Supramolecular systems based on alkylated p-sulfonatocalix[n]arenes: Aggregation and catalytic and biological activity

Article abstract of DOI:10.1007/s11172-009-0351-5

Aggregation, catalytic activity, and the influence of alkylated p-sulfonatocalix[n]arenes (SCA; n = 4, 6, 8) on the energy exchange in cells of wheat roots were studied. In water SCA are surfactants, and their efficiency changes with an increase in the nu

Full text of DOI:10.1007/s11172-009-0351-5

Russian Chemical Bulletin, International Edition, Vol. 58, No. 12, pp. 2506—2511, December, 2009
2506
Supramolecular systems based on alkylated pꢀsulfonatocalix[n]arenes:
aggregation and catalytic and biological activity
I. S. Ryzhkina,a Yu. V. Kiseleva,a S. E. Solov´eva,a L. M. Pilishkina,a
Yu. N. Valitova,b 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) 275 2253. Eꢀmail: ryzhkina@iopc.knc.ru
bKazan Institute of Biochemistry and Biophysics,
Kazan Research Center of the Russian Academy of Sciences,
2/31 ul. Lobachevskogo, 420111 Kazan, Russian Federation
Aggregation, catalytic activity, and the influence of alkylated pꢀsulfonatocalix[n]arenes
(SCA; n = 4, 6, 8) on the energy exchange in cells of wheat roots were studied. In water SCA
are surfactants, and their efficiency changes with an increase in the number of aromatic rings
(n) and the length of hydrocarbon substituents (R) in the molecule. In the range of critical
micelle concentration, SCA form micelles with an effective hydrodynamic diameter of ~200 nm.
The catalytic activity of micellar solutions of SCA (n = 4, 8; R = C12H25) in hydrolysis of ethyl
4ꢀnitrophenyl chloromethylphosphonate (ENCP) decreases with an increase in n, whereas the
binding constant of ENCP increases. The modifying effect of SCA on the membranes and the
energy exchange in cells of wheat roots was revealed: the membranotropic activity of SCA
increases with an increase in the hydrophobicity of substituents R and the macrocycle size.
Key words: alkylated pꢀsulfonatocalix[n]arenes, surfactants, micelle formation, nanoparticles,
catalytic activity, cells of wheat roots, energy exchange, ethyl 4ꢀnitrophenyl chloromethylꢀ
phosphonate, hydrolysis.
great extent, on hydrophobicity of these compounds and
their aggregation state.19—22 Many micelleꢀforming surꢀ
factants possess antimicrobial activity and can enhance
the effect of sulfamide drugs and solubilize hydrophobic
drugs by transforming them into the soluble form.19,23 It is
known that the energy processes in cells are tightly related
to the phosphorylationꢀdephosphorylation reactions of
membrane proteins.24 The study of biological aspects of
application of nonmodified pꢀsulfonatocalix[n]arenes
showed that unsubstituted SCA (n = 4, R = Н) manifest
supramolecular catalytic activity in hydrolysis of ATP,17
which can change substantially in the case of alkylated
SCA. Therefore, the complex study of the aggregation
properties of alkylated SCA, their catalytic activity in the
model reaction of hydrolysis of phosphorus acid esters,
and the influence on biosystems is an urgent problem,
whose solution will help to establish the relationship
“chemical structure—aggregation behavior—biological
activity” and to extend the range of using the SCA derivaꢀ
tives in new technologies.
Considerable attention is recently given to the study
of methods for synthesis, properties, and the scope of
application of pꢀsulfonatocalix[n]arenes (SCA) and their
derivatives.1—16 One of the most promising and interestꢀ
ing directions of using SCA is the medical biological area,17
which is caused by high solubility of SCA in water, low
toxicity,17 and accessibility of functionalization, which
makes it possible to control physicochemical properties of
these compounds by changing the nature of substituents
and the number of aromatic rings. For instance, the inꢀ
troduction of alkyl radicals into the SCA molecule favors
the change in its hydrophilicꢀlipophilic balance and the
appearance of surfactant properties.1,4 A consequence of
an increase in the number of aromatic rings is the conforꢀ
mational mobility of the macrocycle,5,6,9—11,17 resulting in
the appearance of the adaptive ability to substrate binding
(flexible “tuning”).18 Although many publications are deꢀ
voted to pꢀsulfonatocalix[n]arenes, the aggregation beꢀ
havior of SCA modified by alkyl radicals was not systemꢀ
atically studied.
The purpose of this work is the study of the aggregaꢀ
tion behavior of pꢀsulfonatocalix[n]arenes containing
The mechanism of interaction of biologically active
compounds with the cell membrane surface depends, to a
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2424—2429, December, 2009.
1066ꢀ5285/09/5812ꢀ2506 © 2009 Springer Science+Business Media, Inc.

Alkylated pꢀsulfonatocalix[n]arenes
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 12, December, 2009 2507
phonate (ENCP), was studied by spectrophotometry under the
conditions of the pseudoꢀfirstꢀorder reaction that occurs with
4ꢀnitrophenolate formation (λ = 400 nm) on a Perkin—Elmer
Lambda 35 spectrometer at 25 °С, pH 9.2. The observed rate
constants (kobs) were determined by the firstꢀorder equation.
The binding constants of the substrates (Kb) by micelles, the
critical micelle concentrations (CMC), and the rate constants
of the reaction in the micellar pseudoꢀphase (km) were deterꢀ
different numbers of alkylated phenol rings (n = 4, 6, 8;
R = Bun, C8H17, C12H25), the catalytic activity of the SCA
in the model reaction of hydrolysis of ethyl 4ꢀnitrophenyl
chloromethylphosphonate, and their modifying effect on
the membranes and the energy exchange in wheat roots.
mined by the data of the concentration dependences of kobs
.
For this purpose, the equation for the calculation of the kinetic
curves reaching a plateau, which takes into account the subꢀ
strate distribution between the volume and micellar phase, was
used25—28
kH = (kH O + kmKbC)/(1 + KbC),
(1)
2
where kH O/s–1 is the reaction rate constant in the aqueous
phase, an2d C/mol L–1 is the SCA concentration corrected to
the CMC. The object of studies in biological experiments
was the spring wheat “Lyuba” (Triticum aestivum L.), whose
acrospires were grown on distilled water for 4 days.22 Immediꢀ
ately after cutting off, roots of the wheat acrospires were placed
into the working solutions and incubated in the Warburg appaꢀ
ratus.22 The formation and consumption of K+ ions by the root
cells were determined by the change in the potassium content in
the incubation medium. Measurements were carried out on a
PFM flame photometer. Preliminarily the roots were incubated
in the Warburg vessels, which made it possible to detect simultaꢀ
neously the oxygen consumption by the cells.
n = 4: R = Bun (1), C8H17 (2), C12H25 (3), H (6);
n = 6: R = C12H25 (4), H (7); n = 8: R = C12H25 (5), H (8)
Experimental
The SCA under study were synthesized according to proceꢀ
dures described previously.4,7,11,15 The IR and 1H NMR spectra
of compounds 1—8 correspond to the published ones. The surface
activity of the SCA was studied recording the surface tension (σ)
isotherms in water—air systems by the du Nouy ring detachment
method (Sigma 702ET highꢀprecision tensimeter), and the
relative measurement error by results of three independent
experiments did not exceed 1%. The association of the SCA in
water was studied by the conductometric method, determining
the electroconductivity (χ) of solutions at 25 °С (inoLab Cond
Level 1 conductometer, relative measurement error 0.5%). The
temperature was maintained constant by a thermal sensor with
an accuracy of 0.1 °С, and the pH values of solutions was
measured with an Iꢀ160 ionometer. The particle size (effective
hydrodynamic diameter, D) was determined by the light scatꢀ
tering method on a FotoCor Complex photon correlation
spectrometer of dynamic and static light scattering. An He—Ne
gas laser with a power of 10 mW and a wavelength of 633 nm
served as a radiation source. Signals were analyzed with a oneꢀ
plate multichannel correlator, and the data were processed using
programs from the set of the instrument. The function obtained
was processed using the Alango Dynals v2.0 universal program
for processing of dynamic light scattering data. The relative
measurement error of effective hydrodynamic diameters of
associates did not exceed 10%. The electrokinetic potential
(ζꢀpotential) of particles in SCA solutions was measured on a
Malvern Instruments Zetasizer Nano ZS highꢀsensitive analyzer.
The procedure of sample preparation for studies of sizes of the
associates and ζꢀpotential (the use of disposable pipettes, cells
with caps or immersible electrodes from the set of the instrument,
and disposable filters 0.45 μm, Millex HN) provided the
necessary “dustꢀremoval” of solutions. Nanoassociate sizes in
solutions were measured after the control study of freshly
bidistilled water, which was used for the preparation of solutions
only if the analyzer detected the full absence of any particles.
The measurements were carried out under the conditions of
temperature maintenance at 25 °С. The kinetics of hydrolysis
of the substrate, viz., ethyl 4ꢀnitrophenyl chloromethylphosꢀ
Results and Discussion
The surface tension isotherms of the alkylated derivaꢀ
tives of pꢀsulfonatocalix[4]arene with the substituents
R = Bun (1), C8H17 (2), and C12H25 (3) are shown in Fig. 1.
The surface tension isotherm of the micelleꢀforming
surfactant sodium dodecyl sulfate (SDS) is presented for
comparison. In the case of compound 3, micelle formaꢀ
tion is stepwise, which can be due to the formation and
rearrangement of micelles (Table 1, see Fig. 1). The
inflection points in the plot σ = log С correspond to these
processes. The critical micelle concentration of comꢀ
pounds 1—3 is approximately an order of magnitude lower
than the CMC of SDS,23 which is equal to 8•10–3 mol L–1
.
Probably, this is due to the preꢀorganized character of
four polar head groups and nonpolar hydrocarbon radiꢀ
cals in the same SCA molecule, which facilitates micelle
formation similarly to the processes of dimeric surfacꢀ
tants.23 The data in Table 1 show that the CMC of comꢀ
pounds 1—3 change slightly with the elongation of the
hydrocarbon radical, whereas for surfactants of the SDS
type the CMC decreases strongly, as a rule, with the elonꢀ
gation of the alkyl chain of the substituent.23 The surface
tension σ in the CMC point of solutions of SDS 1—3 is
considerably higher than that in the case of SDS. The
concentration dependence of the electroconductivity of
solutions of SCA 3 typical of these compounds is shown
in Fig. 2. The concentration, at which the inflection in

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Russ.Chem.Bull., Int.Ed., Vol. 58, No. 12, December, 2009
Ryzhkina et al.
the χ = f(C) plot is observed, is close to the CMC obꢀ
tained by the tensimetric method (see Fig. 2, Table 1).
To understand principles of selfꢀorganization of miꢀ
celles of alkylated SCA, one needs information about the
influence of the concentration on the nanoparticle size.
The surface tension isotherms and the concentration
dependence of the particle size of SCA 3 are shown in
Fig. 3. A tendency of the nanoparticle to enlarge with an
increase in the SCA concentration and reaching a plateau
after the CMC confirm micelle formation in the solution.
As can be seen from the data in Table 1, micelles of SCA 1
(R = Bun) are larger than micelles of 3 (R = C12H25).
Probably, an efficient micelle formation of SCA requires
the length of the hydrocarbon substituent in the molecule
to be short (R = Bun). The introduction of a longer radiꢀ
cal into the SCA molecule worsens the surfactant properꢀ
ties of the compound and decreases the sizes of the
nanoparticles formed (see Table 1). According to modern
data,23 a sharp increase in the micelle size at low surfacꢀ
tant concentrations is characteristic of rodꢀlike (vermiꢀ
form) micelles with the circular transversal crossꢀsection.
The linear length of rodꢀlike micelles can vary in wide
range: from 10 nm to many hundreds of nanometers.23
According to the conductometric data (see Fig. 2,
Table 1), SCA are electrolytes and, hence, it was interestꢀ
ing to study the electrokinetic characteristics of dispersed
SCA particles. The concentration dependences of the elecꢀ
trokinetic potential (ζꢀpotential) of nanoparticles in soluꢀ
tions of SCA 3 are shown in inset in Fig. 2. The depenꢀ
dences show that the both parameters, viz., χ and ζꢀpoꢀ
tential, increase simultaneously with an increase in the
SCA concentration. The inflection in the dependence
χ = f(С) in the CMC point is accompanied by reaching a
plateau by the ζꢀpotential. The shape of the concentraꢀ
tion dependences of the ζꢀpotential of the nanoparticles
and the electroconductivity of solutions (see Fig. 2) and
of the nanoparticle size and surface tension of solutions
(see Fig. 3) indicate that such properties of SCA soluꢀ
tions as the electroconductivity and surface tension corꢀ
relate with the size of micelles and their surface charge.
σ/mN m–1
75
3
65
55
45
35
2
1
4
–6
–5
–4
–3
–2 log C
Fig. 1. Surface tension (σ) isotherms of aqueous solutions of
SCA 1 (1), 2 (2), and 3 (3) and SDS (4) at 25 °С.
Table 1. Critical micelle concentrations (CMC)
of alkylated pꢀsulfonatocalix[n]arenes 1—5 and
the effective hydrodynamic diameter (D) of miꢀ
celles 1—5 at the concentrations higher than
the CMC, 25 °С
Comꢀ
pound
CMC•104/mol L–1
D/nm
tensiꢀ
conductoꢀ
metry
metry
1
2
3
4
5
8.0
9.0
6.0
6.0
8.0
8.0
10.0
4.0
4.0
5.0
200
200
120
250
200
σ/mN m–1
D/nm
120
χ/μS cm–1
ξ/mV
70
100
1
400
0
80
60
40
20
1
66
62
58
54
300
200
100
0
–20
–40
–60
–80
2
2
C•10–4/mol L–1
0
2
4
6
C•10–4/mol L–1
2
4
6
Fig. 2. Electroconductivity (χ) of an aqueous solution of SCA
3 (1) and the ζꢀpotential of nanoparticles of SCA 3 (2) vs conꢀ
centration (C) at 25 °С.
Fig. 3. Surface tension (σ) isotherm of an aqueous solution of
SCA 3 (1) and the change in the effective hydrodynamic diameter
(D) of nanoparticles of SCA 3 (2) vs concentration (C) at 25 °С.

Alkylated pꢀsulfonatocalix[n]arenes
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 12, December, 2009 2509
It is reasonable to assume that the formation of miꢀ
celles of SCA 3 characterized by the negative value of the
ζꢀpotential (see Fig. 2) is associated with the dissociation
of protons of sulfonate groups, which should decrease the
pH of the solution. However, solutions of SCA 3 in the
studied concentration range have neutral pH values рН
(7.0—7.5), which indirectly indicates that the sulfonate
groups are either nonionized, or weakly ionized. In this
case, the negative ζꢀpotentials of the nanoparticles, posꢀ
sibly, imply that the external electric field applied on the
solution during electrophoretic experiment favors the proꢀ
ton dissociation of the sulfonate groups and the formation
of negatively charged particles, which are uncharged or
weakly ionized under normal conditions.
To study the influence of the macrocycle on the selfꢀ
association of alkylated SCA, we chose compounds 3—5,
whose molecules contain different numbers of aromatic
rings: n = 4 (3), 6 (4), and 8 (5) at the same length of the
hydrocarbon substituent (R = С12Н25). The surface tenꢀ
sion isotherms of these compounds are shown in Fig. 4.
They show that with an increase in the macrocycle size
the surface activity of the SCA decreases, whereas the
CMC value remains almost unchanged (see Table 1). In
all cases, the micelle formation process is stepwise, which
is related to the rearrangement of nanoparticles, as can be
judged from the dynamic light scattering data (see Fig. 3).
The ζꢀpotential values of nanoparticles of SCA 3 and 4
at the concentration 2•10–4 mol L–1 are rather high (apꢀ
proximately –70 mV) but lower than those of nanoparticles
of SCA 5 (–80 mV) at the same concentration. Solutions
of SCA 5 in the concentration ranges below and above the
CMC are nearly neutral (pH 6), i.e., the micelle formaꢀ
tion of SCA 5 does not acidify the medium as in the case
of SCA 3. This indirectly indicates that the sulfonate
groups of micelles of SCA 5 are weakly ionized under
normal conditions, whereas the negative values of the
ζꢀpotential are related, as for SCA 3, to the behavior of
the particles during electrophoresis. Unlike compounds 3
and 5, the micelle formation of SCA 4 is accompanied by
the strong acidification of the medium (pH 2.5) similarly
to the micelle formation of some organic acids in a surꢀ
factant medium.29 Unlike anionic micelles of 4, micelles
of SCA 3 and 5 have no surface charge or ionized weakly,
which was confirmed by us when studying the reactivity
of the supramolecular systems based on these compounds.
The study of the hydrolysis of ethyl 4ꢀnitrophenyl
chloromethylphosphonate in the supramolecular systems
based on SCA 3—5 showed that the observed reaction
rate constants (kobs) depend on the concentration of comꢀ
pounds 3 and 5: they increase with an increase in the
concentrations and reach a plateau, which is typical of
the micelleꢀcatalyzed reactions25 (Fig. 5, inset). The
reaction parameters calculated by Eq. (1) are listed in
Table 2. The reaction rate constants in the micellar phase
of SCA 3 and 5 slightly exceed those for an aqueous
medium (kН О). The catalytic activity of the supraꢀ
2
molecular systems of SCA 3 and 5 is comparable with
that of the systems based on neutral surfactants, such as
TritonꢀXꢀ100 (see Ref. 27) or amphiphilic calix[4]ꢀ
resorcinarenes with nonionogenic moieties.26 The high
constants of binding of the ENCP substrate by the SCA
micelles confirm the earlier established regularity of effiꢀ
cient binding of the substrates by calixarene micelles.26—28
The catalytic activity of micelles of 3 and 5 (n = 4, 8;
R = C12H25) in the hydrolysis of ENCP decreases by an
order of magnitude with an increase in n, whereas the
binding constant of the substrate increases approaching
the Кb value of enzymatic reactions for SCA 5.30 The
kinetic curve of the concentration dependence of SCA 4
differs noticeably from the corresponding curves for other
calixarenes (Fig. 5): the kobs values decrease beginning
k
•103/s–1
obs
σ/mN m–1
1
5.0
4.0
3.0
2.0
1.0
7.5
k
•104/s–1
obs
7.0
10
8
6.5
3
6
C•10–4/mol L–1
C•10–4/mol L–1
2
6.0
0
2
4
2
3
6
9
12
15
5.5
1
Fig. 5. Observed rate constant (kobs) of hydrolysis of ENCP vs
concentration (C) of aqueous solutions of SCA 3 (1) and 4 (2)
(рН 9.2, 25 °С). Inset: the dependence of kobs of hydrolysis
of ENCP on the concentration of aqueous solutions of SCA 5
(рН 9.2, 25 °С).
–5.0
–4.5
–4.0
–3.5
log С
Fig. 4. Surface tension (σ) isotherms of aqueous solutions of
SCA 3 (1), 4 (2), and 5 (3) at 25 °С.

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Russ.Chem.Bull., Int.Ed., Vol. 58, No. 12, December, 2009
Ryzhkina et al.
Table 2. Kinetic parameters of hydrolysis of ethyl 4ꢀnitrophenyl
chloromethylphosphonate in supramolecular systems based on
SCA 3—5
Oxygen consumption/μL g h–1
600
a
500
400
300
200
100
2
1
Comꢀ
pound
Kb
km
CMC
km/kН О
2
/L mol–1
/s–1
/mol L–1
3
4
5
1100
12000
11000
9.2•10–3
3.4•10–4
1.0•10–3
3.0•10–4
3.0•10–4
5.9•10–6
230
8
25
from the concentration 3•10–4 mol L–1 close to the CMC
of this compound (see Table 1). This behavior of the
micellar system in hydrolysis of 4ꢀnitrophenyl esters of
phosphorus acids are usually related to the inhibition
effect of anionic micelles of the surfactant,25 which mainly
occurs due to the electrostatic repulsion of the nucleoꢀ
philes (hydroxyl ions) from the negatively charged surface
of the micelles that solubilize the substrate. Thus, the
assumption that SCA 4, unlike compounds 3 and 5, forming,
most probably, weakly ionized micelles, form micelles
of the anionic type is confirmed by the kinetic data.
We have earlier found that the amphiphilic derivatives
of calix[4]resorcinarenes are membranotropic compounds
capable of exerting different effects on the energy
exchange in plant cells depending on the structure of the
head groups and the size of nanoparticles formed by these
groups.22 In the present work, we revealed the most sigꢀ
nificant structural differences in the series of SCA (macroꢀ
cycle size, n; the presence of hydrophobic substituents,
R) affecting the characteristics of the nanoparticles, probꢀ
ably, respective for the modifying action of SCA solutions
on the energy exchange in plant cells. The study of the
physiological action on the plant cells of solutions of
unmodified 6—8 and alkylated SCA 1—5 showed that
calixarenes can exert different effects on the energy
exchange of plant cells in the presence of the same head
sulfonate groups: they can stimulate, suppress, or exert no
effect. For instance, tetrameric (n = 4) SCA 1—3 and 6
in a concentration of 5•10–5 mol L–1 exerted almost no
effect on the energy exchange in wheat roots. Based on
the results obtained, we may assume that this behavior
of the tetrameric SCA is related to an insufficient hydroꢀ
phobicity and low surface charges of the nanoparticles:
this affects the ζꢀpotential values (changing from –20 to
–40 mV).
1
2
3
4
5
600
560
520
480
440
400
360
320
b
1
2
3
1
2
3
4
Time/h
Fig. 6. Change in the rate of oxygen consumption by cut wheat
roots under the action of SCA solutions: a, reference sample (1)
and SCA 4 (2); b, reference sample (1), SCA 8 (2), and SCA 5 (3).
cities and, hence, the ability to penetrate into the cell
membrane,31 as well as different surface charges of
nanoparticles, which reflects the ζꢀpotential value, which
is much lower for nanoparticles of SCA 7 (–30 mV) comꢀ
pared to that of nanoparticles of SCA 4 (–70 mV).
The further increase in the macrocycle size results in
the situation when octameric SCA 5 (n = 8, R = C12H25)
and 8 (n = 8, R = H) suppress the energy exchange in
cells (Fig. 6, b). Since micelles of 5 possess a high binding
ability toward phosphorus acid esters (see Table 2) comꢀ
pared to the enzymatic ability,30 it can be assumed that
SCA 5 form complexes with components of membranes
or membrane proteins, inhibiting enzymes and violating
metabolism of the cell. The fact that nonalkylated SCA 8
less efficiently affects plant cells than alkylated SCA 5
(see Fig. 6, b) is probably due to the lower ability of
compound 8 to bind with plasmalemma because of the
lower hydrophobicity.
Thus, the study of the modifying effect of a series of
SCA on the membranes and energy exchange in wheat
root cells showed that the biological activity of the SCA
increases with an increase in the macrocycle size and
hydrophobicity of the substituents. This results in subꢀ
stantial differences in the electrokinetic characteristics of
nanoparticles of SCA of different structure and their bindꢀ
ing ability and reactivity toward phosphorus acid esters,
which provides fine control of bioeffects of the supraꢀ
More hydrophobic conformationally mobile SCA 7
and 4 (n = 6; R = OH, C12H25, respectively) in a concenꢀ
tration of 5•10–5 mol L–1 exert a noticeable but opposite
effect on the oxygen consumption by the roots, the pH of
the incubation medium, and the escape of potassium ions
from the cells: SCA 7 suppresses the energy exchange of
cutꢀoff wheat roots, and SCA 4 stimulates it (Fig. 6, a).
The reason for different directions of the bioeffects of
compounds 4 and 7 can be both their different lipophiliꢀ

Alkylated pꢀsulfonatocalix[n]arenes
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 12, December, 2009 2511
19. B. V. Passet, Osnovnye protsessy khimicheskogo sinteza
biologicheski aktivnykh veshchestv [The Main Processes
of Chemical Synthesis of Biologically Active Substances],
GEOTARꢀMED, Moscow, 2002, 376 (in Russian).
20. J. J. Lundquist, E. J. Toone, Chem. Rev., 2002, 102, 555.
21. Kh. Kasumov, J. Bolard, Pol. J. Chem., 2004, 78, 1057.
22. I. S. Ryzhkina, W. D. Habicher, Yu. V. Kiseleva, A. P.
Timosheva, A. I. Konovalov, Yu. N. Valitova, G. N.
Mardanova, A. N. Tsentsevitskii, L. Kh. Gordon, Dokl. Akad.
Nauk, 2007, 413, 557 [Dokl. Biochem. Biophys., 2007, 413,
68].
molecular systems based on these compounds. The results
obtained create prerequisites for the further combined
study of selfꢀorganization in mixed supramolecular sysꢀ
tems “amphiphilic calixarene—biologically important
compound” and bioeffects in these systems.
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 06ꢀ03ꢀ32402a).
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Received July 17, 2008;
in revised form August 21, 2009