Catalytic properties of supramolecular systems based on polyoxyethylated calixarenes and amines

Article abstract of DOI:10.1134/S0023158411040082

The rate of carboxylic ester cleavage by amphiphilic low-molecular-weight and polymeric amines in the presence of polyoxyethylated calix[4]arenes with different degrees of oxyethylation is determined by the formation of mixed aggregates, by the shift of pK _a of the amine, and the character of the distribution of the reactants in functional micelles. All of the systems show a high substrate specificity. In the case of octyl- and decylamines, the reaction of p-nitrophenyl acetate is catalyzed and the reaction of more hydrophobic p-nitrophenyl laurate is inhibited. An opposite situation is observed in the systems based on branched polyethyleneimine: the reaction of p-nitrophenyl acetate is inhibited and the process involving p-nitrophenyl laurate is accelerated.

Full text of DOI:10.1134/S0023158411040082

ISSN 0023ꢀ1584, Kinetics and Catalysis, 2011, Vol. 52, No. 4, pp. 529–535. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © A.B. Mirgorodskaya, E.I. Yatskevich, Yu.R. Kudryashova, S.E. Solov’eva, I.S. Antipin, L.Ya. Zakharova, A.I. Konovalov, 2011, published in Kinetika i
Kataliz, 2011, Vol. 52, No. 4, pp. 540–546.
Catalytic Properties of Supramolecular Systems Based
on Polyoxyethylated Calixarenes and Amines
A. B. Mirgorodskaya*, E. I. Yatskevich, Yu. R. Kudryashova, S. E. Solov’eva,
I. S. Antipin, L. Ya. Zakharova, and A. I. Konovalov
Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center,
Russian Academy of Sciences, Kazan, 420083 Tatarstan, Russia
*
eꢀmail: mirgorod@iopc.ru
Received December 1, 2010
Abstract—The rate of carboxylic ester cleavage by amphiphilic lowꢀmolecularꢀweight and polymeric amines
in the presence of polyoxyethylated calix[4]arenes with different degrees of oxyethylation is determined by
the formation of mixed aggregates, by the shift of pKa of the amine, and the character of the distribution of
the reactants in functional micelles. All of the systems show a high substrate specificity. In the case of octylꢀ
and decylamines, the reaction of
phenyl laurate is inhibited. An opposite situation is observed in the systems based on branched polyethyleneꢀ
imine: the reaction of ꢀnitrophenyl acetate is inhibited and the process involving ꢀnitrophenyl laurate is
accelerated.
pꢀnitrophenyl acetate is catalyzed and the reaction of more hydrophobic pꢀnitroꢀ
p
p
DOI: 10.1134/S0023158411040082
Amphiphilic and polymeric molecules are classiꢀ which combine functions of a nonionic surfactant and
fied as building blocks whose prototypes are lipids and a cyclophane platform. This is reflected in their aggreꢀ
proteins, which are structureꢀforming components of gation behavior and solubilizing properties [10–12].
biological membranes [1–3]. As their natural anaꢀ Unlike typical surfactants, calixarenes are capable of
logues, synthetic amphiphiles and polymers show a forming aggregates due to the hydrophobic effect and
pronounced tendency to selfꢀorganization in soluꢀ also due to inclusive interactions involving their cavity
tions. The resulting nanosized supramolecular aggreꢀ [13–16]. Passing to multicomponent compositions
gates can solubilize organic compounds and control containing calixarenes and other amphiphilic comꢀ
their solubility, acidꢀbase properties, reactivity, and pounds and calixarene immobilization on the polymer
other properties by creating a specific microenvironꢀ matrix can initiate other mechanisms of selfꢀorganizaꢀ
ment [4–9]. Therefore, search for new amphiphilic tion and impart new functional properties to the system.
substances and studies of their selfꢀorganization in the
solution bulk and at interfaces are of considerable amphiphilic or polymeric amines and CO with different
interest.
degrees of oxyethylation having alkyl (tertꢀbutyl, iso
Here, we report supramolecular systems based on
ꢀ
Calix[4]arenes oxyethylated at their lower rim nonyl) substituents on the upper rim. The structural forꢀ
COs) are new types of amphiphilic compounds, mulas and designations of the COs are given below.
(
R
R =
i
ꢀC H ,
n
= 9 (9CO9),
n = 8 (9CO8);
4
9
19
O
R =
t
ꢀC H , = 16 (4CO16)
n
9
4
(
C H O)
2
4
n − 1
CH2
CH2
OH
529

530
MIRGORODSKAYA et al.
obtained in this study were compared with the behavꢀ
ior of supramolecular systems based on oxyethylated
phenol Triton Xꢀ100 (polyethylene glycol ꢀ(1,1,3,3ꢀ
tetramethylbutyl)ꢀphenyl ether) in order to elucidate
the role of the calixarene matrix.
σ
, mN/m
70
65
60
55
50
45
40
35
30
p
1
EXPERIMENTAL
COs were synthesized as described in [17]. Comꢀ
mercial longꢀchain amines (Acros Organics), esters
2
(pꢀnitrophenyl acetate and
pꢀnitrophenyl laurate)
(
Fluka), Triton Xꢀ100, and branched PEI25 (molecuꢀ
3
lar weight of 25000 g/mol) (Aldrich) were used.
Hydrophobized PEI (PEI ꢀ12) was synthesized by
25
reacting PEI with dodecyl bromide in ethanol [18, 19].
25
The average molecular weight of the monomeric unit
of PEI ꢀ12 was determined by potentiometric titraꢀ
25
tion to be 107
alkylation of ~0.2. The
fraction of nonprotonated amino groups (
±
3
, which corresponds to a degree of
Ка values of amines and the
) were
р
α
determined by the potentiometric titration of their
solutions with 0.1 M hydrochloric acid using a pHꢀ340
pH meter. The amphiphile concentration was varied
between 0 and 0.02 mol/l. Molar concentrations
(
mol/l) of PEI in terms of monomeric units were used.
The surfactant properties were studied by the ring
method on a Du Nouy tensiometer (Kruss). The electric
conductivity of solutions prepared in bidistilled water
1
×
10–6
1
×
10–5
1
×
10–4
Camph, mol/l
1
×
10–3
1
10–2
×
with an electric conductivity of at most 1.8 S/cm was
measured using a CDMꢀ2d instrument (Radiometer
Copenhagen).
μ
Fig. 1. Surface tension isotherms for the 9CO8ꢀbased sysꢀ
tems: ( ) (open circles) individual solution, (open trianꢀ
gles) solution containing an equimolar amount of PEI ,
1
25
and (open squares) solution containing an equimolar
amount of PEI ꢀ12; ( ) solution containing an equimolar
amount of decylamine; ( ) fixed PEI ꢀ12 concentration
0.005 mol/l).
The reaction kinetics was studied by spectrophoꢀ
tometry on a Specord UVꢀVis instrument at 25°С in
freshly prepared solutions under pseudoꢀfirstꢀorder
reaction conditions. A constant pH was maintained by
using buffer solutions of sodium tetraborate (pH 9.2 or
2
25
3
25
(
Lowꢀmolecularꢀweight amines (octylꢀ and decyꢀ 10.0). The process was monitored spectrophotometriꢀ
lamines), branched polyethyleneimine with a molecuꢀ cally as the change in the absorbance of the solution at
lar weight of 25000 (PEI ), and its derivatives modiꢀ 400 nm (formation of the
ꢀnitrophenolate anion). The
p
25
–5
fied with longꢀchain (dodecyl) radicals (PEI ꢀ12) initial concentration of the substrate was
5
×
10 mol/l,
and the conversion was higher than 90%. Apparent
The catalytic effect of supramolecular systems is rate constants ( app) were determined from the relaꢀ
associated with the transfer of chemical reactions from tionship log( ) = –0.434 + const, where
the solution bulk to nanosized aggregates and is deterꢀ and are the absorbances of the solution at the
mined by the effect of concentrating and by changes in moment and after the completion of the reaction.
the microenvironment of interacting particles. For The values of
25
were studied.
k
–
A
A
k
app
τ
A
∞
τ
τ
A
∞
τ
k
app were calculated using the leastꢀ
this reason, one of the tasks of this work is to study selfꢀ squares method.
organization in calixarene–amine systems. In addiꢀ
tion, a shift of the рКа of ionogenic compounds can be
observed in microheterogeneous systems. In this conꢀ
nection, we studied the influence of calixarenes on the
RESULTS AND DISCUSSION
The properties of the mixed compositions are
basicity of amines. The data that we obtained served as determined, to a considerable extent, by the properties
the basis for evaluation of the catalytic effect of the of their components. The aggregation behavior of
systems. Oxyethylated calixarene are structurally simꢀ individual solutions of oxyethylated calixarenes was
ilar to nonionic surfactants. For this reason, the results studied earlier [10, 11]. The values of the critical
KINETICS AND CATALYSIS Vol. 52
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2011

CATALYTIC PROPERTIES OF SUPRAMOLECULAR SYSTEMS BASED
531
micelle concentration (CMC) for aqueous solutions
of COs with different structures are similar, being
χ×10 , Ohm cm–1
6
–1
σ
,
mN/m
6
0
0
0.0038, 0.0021, and 0.0022 mol/l for 9CO8, 9CO9,
and 4CO16, respectively. The surface tension isotherm
for 9CO8 is presented as an example in Fig. 1. Note
that the CMC of the structurally similar nonionic surꢀ
factant Triton Xꢀ100 is 0.0002 mol/l [20], one order of
magnitude lower than that of the COs. This distinction
may arise from different mechanisms of selfꢀorganizaꢀ
tion. Both hydrophobic and inclusive interactions and
5
7
0
5
40
30
6
20
10
π
–
π
stacking effects can contribute to the process, and
60
55
50
45
the presence of a large cavity can lead to a specific
packing of calixarene molecules. It was shown [11]
that COs can form micelleꢀlike aggregates and also
lamellar or pile structures.
0
0.01
0.02
0.03
CPEI, mol/l
Lowꢀmolecularꢀweight amines containing hydroꢀ
phobic radicals are prone to micelle formation in
water: octylamine in neutral form is characterized by a
CMC value of 0.008 mol/l, while the CMC of decyꢀ
lamine is 0.00095 mol/l [21]. In the case of
polyamines, the tensiometric data indicate that
unsubstituted PEI25 is surfaceꢀinactive, whereas
hydrophobized PEI25ꢀ12 exhibit properties of a typical
surfactant (Fig. 2). The concentration of PEI25ꢀ12
corresponding to the inflection in the surface tension
10–4
10–3
CPEI, mol/l
10–2
1
×
1
×
1
×
isotherm (critical aggregation concentration CAC =
Fig. 2. Surface tension isotherm for an aqueous solution of
PEI ꢀ12; 25 C. Inset: concentration dependence of the
electric conductivity of aqueous solutions of PEI ꢀ12;
1
°
0.0012 mol/l) indicates the commencement of aggreꢀ
25
25
gation in the system. The inflection in the conductivity
versus concentration curve is observed in the same
25°C.
region, and another one (CAC ) occurs at a higher
2
concentration of ~0.01 mol/l (Fig. 2, inset). It is likely arenes (Fig. 1). In the systems based on PEI25ꢀ12 and
that, at low polymer concentrations, aggregation 9CO8, the CMC determined from the surface tension
occurs due to interactions inside one polymer moleꢀ isotherm both at a constant molar ratio of components
cule. An increase in the polymer concentration (1 : 1) and at a fixed PEI concentration (0.05 mol/l) also
increases the probability of intermolecular interacꢀ insignificantly differs from the CMC of the individual
tions, including hydrogen bond formation, which calixarene. These results are in agreement with the
results in the formation of aggregates containing sevꢀ known facts that the addition of a polymer to solutions
eral macromolecules.
of nonionic surfactants does not usually decrease the
In binary systems, nonmicellizing hydrophilic CMC [22]. This was confirmed in our recent study of
amines (both lowꢀmolecularꢀweight butylamine and the surface properties of the Triton Xꢀ100–PEI system
polymeric PEI ) do not shift the CMC of the calixꢀ [23]. Decylamine exerts the most significant effect on
25
Fraction of the neutral form of amines (
α
) in aqueous solutions at pH 9.2 in the presence and in the absence of CO
α
CO
Octylamine
Decylamine
PEI25
PEI ꢀ12
25
No surfactant
0.02
0.11
0.12
0.13
0.39
0.38
0.92
0.92
0.91
0.96
0.97
0.96
9
CO9 (
C
= 0.01 M)
= 0.01 M)
4CO16 (
C
KINETICS AND CATALYSIS Vol. 52
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2011

532
MIRGORODSKAYA et al.
CMC value: at the 1 : 1 molar ratio of the components,
pKa
the 9CO8–decylamine system is characterized by
CMC = 0.0007 mol/l. It should be mentioned that this
system can strongly decrease the the water–air interꢀ
facial tension (Fig. 1).
10.8
10.6
10.4
10.2
10.0
1
The formation of mixed aggregates in the systems
based on the calix[4]arenes and lowꢀmolecularꢀweight
2
3
hydrophobic amines decreases the
рКа of the latter
(
Fig. 3, table). The higher the hydrophobicity of the
amine, the stronger this influence; however, the role of
the change in the calixarene structure is insignificant.
A decrease in the
рКа of amines is accompanied by an
4
increase in the fraction of their neutral form (
α
) at a
given pH of the solution. For both unsubstituted and
alkylated PEIs, the addition of a CO almost does not
change the value of
α
(table), which probably reflects
the weak binding between the components of the sysꢀ
tem. For more basic, longꢀchain amines, the formaꢀ
tion of mixed aggregates is facilitated by the possibility
of stronger hydrogen bonding between the amine and
the calixarene.
9
9
9
.8
.6
.4
5
6
7
It is the neutral form of amines that manifests the
nucleophilic properties observed in chemical reacꢀ
tions. Accordingly, a decrease in рКа usually accelerꢀ
ates processes involving amines. In this work, we studꢀ
ied the influence of CO–amine binary systems on
nucleophilic substitution in carboxylic esters, namely,
0
0.002 0.004 0.006 0.008 0.010
Camph, mol/l
Fig. 3. Plot of p a
tration in the amine–nonionic amphiphile binary systems:
) butylamine–9CO8, ( ) octylamine–Triton Xꢀ100;
) octylamine–9CO8, ( ) octylamine–4CO16, ( ) decyꢀ
lamine–Triton Xꢀ100, decylamine–9CO8, and
) decylamine–4CO16; Camine = 0.005 mol/l, 25 C.
K of amines versus the amphiphile concenꢀ
pꢀnitrophenyl acetate (PNPA) and pꢀnitrophenyl lauꢀ
(
1
2
rate (PNPL). In weakly alkaline media, this process
proceeds via two routes. The main route is aminolysis,
which, in the case of branched PEIs, involves the terꢀ
minal primary amino groups and secondary amino
groups included in the main chain. In addition, alkaꢀ
line and neutral hydrolyses can occur. The scheme of
the process is presented below.
(3
4
5
(6)
(7
°
the character of the surface tension isotherm of the
COs. It affects both the slope of the curve and the
O
R
R
C N
+
HO
NO2
NH
+
O
R
C
O
NO22
+
2OH–
O
−
+ −
C
O
O
NO2
+ H O
2
Note that this choice of objects of investigation biocatalysis, is the shift of the рКа of ionogenic groups
makes it possible to simulate a set of factors characterꢀ (amino groups in our case) in micellar systems.
istic of enzyme catalysis. In these systems, polymeric Kinetic studies of a reaction of two substrates differing
and higher monomeric amines act both as reactants in hydrophobicity make it possible to evaluate the subꢀ
and as structureꢀforming components, thus forming strate specificity, one of the most important parameꢀ
functional micelles. These aggregates allow one to ters of the efficiency of catalytic systems.
attain the maximum reactant concentrating effect.
Kinetic studies of ester cleavage in the presence
Another important factor, which plays the key role in and absence of an amine (at a fixed pH) make it possiꢀ
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CATALYTIC PROPERTIES OF SUPRAMOLECULAR SYSTEMS BASED
533
kapp, s–1
kapp, s–1
0
.05
.04
.03
0
0
0
0
0
0
.030
.025
.020
.015
.010
.005
1
0
0
, s–1
k
app
.25
0
0.20
0.15
0.10
1
2
1
0
.02
.01
0
0.05
2
0
0.005 0.010 0.015 0.020
CCO, mol/l
3
4
0
2
0
0.002 0.004 0.006 0.008 0.010
CCO, mol/l
0
0.002 0.004 0.006 0.008 0.010
Camph, mol/l
Fig. 5. Apparent rate constant for the reactions of octyꢀ
lamine with ( ) PNPA and ( ) PNPL versus the calixarene
concentration in the binary system octylamine–9CO9;
Camine = 0.0025 mol/l, pH 10, 25 C. Inset: apparent rate
constant for the reactions of decylamine with ( ) PNPA
and ( ) PNPL versus the calixarene concentration in the
decylamine–9CO9 binary system; Camine = 0.0025 mol/l,
pH 10, 25 C.
1
2
Fig. 4. Apparent rate constant for the reactions of carboxꢀ
ylic esters with decylamine versus the amphiphile concenꢀ
tration in the decylamine–nonionic amphiphile binary
°
1
systems: (
1
) PNPA–Triton Xꢀ100, (
) PNPL–Triton Xꢀ100, and ( ) PNPL–9CO9; Camine
.0025 mol/l, pH 9.2, 25 C.
2
) PNPA–9CO9,
2
(3
4
=
0
°
°
ble to separate the contributions from aminolysis and The rate constant of the reaction of PNPA with lowꢀ
hydrolysis to the overall process rate. Figures 4–6 molecularꢀweight amines containing hydrophobic
illustrate the influence of COs on the apparent rate radicals (decylamine) in solutions of 9CO9 increases.
constant (kapp) of PNPA and PNPL cleavage in the This possibly reflects the decrease in the
рКа of the
systems containing both lowꢀmolecularꢀweight and amines and the increase in the fraction of their neutral
polymeric amines, specifically, unsubstituted PEI25
form. A similar dependence is observed for the aminolyꢀ
and alkylated PEI ꢀ12. The rate constant for the alkaꢀ
25
sis of PNPA in solutions of Triton Xꢀ100 (Fig. 4). In spite
of the decrease in the Ка of decylamine in CO
line hydrolysis of PNPA was preliminarily estimated
by spectrophotometry at pH 9.2 (borate buffer) in the
absence of amines. The addition of 9CO9 exerts an
insignificant effect on the process rate: kapp decreases
р
micelles, the reaction of decylamine with PNPL is
inhibited (Fig. 4). Laurate is selfꢀassociated in aqueꢀ
ous solutions, resulting in the screening of the active
sites of the substrate and making it anomalously less
reactive than PNPA [24]. Some amphiphilic reacꢀ
tants, including hydrophobic amines, can form mixed
aggregates with PNPL. In these aggregates, the two
reactants are in intimate contact, resulting in high
process rates [25]. The addition of a CO to the system
containing highly reactive association species of decyꢀ
–1
from 0.0005 to 0.0004 s . Thus, under our experiꢀ
mental conditions, the contribution from hydrolysis
can be ignored. Therefore, the curves presented in
Figs. 4–6 reflect the influence of the COs on aminolꢀ
ysis. However, passing to a more alkaline medium can
increase the contribution from hydrolysis, and this
should be taken into account.
The influence of calixarenes on the aminolysis rate lamine and PNPL is accompanied by the formation of
depends on the structures of the amine and substrate. new multicomponent mixed micelles and by the sepaꢀ
KINETICS AND CATALYSIS Vol. 52
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2011

534
MIRGORODSKAYA et al.
, s–1
app
philic amines, for example, butylamine. The same insigꢀ
k
nificant influence of nonionic amphiphiles is observed in
the case of the hydrophilic polyamine, which is exempliꢀ
fied by the PNPA–PEI system (Fig. 6).
0
.006
.005
.004
.003
.002
.001
kapp, s–1
0
0
0
0
0
25
A quite different situation is observed in the reacꢀ
tion of esters with hydrophobized PEI25ꢀ12, as comꢀ
pared to lowꢀmolecularꢀweight hydrophobic amines:
in the presence of nonionic amphiphiles, the aminolꢀ
ysis of PNPA is inhibited (by a factor of 1.5 and 3 for
9CO9 and Triton Xꢀ100, respectively), while this proꢀ
cess for PNPL is somewhat accelerated (Fig. 6). The
influence of the CO and nonionic surfactant on the
0.06
0.04
0.02
1
2
0
0.002
0.006
0.010
Camph, mol/l
р
Ка of the polyamine is nearly absent (table); i.e., in
this case, the change in the fraction of the neutral
form of amine is not the cause the change in the amiꢀ
nolysis rate.
3
The influence of micelles on the process rate is
determined by two main factors [4]: concentrating of
the reactants and the change in their microenvironꢀ
ment. The functional micelles considered in this work
contain reactive nucleophilic groups, and, in the case
of PNPL, the substrate molecules are also involved in
aggregation. Probably, the character of distribution
and localization and the fraction of reactants in mixed
ensembles play an important role in these functional
micelles. Therefore, the inhibition of the reaction of
PEI25ꢀ12 with PNPA in solutions of nonionic surfactants
reflects the redistribution of PNPA between individual
4
5
0
0.002 0.004 0.006 0.008 0.010
Camph, mol/l
aggregates of the polymer and mixed PEI ꢀ12–CO
aggregates in which the fraction of nucleophilic groups
decreases with an increase in the calixarene content.
Fig. 6. Apparent rate constant for the aminolysis of PNPA
25
versus the amphiphile concentration in the PEI–nonionic
amphiphile binary systems: (
1) PEI ꢀ12–Triton Xꢀ100,
25
(
2
) PEI ꢀ12–9CO8; ( ) PEI ꢀ12–9CO9; (
3
4
) PEI25–
25
25
9
CO9, and (
pH 9.2, 25 C. Inset: apparent rate constant of the reaction
of PNPL with PEI ꢀ12 (0.01 mol/l) versus the 9CO9 conꢀ
5) PEI –Triton Xꢀ100; 0.01 mol/l PEI,
25
In the case of PNPL, the low rate constant for the
reaction of the substrate in the absence of CO (point
on the ordinate axis) can be due to the low reactivity of
aggregated PNPL and the inability of PEI25ꢀ12 to
decompose individual micelles of the substrate and
activate the substrate. The increase in the rate constant
in the PEI ꢀ12–9CO9 binary system is probably
°
25
centration; pH 9.2, 25°C.
ration of molecules of decylamine and the substrate,
making their interaction difficult and thus slowing
down the reaction. A decreases in the process rate is
also observed in the interaction of PNPL with decyꢀ
lamine in solutions of Triton Xꢀ100, but the inhibiting
effect of this surfactant is somewhat weaker than that
of the COs. Octylamine behaves similarly in CO soluꢀ
tions; however, the influence of the calixarene on amiꢀ
nolysis is not so pronounced in this case. The fivefold
acceleration of the reaction of octylamine with PNPA
and the fivefold deceleration of its reaction with PNPL
can be achieved in CO solutions at pH 10.0 (Fig. 5).
Under the same conditions, the reaction of decyꢀ
lamine with PNPA is accelerated by a factor of 6 and
the reaction between decylamine and PNPL is slowed
down by a factor of 50 (inset in Fig. 5).
25
caused by the formation of functional aggregates
involving both reactants. The extremum in this depenꢀ
dence can be due to the dilution of the reactants
because of the increase in the micelle concentration
and the decrease in the fraction of reactive compoꢀ
nents in the micelles.
Thus, supramolecular systems were formed from
amphiphilic oxyethylated calixarenes and from higher
or polymeric amines. They exhibit the properties of
functional catalysts in nucleophilic substitution in carꢀ
boxylic esters. A high substrate specificity of the proꢀ
cess was observed: acceleration (by approximately one
order of magnitude) of the reaction of PNPA and inhiꢀ
bition (by a factor of up to 50) of the reaction of PNPL
The influence of 9CO9 and Triton Xꢀ100 is almost in the case of decylamine. The opposite situation is
absent for the reactions of the substrates with hydroꢀ observed in the PEIꢀbased systems: inhibition of the
KINETICS AND CATALYSIS Vol. 52
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CATALYTIC PROPERTIES OF SUPRAMOLECULAR SYSTEMS BASED
535
reaction of PNPA and acceleration of the process 13. Syakaev, V., Mustafina, A., Elistratova, Yu., Latypov, Sh.,
and Konovalov, A., Supramol. Chem., 2008, vol. 20,
no. 5, p. 453.
involving PNPL.
1
4. Zakharova, L., Syakaev, V., Voronin, M., Valeeva, F.,
Ibragimova, A., Ablakova, Yu., Kazakova, E., Latypov, Sh.,
and Konovalov, A., J. Phys. Chem. C, 2009, vol. 113,
p. 6182.
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