Supramolecular catalytic systems based on anionic amphiphiles and polyethyleneimine for hydrolytic cleavage of phosphorus ester bonds

Article abstract of DOI:10.1007/s11172-008-0057-0

Self-organization in individual and binary systems based on polyethyleneimine (PEI) and amphiphilic sulfonatocalix[4]resorcinarene was studied by conductometry, tensiometry, dynamic light scattering, and ¹H NMR spectroscopy. The critical concen

Full text of DOI:10.1007/s11172-008-0057-0

Russian Chemical Bulletin, International Edition, Vol. 57, No. 2, pp. 374—382, February, 2008
374
Supramolecular catalytic systems based on anionic amphiphiles
and polyethyleneimine for hydrolytic cleavage of phosphorus ester bonds
L. Ya. Zakharova,aꢀ F. G. Valeeva,a A. R. Ibragimova,a M. A. Voronin,a,b L. A. Kudryavtseva,a V. V. Syakaev,a
E. Kh. Kazakova,a Yu. E. Morozova,a N. A. Makarova,a N. B. Mel´nikova,c O. E. Zemnyakova,c and A. I. Konovalova
aA. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center of the Russian Academy of Sciences,
8 ul. Akad. Arbuzova, 420088 Kazan, Russian Federation.
Fax: +7 (843) 273 2253. Eꢀmail: lucia@iopc.knc.ru
bKazan State Technological University,
68 ul. K. Marksa, 420015 Kazan, Russian Federation
cNizhny Novgorod State Medical Academy,
10/1 pl. Minina, 603600 Nizhny Novgorod, Russian Federation
Selfꢀorganization in individual and binary systems based on polyethyleneimine (PEI) and
amphiphilic sulfonatocalix[4]resorcinarene was studied by conductometry, tensiometry,
1
dynamic light scattering, and Н NMR spectroscopy. The critical concentrations of micelle
formation and aggregate sizes were determined. The enhancement of the catalytic effect on the
hydrolysis of Oꢀethyl Oꢀpꢀnitrophenyl chloromethylphosphonate was shown in the following
series of the systems: PEI—water < PEI—calixarene—water < PEI—calixarene—LaIII—water.
Key words: amphipilic sulfonatocalix[4]resorcinarenes, polyethyleneimine, lanthanum ions,
selfꢀorganization, esters of phosphorus acids, hydrolysis, kinetics, supramolecular catalysis.
Supramolecular catalysis is presently being developed
in two directions: catalysis in organized media (micelles,
microemulsions, vesicles, liquid crystals)1—5 and catalysis
involving inclusion complexes based on cyclodextrins,
calixarenes, crown ethers, podands, etc.6,7 The reaction
mechanism of such catalysts includes the formation of
host—guest complexes, which fact brings together
supramolecular catalysis and enzymatic systems. Binding
of “guest” reactants creates a specific microenvironment
and concentration gradient compared to their state in
solution and makes the main contribution to the catalytic
effect.
We have previously8—12 obtained results indicating that
the simulation of the polyfunctional mechanism of the
enzyme action (using the synthetic supramolecular
systems as an example) leads, possibly, to high catalytic
effects. In particular, ensembles of the ionic and nonionic
surfactants were modified stepꢀbyꢀstep using polymers
and LnIII compounds,9—12 which made it possible to form
efficient supramolecular catalytic systems for the hydroꢀ
lytic decomposition of toxic organophosphorus comꢀ
pounds working under mild conditions.9,11
salts exist in solution as tetraanions and are capable of
forming inclusion complexes with biologically active
compounds, metal complexes, and polyfunctional organic
derivatives.
The purpose of the present work is to study selfꢀorgaꢀ
nization and catalytic activity of the complexes of
amphiphilic sulfonatocalix[4]resorcinarene (1) containꢀ
ing the pentyl substituent at the lower rim of the molecule
with polyethyleneimine (PEI) of branched structure (moꢀ
lecular weight 50 000). We compared the results for comꢀ
pound 1 and a typical anionic surfactant, sodium dodecyl
sulfonate (2), whose head group is identical in structure
to the charged moiety of sulfonatocalixresorcinarene.
In addition, we studied the effect of LaIII on the cataꢀ
lytic effect and hydrolysis of Oꢀethyl Oꢀpꢀnitrophenyl
chloromethylphosphonate (3) (Scheme 1), which has
earlier8 been studied in aqueous and individual micellar
solutions.
Each component of the ensembles under study posꢀ
sesses catalytic activity and can participate in selfꢀorganiꢀ
zation processes. Lanthanide complexes and polyamines
are widely known as homogeneous catalysts that are able
to accelerate nucleophilic substitution in esters of phosꢀ
phorus acids via the mechanism of electrophilic and genꢀ
eral basic catalysis.19—21 Compounds 1 and 2 are typical
supramolecular catalysts capable of solubilizing or incluꢀ
sively binding reactants to form host—guest complexes,
In the present work, we applied this methodology
to another type of supramolecular catalysts based
on cyclophanes. We have previously13—18 synthesized
amphiphilic sulfonatocalix[4]resorcinarenes with four
methylsulfonate groups at the upper rim. Their sodium
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 366—373, February, 2008.
1066ꢀ5285/08/5702ꢀ0374 © 2008 Springer Science+Business Media, Inc.

Supramolecular catalytic systems
Russ.Chem.Bull., Int.Ed., Vol. 57, No. 2, February, 2008
375
tion spectrometer. A He—Ne gas laser with a power of 10 mW
and a wavelength of 633 nm served as the laser radiation source.
The light scattering angle was 90°, and the pulse accumulation
time was several minutes. The signals were analyzed by a oneꢀ
plate multichannel correlator conjugated with an IBM PCꢀcomꢀ
patible computer. Experimental data were processed using the
method of cumulants included in the program package of the
goniometer. The method is based on the expansion of the correꢀ
lation function to the series including 2—3 cumulants. The first
cumulant reflects the aggregate radius, the second cumulant is
responsible for polydispersity, and the third one reflects the
asymmetric character of particles. The effective radii (R) of PEI
and polymerꢀcolloidal structures were calculated from the difꢀ
fusion coefficients (D) using the Stokes—Einstein equation based
on the first cumulant
D = kT/6πηR,
where k is the Boltzmann constant, T is the absolute temperaꢀ
ture, and η is the solvent viscosity. Prior to measurements soluꢀ
tions were filtered through Millipore filters to remove dust.
NMR experiments were carried out on a Bruker AVANCEꢀ600
instrument. An inverse probe (5 mm) with the maximum magꢀ
netic field pulse gradients in the Z axis direction ~50 G cm–1
was used for the measurements. Chemical shifts are presented
relative to HDO as the internal standard. In experiments on
measuring the selfꢀdiffusion coefficients with the pulse magnetic
field gradient, the increment of the pulse gradient in the interval
from 0 to 32 G cm–1 was increased by 32 steps. The gradient
duration was established to be 4.6 ms; in all cases, the diffusion
time ∆ was 120 ms. Experiments on diffusion were carried out at
least 3 times, and the results were used with the correlation
coefficient ln(I/I0) and γ2δ2g2(∆ – δ/3) > 0.999 (I/I0 is the
relative decrease in the NMR signal as a function of the magꢀ
netic field pulse gradient; γ is the gyromagnetic ratio for protons;
g is the amplitude of pulses of the magnetic field gradient; ∆ is
the interval between the gradient pulses; δ is the duration of the
gradient pulse). All resolved signals were analyzed, and their
average values for the molecule were used. In all cases, the rootꢀ
meanꢀsquare error in the determination of the selfꢀdiffusion
coefficients was at most 5%. The 2D NOESY experiments were
carried out with a mixing time of 400 ms using the gradient
filtration of signals. The pulse programs for all NMR experiꢀ
ments were taken from the Bruker software library.
Scheme 1
changing their local concentrations, properties of the miꢀ
croenvironment, etc.
Experimental
Compound 1 was synthesized using a known procedure.13
Compound 3 was prepared according to a described procedure.22
Commercial La(NO3)3•6H2O (Aldrich), sodium dodecyl sulꢀ
fonate, and PEI of branched structure with a nominal molecular
weight of 50 000 (Sigma) were used. Molar concentrations of
PEI are based on a monomeric unit. Twice distilled water was
used to prepare all solutions.
The hydrolysis kinetics was studied spectrophotometrically
on a Specord Мꢀ400 instrument in the pseudoꢀfirst order condiꢀ
tions by a change in the absorption of the anion of the leaving
group. The apparent rate constants (kapp) were determined from
the equation
Results and Discussion
Investigation of selfꢀorganization. The results of the
tensimetric study of the aggregation of compounds 1 and
2 in aqueous solutions are presented in Fig. 1. Since the
calixarene molecule contains four pentyl substituents at
the lower rim, we can a priori propose the formation of
aggregates of 1 caused by the hydrophobic effect similarly
to aqueous solutions of standard surfactants. As can be
seen from the data in Fig. 1, the surface tension isotherms
of compounds 1 and 2 are identical in shape. The inflecꢀ
tion points in the γ—logC plots correspond to the critical
micelle formation concentrations (CMC), which differ
insignificantly. Analogous results were obtained by
ln(А∞ – А) = –kappt + const,
where A and A∞ are the absorbances of the solution at the time
moment t and at the end of the reaction. The methods of weighed
least squares was used in the calculation, taking into account the
arithmetic mean values of three measurements that differ by at
most 5%. The conductivity was measured with an Ino Lab
conductometer. The surface tension was determined by the ring
detachment method with a DuꢀNouy tensiometer. The experiꢀ
mental details were described.23
Aggregate sizes were determined by the dynamic light scatꢀ
tering (DLS) method on a PhotoCor Complex photonꢀcorrelaꢀ

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Zakharova et al.
Fig. 1. Surface tension (γ) isotherms for the 1—H2O (1),
2—H2O (2), and PEI—2—H2O (3) systems at 25 °C (C is conꢀ
centration).
Fig. 2. Conductivity (χ) of aqueous solutions of compounds 1
and 2 vs their concentration at 25 °C.
measurements of the conductivity of solutions of comꢀ
pounds 1 and 2 (Fig. 2).
it increases to ~80 nm. Such a sharp increase in the size,
probably, reflects a change in the type of formed aggreꢀ
gates. Taking into account the Н NMR data, which are
1
The CMC in a PEI—2 binary system decreases noꢀ
ticeably, indicating the combined aggregation to form
polymerꢀcolloidal complexes. As shown previously by poꢀ
tentiometric titration,11 рН ~10.5 is maintained in a PEI
solution in the absence of a buffer. At this pH value, the
macromolecule contains only an insignificant number of
protonated amino groups (<1%). Thus, aqueous solutions
of PEI are similar in properties to systems based on neuꢀ
tral polymers. According to literature data,24,25 aggregaꢀ
tion in solutions of anionic surfactants and uncharged
polymers results in the formation of structures of the
“necklace” type presented by micellar aggregates peripherꢀ
ally linked to the macromolecules. The sizes of the aggregates
in the PEI—2 system were determined by the DLS method
and are equal to 40 nm, which agrees with the results
obtained for the PEI—sodium dodecyl sulfate system.11
Selfꢀorganization in the PEI—1 binary system was
studied by tensiometry, conductometry, DLS, and NMR
spectroscopy. The measurements of the surface tension
and conductivity revealed no critical concentrations corꢀ
responding to structural rearrangements. This indicates,
most likely, a change in the selfꢀorganization mode in a
binary solution.
discussed below, one can propose the transition from the
formation of aggregates of the structural type I in a dilute
solution of calixarene to structural organization accordꢀ
ing to the type II or III (Scheme 2).
Scheme 2
+ PEI
Individual solutions of calixarene 1 were studied by
the DLS method in the region of dilute solutions (below
CMC that was determined tensiometrically) and at high
concentrations exceeding the CMC. At the concentration
of calixarene 1 equal to 0.004 mol L–1, the average hyꢀ
drodynamic radius (RH) is 34 nm, whereas at C = 0.03 mol L–1
The average hydrodynamic radius of PEI (0.05 М soꢀ
lution) determined the DLS method is 30 nm. Aggregates
of the same size were observed in the PEI—1 binary system

Supramolecular catalytic systems
Russ.Chem.Bull., Int.Ed., Vol. 57, No. 2, February, 2008
377
(0.05 mol L–1 PEI, 0.001 mol L–1 1). However, in the
latter case, polydispersity increased. An analysis of the
particle size distribution by the DynaLS program showed
the presence of aggregates, whose size corresponded to
PEI or was much smaller than that of PEI (RH ≈ 8 nm).
These aggregates can probably be assigned to the aggreꢀ
gated form of compound 1 (see Scheme 2, structure I).
The selfꢀassociation of calixarene 1 in aqueous soluꢀ
tions has earlier26 been studied in detail by various NMR
methods. It was shown that associates with an unusual
“headꢀtoꢀtail” packing of calixarene molecules (see
Scheme 2, structure I) were formed at the concentrations
exceeding 0.001 mol L–1. Binding of the guest molecules
(tetramethylammonium or Nꢀmethylpyridinium), i.e.,
inclusion of the guest into the complex, increases the
aggregation number with the retention of the “headꢀtoꢀ
tail” packing of the calixarene molecules.
(CH2)3 (1)
(CH2) (1)
1
In the Н NMR spectra of the PEI—1 system, the
signal of the polymer is strongly broadened and split into
two peaks, i.e., the slow exchange in the NMR scale is
observed. The signal of free PEI retains its value (δ 2.8),
and the signal of the bound polymer appears at δ 0.5. The
measurements of the spectra of the PEI—1 system under
the temperature variation conditions proved that the upfield
shift was related to the bound polymer (and/or its particular
units). When the temperature increases, the upfield signal
of PEI shifts to the left (Fig. 3), the intensity of the signal
ascribed to the free polymer increases, and the both peaks
are narrowed. These changes indicate an increase in the
rate of the bound PEI—free PEI exchange and a simultaꢀ
neous increase in the fraction of the unbound polymer.
The high upfield shift of the signals from PEI (∆δ = –2.3)
indicates that some polymer regions are included into the
calixarene cavity (see Scheme 2). As shown,27 the formaꢀ
tion of inclusion complexes leads to the upfield shift of
the signals in the NMR spectra of the guest molecules
included into the cavity of the calixarene molecules. Such
great shifts caused by aromatic currents of the benzene
rings of sulfonatocalix[4]resorcinarene could not be obꢀ
tained if the polymer would simply cover a calixarene
molecule. In this case, the aromatic circular currents of
only one aromatic fragment of calixarene would affect a
particular region of the polymer chain, and the maximum
shift value would not exceed 1.5 ppm (see Ref. 28). The
observed upfield shift could appear only under the action
of all aromatic rings of calixarene when a polymer molꢀ
ecule is deeply included into its cavity. This is indicated
by the 2D NOESY spectra containing the crossꢀpeaks of
PEI with both protons of the pentyl substituents and the
СН2SO3 groups of calixarene (Fig. 4). This asserts reliably
that the macromolecule does not cover the pentyl subꢀ
stituents, otherwise the influence of the aromatic fragꢀ
ments of calixarene 1 would be minimum.
δ
Fig. 3. Change in the shape of the 1Н NMR spectra of the PEI—1
system with the temperature increase. The deconvolution peaks
are given below the real spectra.
transform pulsedꢀgradient spintꢀecho (FTꢀPGSE) NMR
technique (Table 1). With an increase in the calixarene
concentration in the PEI—1 binary system, its DS values
first decrease sharply and by the order of magnitude apꢀ
proach DS for the polymer, indicating that calixarene 1 is
completely bound. Then a sharp increase in DS is obꢀ
Additional data can be extracted from measurements
of the selfꢀdiffusion coefficients (DS) using the Fourier

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Zakharova et al.
δ
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
δ
Fig. 4. 2D NOESY spectrum of the PEI—1 system. Crossꢀpeaks between PEI and protons of the СН2SO3 group are designated by the
small circle, and those between PEI and protons of the pentyl substituent in 1 are shown by the large circle; CPEI = 0.05 mol L–1, C1 =
0.001 mol L–1
.
the selfꢀdiffusion coefficients by the integral intensities of
signals is impossible in this case, because the base line of
the spectrum is distorted by strongly broadened lines of
the polymer. Nevertheless, it can be concluded that the
inflection point in the concentration dependence of DS
(in an interval of concentrations of 1 of (1—20)•10–3
mol L–1 at a fixed polymer concentration of 0.05 mol L–1)
corresponds to the stoichiometry of the PEI—1 aggreꢀ
gates. Thus, for equilibrium stoichiometry ~30 units of
PEI or 20 units of the main chain fall on one molecule of
compound 1, if the ratio of the primary, secondary, and
tertiary amino groups, being ∼1 : 2 : 1, is taken into
account.
Based on the results of studying aqueous solutions
of the PEI—1 system by a complex of methods, we
can propose the following scheme of selfꢀorganization.
According to published data,26 the “headꢀtoꢀtail” aggreꢀ
gates (see Scheme 2, structure I) are formed in an indiꢀ
vidual solution of 1 at low concentrations (below the
CMC). At high concentrations (above the CMC), they
form pile structures (II) or layers of the “tailꢀtoꢀtail” type
served up to the value virtually equal to DS for free
calixarene, i.e., free calixarene 1 appears, whose signal is
detected in the spectrum. The effect observed is due to
the fact that the signals of bound calixarene 1 are strongly
broadened and have a low absolute (nonꢀintegral) intenꢀ
sity, whereas the narrower signals of free calixarene give
the main contribution in calculation. The calculation of
Table 1. Selfꢀdiffusion coefficients (DS) in PEI—1 binary aqueous
solutions at the fixed PEI concentration 50 mmol L–1
С1/mmol L–1
DS•10–10/m2 s–1
PEI
1
0.5
1
2
0.68
0.74
1.24
1.22
1.49
1.28
3.39
3.20
5
Note. For an individual solution of PEI DS = 0.44•10–10 m2 s–1, and
for free calixarene 1 DS = 3.26•10–10 m2 s–1 (see Ref. 24).

Supramolecular catalytic systems
Russ.Chem.Bull., Int.Ed., Vol. 57, No. 2, February, 2008
379
(structure III), which is best consistent with the large
sizes of the aggregates obtained by the DLS method. The
addition of PEI results, probably, in the destruction of
intrinsic aggregates of compound 1 and the formation of
mixed structures of the type IV (see Scheme 2). Accordꢀ
The plots of the apparent rate constant for the
hydrolysis of substrate 3 in the PEI—1 binary system
vs concentration of calixarene or polymer at a fixed conꢀ
centration of another component are shown in Figs 6
and 7. The data for the PEI—1 system are presented for
1
ing to the Н NMR data, supramolecular ensembles can
kapp·103/s–1
be formed according to the type of pseudopolyrotaxanes
(see Scheme 2, structure V).29
A more precise scheme of selfꢀorganization can be
constructed after additional studies.
Kinetics of hydrolysis of phosphonate 3. The kinetics
of hydrolysis of phosphorus acid esters in solutions of
polyethyleneimines with different molecular weights has
been studied previously.11,30,31 In the presence of amines,
including polymeric amines, the hydrolysis of esters of
phosphorus acids is catalyzed via the general basic mechaꢀ
nism.19 The pH plots of the hydrolysis of substrate 3 in
individual and binary PEIꢀbased systems are shown in
Fig. 5. An increase in the rate was observed at pH 9.5
in an individual solution of PEI. The concentration of
the unprotonated PEI amino groups involving in catalysis
of the general basic hydrolysis increases in this pH region.
In strongly alkaline solutions, it is probable that the alkaꢀ
line hydrolysis of the substrates would contribute to the
rate constant. As can be seen from the data shown in Fig.
5, the addition of calixarene sharply increases the apparꢀ
ent rate constant and shifts the kinetic dependences to the
region of lower pH values. Thus, the PEI—1 binary sysꢀ
tem manifests a higher catalytic activity under mild conꢀ
ditions.
Fig. 6. Plots of the apparent rate constant for hydrolysis of
phosphonate 3 (kapp) in an individual solution of PEI (1)
and in the PEI—1 binary system (2) vs PEI concentration
(С1 = 0.0001 mol L–1, 25 °C).
kapp/s–1
Fig. 5. Plots of the apparent rate constant for hydrolysis of
phosphonate 3 (kapp) in an individual solution of PEI (1) and
Fig. 7. Plots of the apparent rate constant for hydrolysis of
phosphonate 3 (kapp) in PEI—1 (1) and PEI—2 (2) binary soluꢀ
tions and in the PEI—1—LaIII ternary system (3) vs amphiphile
concentration (CPEI = 0.05 mol L–1, СLaIII = 0.008 mol L–1, 25 °C).
in the PEI—1 binary system (1´) vs pH (С1 = 0.001 mol L–1
СPEI = 0.05 mol L–1, 25 °C).
,

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Russ.Chem.Bull., Int.Ed., Vol. 57, No. 2, February, 2008
Zakharova et al.
comparison. An increase in the polymer or amphiphile
concentration results in a nonlinear increase in the apparꢀ
ent rate constant, and the plots reach a plateau in the
region of high concentrations (see Figs 6 and 7). This type
of kinetic curves is characteristic of reactions preceded by
an equilibrium process, such as the formation of a cataꢀ
lytic complex according to the host—guest principle.
In this case, the apparent rate constant is described by the
equation1
binding constant calculated by the analysis of the kinetic
curves (see Fig. 7) and reflecting the binding of
phosphonate 3 by the calixareneꢀbased structures is
134 L mol–1. This is much higher than the binding conꢀ
stants determined for PEI by the analysis of the kinetic
data in the kapp—CPEI coordinates (see Fig. 6 and Table 2).
The higher KS value for calixarene can be due to a change
in the mechanism of reactant binding: transition from
complex formation according to the type of multicenter
binding with a macromolecule to the solubilization
mechanism, which is indirect evidence for the participaꢀ
tion of the aggregated form of 1 in catalysis. The same is
indicated by similarity of the binding constants for
calixarene and micelles of 2, which are characterized by
reactant solubilization. It is important that in the PEI—1
system the kcat rate constant is significantly higher than
that in the PEI—2 system (see Table 2).
kapp = (k0 + kcatK´SC)/(1 + K´SC),
(1)
where kapp is the apparent pseudoꢀfirst rate constant; k0
and kcat are the pseudoꢀfirst rate constants in solution and
in the catalytic complex, respectively; К´S is the reduced
binding constant of the substrate; C is the concentration
of the polymer or amphiphile in the composition of the
catalytic complex.
An analysis of the kinetic dependences shown in
Figs 6 and 7 using Eq. (1) makes it possible to estimate the
critical concentrations of PEI and 1 corresponding to
the beginning of the catalytic effect, which coincides, as a
rule, with the beginning of aggregation in solution, and to
determine the binding constants of the substrate with
the polymer and aggregated amphiphile (surfactant or
calixarene) in individual or binary systems. As can be seen
from the data in Table 2, the addition of 1 to a solution of
PEI sharply decreases the critical concentration of PEI corꢀ
responding to the catalysis onset (in Table 2 this parameter
is designated as CMC by analogy to micellar solutions).
In addition, the binding constant increases more than by
4 times upon the introduction of compound 1.
The introduction of LaIII into the PEI—1 system inꢀ
creases the rate constant and catalytic effect (Figs 7 and
8). In addition, in a ternary system the pH of the solution
decreases by 2—3 units due to the hydrolysis of the lanꢀ
thanum salt, and catalysis occurs under milder conditions
(pH ~8.5). At the same time, the apparent rate constant
for phosphonate hydrolysis decreases with an increase in
the calixarene concentration in the PEI—1—LaIII system
(see Fig. 7), although an opposite tendency is observed in
the absence of lanthanum ions: the PEI—1 behaves as a
typical supramolecular catalyst. This transition from caꢀ
talysis to inhibition can be caused by various factors. If
catalysis occurs in polymer—calixarene complexes, whose
formation involves the electrostatic and inclusive interacꢀ
tions of the components, then the multicharge LaIII ions
capable of efficiently binding with 1 15 would neutralize
the potential of the upper rim of calixarene weakening its
interaction with PEI. The acceleration values in the biꢀ
nary and ternary systems with respect to hydrolysis in an
individual solution of PEI or with respect to the alkaline
hydrolysis of phosphonate 3 are presented in Fig. 8.
It should be mentioned that the efficiency of the
PEI—1—LaIII ternary system is higher even compared to
the catalytic process effected by PEI, despite the decrease
According to the kinetic data (see Fig. 7 and Table 2),
the CMC values for calixarene 1 are considerably lower
than the CMC determined tensiometrically (see Fig. 1).
Taking into account the absence of a pronounced surface
1
activity in the binary system and the Н NMR data, we
can assume the following. Probably, not only aggregates
of compound 1 formed at the CMC equal to 0.011 mol L–1
(according to the data of tensiometry) can be catalytically
active, but the complexes of PEI and compound 1 in
the monomeric form can also be active in catalysis. The
Table 2. Results of the analysis of the kinetic data using Eq. (1)
System
kapp/k0
CMC/mol L–1
К´S
kcat/s–1
/L mol–1
Kinetics
Tensioꢀ
metry
Conductoꢀ
metry
PEI—H2O (see Fig. 6)
PEI—1—H2O (see Fig. 6)
PEI—1—H2O (see Fig. 7)
PEI—2 (see Fig. 7)
7a
15a
19b
12b
0.024
—
—
0.011
0.0009,
0.0085c
—
—
0.01
0.009c
5
23
134
115
0.0036
0.0043
0.06
0.0029
0.00007
0.0013
0.009
a k0 corresponds to the rate constant of alkaline hydrolysis at pH 10.
b k0 corresponds to the hydrolysis rate constant in an individual solution of PEI.
c The CMC values of individual solutions of compound 2.

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Russ.Chem.Bull., Int.Ed., Vol. 57, No. 2, February, 2008
381
3. L. S. Romsted, Surfactants in Solution, Ed. K. L. Mittal,
Plenum Press, New York—London, 1984, 4, 1015.
4. K. Holmberg, Curr. Opin. Colloid Interface Sci., 2003, 8, 187.
5. T. Dwars, E. Paetzold, G. Oehme, Angew. Chem., Int. Ed.,
2005, 44, 7174.
6. A. L. Maksimov, D. A. Sakharov, T. Yu. Filippova, A. Ya.
Zhuchkova, E. A. Karakhanov, Ind. Eng. Chem. Res., 2005,
44, 8644.
7. E. Engeldinger, D. Armspach, D. Matt, Chem. Rev., 2003,
103, 4147.
8. L. Ya. Zakharova, A. B. Mirgorodskaya, E. P. Zhil´tsova,
L. A. Kudryavtseva, A. I. Konovalov, Izv. Akad. Nauk, Ser.
Khim., 2004, 1331 [Russ. Chem. Bull., Int. Ed., 2004, 53,
1385].
9. L. Y. Zakharova, F. G. Valeeva, A. R. Ibragimova, L. A.
Kudryavtseva, A. I. Konovalov, D. W. Bruce, F. K. Gainullina,
Y. G. Galymetdinov, J. Mol. Liq., 2002, 100, 229.
10. L. Ya. Zakharova, F. G. Valeeva, A. R. Ibragimova, L. A.
Kudryavtseva, Yu. F. Zuev, L. V. Avvakumova, V. I. Kovalenko,
A. I. Konovalov, Izv. Akad. Nauk, Ser. Khim., 2007, 60 [Russ.
Chem. Bull., Int. Ed., 2007, 56, 62].
11. L. Ya. Zakharova, A. R. Ibragimova, F. G. Valeeva, A. V.
Zakharov, A. R. Mustafina, L. A. Kudryavtseva, H. E.
Harlampidi, A. I. Konovalov, Langmuir, 2007, 23, 3214.
12. L. Ya. Zakharova, F. G. Valeeva, A. R. Ibragimova, L. A.
Kudryavtseva, N. M. Selivanova, Yu. G. Galyametdinov,
Tez. dokl. Mezhdunar. konf. po liotropnym zhidkim kristallam
[Abstrs Intern. Conf. on Lyotropic Liquid Crystals] (Ivanovo,
2006), Ivanovo, 38 (in Russian).
Fig. 8. Plots of the catalytic effect (kapp/k0) of the PEI—1 system
in the hydrolysis of phosphonate 3 in the absence (1) and presꢀ
ence (2, 3) of the LaIII ions vs concentration of compound 1
(25 °C); k0 corresponds to the hydrolysis rate constant in an
individual solution of PEI (1, 2); k0 corresponds to the rate
constant of alkaline hydrolysis at pH 8 (3).
13. E. Kh. Kazakova, N. A. Makarova, A. Yu. Ziganshina, L. A.
Muslinkina, A. A. Muslinkin, W. D. Habicher, Tetrahedron
Lett., 2000, 41, 10111.
14. J. E. Morozova, E. Kh. Kazakova, Ed. Ph. Gubanov, N. A.
Makarova, V. P. Archipov, T. V. Timoshina, Z. Sh. Idijatullin,
W. D. Habicher, A. I. Konovalov, J. Inclus. Phenom., 2006,
55, 173.
in the rate constant in a specific interval of calixarene
concentrations (hatched section in Fig. 8). Taking into
account the decrease in the pH of the solution, we can say
that the catalytic effect in the presence of the LaIII ions is
more than 2 orders of magnitude compared to the alkaꢀ
line hydrolysis of substrate 3 (see Fig. 8).
Thus, in the present study, we determined the critical
micelle formation concentrations and aggregate sizes in
the individual and binary systems based on polyethyleneꢀ
imine and amphiphilic sulfonatocalix[4]resorcinarene.
The kinetics of hydrolysis of phosphonate 3 was studied in
the series of the PEI—water, PEI—calixarene—water, and
PEI—calixarene—LaIII—water systems. The ternary cataꢀ
lytic system, which represents lanthanum ions immobiꢀ
lized on the supramolecular platform, provides a complex
mechanism of catalysis (catalytic effect is more than two
orders of magnitude) including the contribution of the
general basic, electrophilic, and supramolecular catalyses.
15. A. R. Mustafina, V. V. Skripacheva, E. Kh. Kazakova, N. A.
Makarova, V. E. Kataev, L. V. Ermolaeva, W. D. Habicher,
J. Inclus. Phenom., 2002, 42, 77.
16. A. R. Mustafina, S. V. Fedorenko, N. A. Makarova, E. Kh.
Kazakova, Z. G. Bazhanova, V. E. Kataev, A. I. Konovalov,
J. Inclus. Phenom., 2001, 40, 73.
17. E. Kh. Kazakova, V. V. Syakaev, Ju. E. Morozova, N. A.
Makarova, A. R. Mustafina, W. D. Habicher, J. Inclus.
Phenom. Macrocycl. Chem., 2002, 43, 65.
18. R. R. Amirov, Z. T. Nugaeva, A. R. Mustafina, S. V.
Fedorenko, V. I. Morozov, E. Kh. Kazakova, W. D. Habicher,
A. I. Konovalov, Colloid Surf. A: Physicochem. Eng. Aspects,
2004, 240, 35.
19. R. F. Bakeeva, L. A. Kudryavtseva, V. E. Bel´skii, B. E.
Ivanov, Zh. Obshch. Khim., 1983, 53, 1058 [J. Gen. Chem.
USSR, 1983, 53 (Engl. Transl.)].
20. J. Chin, J. Acc. Chem. Res., 1991, 21, 145.
21. A. Tsubouchi, Th. Bruice, J. Am. Chem. Soc., 1994, 116,
11614.
22. US Pat. 2922810; Chem. Abstr., 1960, 54, 9848.
23. L. Zakharova, F. Valeeva, A. Zakharov, A. Ibragimova,
L. Kudryavtseva, H. Harlampidi, J. Colloid Interface Sci.,
2003, 263, 597.
24. J. C. Brackman, J. B. F. N. Engberts, Chem. Soc. Rev., 1993,
22, 85.
This work was financially supported by the Russian
Foundation for Basic Research (Project Nos 05ꢀ03ꢀ32558a
and 06ꢀ03ꢀ32189).
References
1. I. V. Berezin, K. Martinek, A. K. Yatsimirskii, Usp. Khim.,
1973, 42, 1729 [Russ. Chem. Rev., 1973, 42, 1343 (Engl.
Transl.)].
2. C. A. Bunton, G. Savelli, Adv. Phys. Chem., 1986, 22, 213.

382
Russ.Chem.Bull., Int.Ed., Vol. 57, No. 2, February, 2008
Zakharova et al.
25. E. D. Goddard, Colloid Interface Sci., 2002, 256, 228.
26. V. V. Syakaev, A. R. Mustafina, Yu. G. Elistratova, Sh. K.
Latypov, A. I. Konovalov, Tez. dokl. XIV Vseros. konf.
“Struktura i dinamika molekulyarnykh sistem” [Absrs XIV Allꢀ
Russia Conf. “Structure and Dynamics of Molecular Systems”]
(Yal´chik, June 27—July 1, 2007), Kazan—IoshkarꢀOla—
Ufa, 2007, 230 (in Russian).
27. Y.ꢀJ. Schneider, A. K. Yatsimirsky, Principles and Methods
in Supramolecular Chemistry, J. Wiley and Sons, New York,
2000.
29. G. Wenz, B.ꢀH. Han, A. Muller, Chem. Rev., 2006, 106, 782.
30. L. Ya. Zakharova, F. G. Valeeva, D. B. Kudryavtsev, A. R.
Ibragimova, L. A. Kudryavtseva, A. P. Timosheva, V. E.
Kataev, Kinet. Katal., 2003, 44, 599 [Kinet. Catal., 2003, 44
(Engl. Transl.)].
31. L. Ya. Zakharova, F. G. Valeeva, D. B. Kudryavtsev, A. V.
Bilalov, A. Ya. Tret´yakova, L. A. Kudryavtseva, A. I.
Konovalov, V. P. Barabanov, Izv. Akad. Nauk, Ser. Khim.,
2005, 630 [Russ. Chem. Bull., Int. Ed., 2005, 54, 641].
28. H. Cunther, NMR Spectroscopy: An Introduction, Wiley, New
York, 1980.
Received May 31, 2007