size decreases from 30 to 7 nm as the surfactant
In the presence of a lanthanum salt, polymeric
hydroxo complexes form in the solution according to
the following scheme [15]:
3+
[La(H O) (OH)k](3 – k)+,
[La(H O) ]
2
n
2 n – k
where k = 1–3, and n can be fairly large, as in typical
polymers. As a consequence, a sharp increase in the
aggregate size takes place in the systems containing
PEI and lanthanum ions (Fig. 3), which is accompaꢀ
concentration is raised. As is clear from the data preꢀ nied by gelation and by a decrease in the pH of the
sented in the inset in Fig. 2, the binary solutions are solution at high lanthanum salt concentrations.
polydisperse and contain two types of particles,
namely, large particles with an average hydrodynamic
Catalytic Properties
radius of 50
±
5 nm and small particles 4–6 nm in
radius. The former can be assumed to be polymer molꢀ
ecules. Their size in the binary system is larger than aqueous solutions of an alkali and PEI was studied in
their size in the solution of the polymer alone. This is our earlier works [4, 16]. The secondꢀorder rate conꢀ
The hydrolysis kinetics of phosphonates 1 and 2 in
KINETICS AND CATALYSIS Vol. 52
No. 1
2011

58
KUDRYASHOVA et al.
kapp
10 , s−
10 , s−
2
1
×
4
1
kapp
×
4.0
3.8
3.6
3.4
3.2
3.0
2.8
2.6
2.4
2.2
2.0
1.8
1.6
1.4
1.2
1.0
3
3
2
2
1
1
5
0
5
0
5
0
5
3
1
2
1
2
0
0.01
0.02
0.03
0.04
[Surfactant], mol/l
0
0.01
0.02
0.03
[Surfactant], mol/l
Fig. 5. Apparent rate constant of the hydrolysis of subꢀ
strate as a function of the Triton Xꢀ100 concentration at
a constant PEI concentration of ( ) 0.05, ( ) 0.1, and
) 0.5 mol/l. 25°C
Fig. 4. Apparent rate constant of the alkaline hydrolysis of
substrates ( and ( as a function of the Triton Xꢀ100
concentration at 25°С and [NaOH] = 0.01 mol/l.
1
1)
1
2)
2
1
2
(
3
T
=
.
stants of the alkaline hydrolysis of
3
1
and
.0 l mol s , respectively. In the aqueous solutions substrate
containing PEI, general base catalysis takes place and ions in the polyoxyethylene mantle of the nonionic
phosphonate , which is less hydrophobic than , is micelles of Triton Xꢀ100 decreases, which is likely due
2
are 4.0 and surfactant effect is greater for the more hydrophobic
–1 –1
2
(Fig. 4). The concentration of hydroxide
1
2
more reactive [16, 17]. Investigation of the hydrolysis to the strong affinity of these ions for the aqueous
of esters with different hydrophobicities in surfactant– pseudophase, and this leads to the separation of the
polymer systems provides information concerning the
contributions from the micellar catalysis and macroꢀ
molecular catalysis to the overall catalytic effect,
which can be characterized by the ratio of the rate
constant in the catalytic complex medium to the rate
reactants, as in the micelles of anionic surfactants. The
hydrolysis of the phosphonates in the aqueous solution
of PEI accelerates with an increasing PEI concentraꢀ
tion. This is due the contribution from two processes,
namely, the binding of the reactants by the macromolꢀ
ecules and general base catalysis by the amino groups
constant in water (kcat/kw) at a fixed pH. In the case of
micellar catalysis, in which the solubilization mechaꢀ
nism of substrate binding takes place, the hydrolysis
rate constant usually increases considerably with an
increasing hydrophobicity of the substrate. In polymer
solutions in which a catalytic substrate–polymer
complex forms, the hydrophobicity factor is insignifꢀ
icant [16].
[
4]. In the Triton Xꢀ100–PEI system, the reaction is
inhibited (kcat kw < 1; see the table), and this effect is
again more pronounced for the more hydrophobic
phosphonate (Figs. 5, 6). As was mentioned above,
/
2
this is evidence that the micellar effect makes the
major contribution to the overall change in the reacꢀ
tion rate. On the whole, the degree of inhibition
Figures 4–8 plot the apparent rate constant of increases with an increasing PEI concentration. The
hydrolysis of the substrates as a function of the conꢀ deceleration of the reaction in the surfactant–PEI sysꢀ
centrations of the components of the supramolecular tems is an unusual observation. It was demonstrated
system. In the aqueous solution of Triton Xꢀ100, the earlier [4–6] that the hydrolysis of phosphonates
alkaline hydrolysis of the phosphonates slows down
accelerates in similar systems containing surfactants
with an increasing surfactant concentration, and this of various natures, including nonionic surfactants [6].
1 and
2
KINETICS AND CATALYSIS Vol. 52
No. 1
2011

SUPRAMOLECULAR CATALYTIC SYSTEM TRITON
59
10 , s−
3
1
kapp
10 , s−
×
3
1
kapp
×
3
10
8
6
4
2
2
1
0
3
1
2
2
1
0
0.01
0.02
0.03
La], mol/l
0.01
0.02
[
0.03
0.04
[
Surfactant], mol/l
Fig. 7. Apparent rate constant of the hydrolysis of subꢀ
strates ( and ( in the Triton Xꢀ100–PEI–La(III)–
Fig. 6. Apparent rate constant of the hydrolysis of subꢀ
strate as a function of the Triton Xꢀ100 concentration at
a constant PEI concentration of ( ) 0.05, ( ) 0.1, and
) 0.5 mol/l. 25°C
1)
1
2) 2
2
H O system as a function of the La concentration at conꢀ
2
1
2
stant PEI and Triton Xꢀ100 concentrations of 0.05 and
(
3
T
=
.
0.005 mol/l, respectively. T = 25°C.
The causes of the total suppression of the catalytic two orders of magnitude in the case of
1) as the PEI
action of the amino groups of PEI will be discussed concentration is raised (table). This tendency is likely
below.
Kinetic data were analyzed within the pseudophase
model using Eq. (1). As is clear from the table, the
stronger inhibition of the hydrolysis of (threefold
decrease in the reaction rate) as compared to the
hydrolysis of is due to the larger values of the binding
constants of the hydrophobic substrate. The binding
constants of the substrates decrease on passing from
the Triton Xꢀ100 solution to the Triton Xꢀ100–PEI ence of the polymer, as is indicated by the fairly large
due to the crossover from the more effective, solubiliꢀ
zation mechanism of substrate binding in Triton Xꢀ
1
00 micelles to the sorption mechanism involving PEI
macromolecules in the polymer–colloid systems.
However, in the case of , the more hydrophobic
2
2
1
phosphonate, the solubilization mechanism makes a
considerable contribution to hydrolysis in the presꢀ
systems. In addition, they decrease sharply (by up to KS values (table).
Results of quantitative analysis of the kinetic data presented in Fig. 4 within the pseudophase model of micellar catalysis (T = 25°C)
System
PEI concentration, mol/l
Substrate
KS,
l/mol
kcat, s–1
kcat/kw
Triton Xꢀ100
Triton Xꢀ100
0
0
1
2
1
2
1
2
1
2
240
0.021
0.012
0.52
0.38
0.44
0.27
0.60
0.47
0.62
0.30
2100
590
2500
18
540
19
Triton Xꢀ100–PEI
Triton Xꢀ100–PEI
Triton Xꢀ100–PEI
Triton Xꢀ100–PEI
Triton Xꢀ100–PEI
Triton Xꢀ100–PEI
0.05
0.05
0.1
0.1
0.5
0.5
0.00028
0.00011
0.0008
0.0005
0.002
330
0.0008
KINETICS AND CATALYSIS Vol. 52
No. 1
2011

6
0
KUDRYASHOVA et al.
3
10 , s−
1
bution to the inhibition effect is made by the alkaline
hydrolysis of the substrates as a side reaction.
kapp
×
Figures 7 and 8 present the kinetic data obtained
for the hydrolysis of the phosphonates in the Triton Xꢀ
6
1
00–PEI–La(III) system. As the lanthanum ion conꢀ
centration is increased at fixed concentrations of the
other components, the apparent rate constant initially
increases sharply (by a factor of 4 and 80 for
1 and 2,
5
4
3
2
1
respectively) relative to the rate constant for the Triton
Xꢀ100–PEI binary system (Fig. 7). As the lanthanum
ion concentration is further raised, the hydrolysis rate
constant of
while that of
1
gradually decreases to a constant level,
, a more hydrophobic substrate, passes
2
through a maximum. This kind of dependence can be
due to the competitive character of component interꢀ
action in the system. It is likely that the lanthanum
ions saturate the surface layer of the micelles and, as a
consequence, there is Coulomb repulsion between the
positively charged ions and the protonated groups of
PEI. The number of the latter increases as the pH of
the solution decreases. This can destabilize the polyꢀ
mer–colloid complexes in which the reaction takes
place and cause a decrease in the substrate binding
constant.
Based on the above data, we chose a lanthanum
nitrate concentration of 0.008 mol/l as the optimum
concentration. It is at this concentration that we studꢀ
ied the dependence of the apparent rate constant of
phosphonate hydrolysis in the ternary system on the
surfactant concentration (Fig. 8). The rate constant
2
1
0
0.01
0.02
[
0.03
0.04
Surfactant], mol/l
Fig. 8. Apparent rate constant of the hydrolysis of subꢀ
strates ( and ( in the Triton Xꢀ100–PEI–La(III)–
H O system as a function of the Triton Xꢀ100 concentraꢀ
tion at constant PEI and La(NO ) concentrations of 0.05
and 0.008 mol/l, respectively.
1)
1
2) 2
2
for
decreases with an increasing surfactant concentration,
while the rate constant for passes through an extreꢀ
1, the less hydrophobic substrate, gradually
3
3
T = 25°C.
2
mum. However, even for the descending branches of
these kinetic curves, the hydrolysis rate is higher than
is observed for the solution of PEI alone. As is clear
Taking into account the above quantitative data, we
will analyze the uncommon inhibition effect observed
in the Triton Xꢀ100–PEI system, in contradistinction
from Figs. 7 and 8, the more hydrophobic substrate
2
is more reactive, indicating that the micellar catalysis
makes the dominant contribution to the overall cataꢀ
lytic effect.
to the acceleration of the hydrolysis of
1 and 2 in the
presence of the nonionic surfactant С ЕО and PEI
12
10
[
6]. Note that, although PEI exerts no effect on the
micellization properties of the surfactants (Fig. 1), the
existing kinetic data provide indirect evidence in favor
Addition of the lanthanum salt reduces the alkalinꢀ
ity of the solution to pH 8. The hydrolysis rate of
1 and
2
in the ternary system is higher than the rate of the
of the formation of mixed aggregates involving Triton alkaline hydrolysis of the same compounds by a factor
Xꢀ100. This is indicated by the fact that the substrate of 600 and 3000, respectively.
binding constants for the binary systems are much
Thus, we investigated the selfꢀorganization of the
larger than those for the solution of PEI alone [4], as singleꢀcomponent micellar system Triton Xꢀ100, the
binary system Triton Xꢀ100–PEI, and the ternary sysꢀ
tem Triton Xꢀ100–PEI–La(III). Surface tension
measurements revealed no change in the CMC on
passing from the individual nonionic micelles to the
binary or ternary system. The catalytic effect on the
hydrolysis of phosphorus acid esters was studied in
these systems. Triton Xꢀ100 and the Triton Xꢀ100–
PEI system inhibit phosphonate hydrolysis, reducing
the reaction rate by a factor of 3. The ternary system is
an effective catalyst acting under mild conditions
well as by the pronounced dependence of these conꢀ
stants on the polymer concentration. In the case of
separate aggregation, the contribution from substrate
binding by the polymer should not have a significant
effect on the binding constants. The observed inhibiꢀ
tion effect provides further indirect evidence in favor
of surfactant aggregation through micelle immobilizaꢀ
tion on macromolecules. In this case, the slowdown of
the reaction in the bound micelles can dominate over
the catalytic acceleration of the reaction by the free
(
25°С, pH 8) and showing substrate specificity toward
PEI molecules. It is not impossible that some contriꢀ the more hydrophobic phosphonate. As compared to
KINETICS AND CATALYSIS Vol. 52
No. 1
2011

SUPRAMOLECULAR CATALYTIC SYSTEM TRITON
61
alkaline hydrolysis, the hydrolysis of phosphonates
1
6. Zakharova, L.Ya., Ibragimova, A.R., Valeeva, F.G.,
Kudryavtseva, L.A., Konovalov, A.I., Zakharov, A.V.,
Selivanova, N.M., Osipova, V.V., Strelkov, M.V., and
Galyametdinov, Y.G., J. Phys. Chem. C, 2007, vol. 111,
p. 13 839.
and in the Triton Xꢀ100–PEI–La(III) system is,
2
respectively, 600 and 3000 times more rapid. The
shapes of the kinetic profiles and the quantitative data
characterizing the reactivity of the phosphonates in
the binary and ternary systems differ from the correꢀ
sponding hydrolysis characteristics observed for the
singleꢀcomponent systems. This is evidence that the
reaction occurs in polymer–colloid complexes.
7
8
9
. Jencks, W., Catalysis in Chemistry and Enzymology
New York: Dover, 1987.
. Yang, Y.C., Bakker J.A., and Ward J.R., Chem. Rev.
,
,
1992, vol. 92, p. 1729.
. Loshadkin, N.A., Toksichnye efiry kislot fosfora (Toxic
Esters of Phosphorus Acids), Moscow: Mir, 1964.
ACKNOWLEDGMENTS
10. US Patent 2922810.
1
1. Holmberg, K., Jonsson, B., Kronberg, B., and Lindꢀ
This study was supported by the Russian Foundaꢀ
tion for Basic Research, grant no. 09ꢀ03ꢀ00572ꢀa.
man, B., Surfactants and Polymers in Aqueous Solution
,
London: Wiley, 2002.
1
2. Rusanov, A.I., Mitselloobrazovanie v rastvorakh poꢀ
verkhnostnoꢀaktivnykh veshchestv (Micellization in
Surfactant Solutions), St. Petersburg: Khimiya, 1992.
REFERENCES
1
2
3
4
. Berezin, I.V., Martinek, K., and Yatsimirskii, A.K., 13. Serdyuk, A.I. and Kucher, R.V., Mitsellyarnye
Usp. Khim., 1973, vol. 42, p. 1729.
perekhody v rastvorakh poverkhnostnoꢀaktivnykh veꢀ
shchestv (Micellar Transitions in Surfactant Solutions),
Kiev: Naukova Dumka, 1987.
. Bunton, C.A. and Savelli, G., Adv. Phys. Org. Chem.
,
1986, vol. 22, p. 213.
1
4. Zakharova, L.Y., Valeeva, F.G., Kudryavtseva, L.A.,
and Konovalov, A.I., Mendeleev Commun., 2000,
vol. 10, no. 6, p. 241.
. Dwars, T., Paetzold, E., and Oehme, G., Angew. Chem.,
Int. Ed. Engl., 2005, vol. 44, p. 7174.
. Zakharova, L., Ibragimova, A., Valeeva, F., Zakharov, A., 15. Bentouhami, E., Bouet, G.M., Meullemcestre, J.,
Mustafina, A., Kudryavtseva, L., Harlampidi, H., and
Konovalov, A., Langmuir, 2007, vol. 23, p. 3214.
Vierling, F., and Khan, M.A., C. R. Acad. Sci., Ser. IIc:
Chim., 2004, vol. 7, p. 537.
1
6. Zakharova, L.Ya., Mirgorodskaya, A.B., Zhil’tsova, E.P.,
Kudryavtseva, L.A., and Konovalov, A.I., Izv. Akad.
Nauk, Ser. Khim., 2004, no. 7, p. 1331.
5
. Zakharova, L.Ya., Semenov, V.E., Voronin, M.A., Valeꢀ
eva, F.G., Ibragimova, A.R., Giniatullin, R.Kh., Cherꢀ
nova, A.V., Kharlamov, S.V., Kudryavtseva, L.A., Latyꢀ
pov, Sh.K., Reznik, V.S.,and Konovalov, A.I., J. Phys. 17. Bakeeva, R.F., Kudryavtseva, L.A., Bel’skii, V.E., and
Chem. B, 2007, vol. 111, p. 14152.
Ivanov, B.E., Zh. Obshch. Khim., 1983, vol. 53, p. 1058.
KINETICS AND CATALYSIS Vol. 52
No. 1
2011