Catalytic properties of polymer-colloid complexes based on polyethyleneimines and mono- and diquaternized 1,4-diazabicyclo[2.2.2]octane derivatives in the hydrolysis of phosphorus acids esters

Article abstract of DOI:10.1007/s11172-015-1242-6

It is established by spectrophotometry that polyethyleneimines, mono- (MQD) and diquaternized (DQD) hexadecyl derivatives of 1,4-diazabicyclo[2.2.2]octane, and mixed polymercolloid systems based thereon catalyze the hydrolysis of p-nitrophenyl alkyl chloromethylphosphonates. The catalysis efficiency depends on the structures of substrate, 1,4-diazabicyclo-[2.2.2]octane derivatives, and polyethyleneimine, pH of the medium, and the temperature. In the case of MQD, the catalytic effect changes from 20 to 80-fold with an increase in the length of phosphonate alkyl radical from R = OEt to R = OC₆H₁₃; the DQDs exhibit lower catalytic activity compared to the MQD. The most efficient catalysis (up to 90-fold acceleration) is observed for a mixed polyethylene—dicationic surfactant system where the surfactant contains the hydroxyethyl fragment in the head group, which is due to a favorable effect of the micellar microenvironment of reagents.

Full text of DOI:10.1007/s11172-015-1242-6

Russian Chemical Bulletin, International Edition, Vol. 64, No. 12, pp. 2879—2884, December, 2015
2879
Catalytic properties of polymerꢀcolloid complexes based on polyethyleneimines
and monoꢀ and diquaternized 1,4ꢀdiazabicyclo[2.2.2]octane derivatives
in the hydrolysis of phosphorus acids esters*
T. N. Pashirova, E. P. Zhil´tsova, S. S. Lukashenko, L. Ya. Zakharova, and A. I. Konovalov
A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center of the Russian Academy of Sciences,
8
ul. Akad. Arbuzova, 420088 Kazan, Russian Federation.
Fax: +7 (843) 273 2253. Eꢀmail: tatyana_pashirova@mail.ru
It is established by spectrophotometry that polyethyleneimines, monoꢀ (MQD) and diquatꢀ
ernized (DQD) hexadecyl derivatives of 1,4ꢀdiazabicyclo[2.2.2]octane, and mixed polymerꢀ
colloid systems based thereon catalyze the hydrolysis of pꢀnitrophenyl alkyl chloromethylphosꢀ
phonates. The catalysis efficiency depends on the structures of substrate, 1,4ꢀdiazabicycloꢀ
[
2.2.2]octane derivatives, and polyethyleneimine, pH of the medium, and the temperature. In
the case of MQD, the catalytic effect changes from 20 to 80ꢀfold with an increase in the length
of phosphonate alkyl radical from R = OEt to R = OC H ; the DQDs exhibit lower catalytic
6
13
activity compared to the MQD. The most efficient catalysis (up to 90ꢀfold acceleration) is
observed for a mixed polyethylene—dicationic surfactant system where the surfactant contains
the hydroxyethyl fragment in the head group, which is due to a favorable effect of the micellar
microenvironment of reagents.
Key words: polyethyleneimine, 1,4ꢀdiazabicyclo[2.2.2]octane, polymerꢀcolloid complex,
alkaline hydrolysis, phosphorus acids esters.
Systems based on polymers and surfactants have found
ions, peptides,21—23 and proteins24 and is applied for imꢀ
2
5—27
a wide application in cosmetic, pharmaceutical, paintꢀ
andꢀvarnish, petrochemical, and other fields of industry,
and, in recent years, in nanomedicine upon the design of
drug and genetic material delivery systems.1 The efficacy
of mixed surfactant—polymer compositions is known to
be caused by the formation of joint structures or polymerꢀ
mobilization and stabilization of metal nanoparticles
2
8—31
and enzymes.
The nanocatalyst obtained involving
polyethyleneimine possess some advantages over convenꢀ
tional ones (low cost, the absence of reducing and stabilizꢀ
,2
3
2,33
ing agents, recoverability, etc.).
There are also sucꢀ
cessful works on the design of platinum catalysts using
3
—5
34,35
colloid complexes
and depends on the surfactant
polyethyleneimine for fuel cells.
6
,7
type and the ratio between the system components.
Polyethyleneimines are known to catalyze the transfer
Earlier,8 we have shown that the use of polymerꢀcolloid
systems based on surfactants and polymers (polyethylene
glycols, polyethyleimines, block copolymers) makes it posꢀ
sible to control the rate of hydrolysis of phosphorus and
carboxylic acids esters and to decrease the concentration
of catalytic agents.
,9
of acyl and phosphoryl groups.
surfactants
36—38
In the presence of
39,40
and amphiphilic cyclophanes,41,42 polyꢀ
ethyleneimines form polymerꢀcolloid complexes exhibitꢀ
ing catalytic activity in the hydrolysis of carboxylic and
4
3,44
phosphorus acid esters.
In continuation of our studꢀ
ies, in the present work we evaluated the catalytic properꢀ
ties of polyethyleneimine (PEI) and its hydrophobized anꢀ
alog (HPEI) in the absence and in the presence of monoꢀ
and dicationic surfactants, viz., monoꢀ and diquaterꢀ
nized 1,4ꢀdiazabicyclo[2.2.2]octane hexadecyl derivaꢀ
tives (MQD and DQD, respectively). The cationic surꢀ
factants (CSs) under study are known to possess lower
Polyethyleneimine is widely used as the gene transfecꢀ
tion agent; it is available in commercial forms which posꢀ
1
0,11
sess low toxicity in vivo
and approved themselves in
clinical trials.12 Many recent studies13 show that the transꢀ
fection efficiency and the cytotoxicity upon application of
polyethyleneimine—DNA complexes depend significantly
on the polymer molecular weight and concentration ,
as well as on its chemical modification.1
1
4
15
45
toxicity compared to their classical analog, cetyltriꢀ
6—20
Polyethyleneꢀ
methylammonium bromide. Addition of cationic surfacꢀ
tants with a variable number of cationic centers to the
polymer composition will allow one to control the polyꢀ
funcitonal properties of the system by optimization of its
composition.
imine forms nanoassemblies with naturally occurring polyꢀ
*
Dedicated to Academician of the Russian Academy of Sciences
N. S. Zefirov on occasion of his 80th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2879—2884, December, 2015.
066ꢀ5285/15/6412ꢀ2879 © 2015 Springer Science+Business Media, Inc.
1

2
880
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 12, December, 2015
Pashirova et al.
(3)
where km and k0 (s–1) are the rate constants in the micellar
pseudophase and the bulk of solvent, respectively; C is the
Surf
–
1
surfactant concentration (mol L ); CMC is the critical micelle
concentration (mol L–1); k2,app (L mol–1
ondꢀorder rate constant obtained upon division of k
s
–1
) is the apparent secꢀ
by the
MQD
R = Et (DQDꢀ1), C H OH (DQDꢀ2)
2
4
app
nucleophile concentration; k2,0 and k2,m (L mol– s–1) are the
1
Experimental
HPEI compounds were obtained by the reaction of PEI (the
secondꢀorder rate constants in the bulk of solvent and the micelꢀ
–
1
lar pseudophase, respectively, V (L mol ) is the molar volume
of surfactant; K and K (L mol– ) are the constants for subꢀ
1
S
Nu
molecular weight is 25000) (Aldrich) with nꢀdodecyl bromide
according to the earlier described procedure.4 Complete characꢀ
terization of the HPEI sample under study has been given in Ref. 47.
The molecular weight of HPEI monomer unit was determined
by potentiometric titration, which was found to be efficient. The
preparation of MQD from 1,4ꢀdiazabicyclo[2.2.2]octane and
hexadecyl bromide has been described previously.4 DQDꢀ1 and
DQDꢀ2 were synthesized by quaternization of MQD with
strate and nucleophile binding to micelles. In terms of the model
proposed in Ref. 54 (see Eq. (3)), the maximum acceleration of
the process is described by Eq. (4):
6
(4)
9
where the first multiplier in the right side of the equation reflects
the factor of change in the microenviroment of reagents on their
5
0
1
ꢀbromoethane and 2ꢀbromoethanol, respectively. The subꢀ
strates, Oꢀ4ꢀnitrophenylꢀOꢀalkyl chloromethylphosphonates (1—3)
Scheme 1), were prepared according to the procedure described
going from a solvent to the micellar phase (F ) and the second
m
multiplier corresponds to the effect of reagents concentrating in
(
the micellar phase (F ).
in Refs 51 and 52. The polymer concentration is expressed as the
molar concentration of monomer unit, which was calculated
based on the data from potentiometric titration of the polymer;
it corresponds to the number of its ionic groups capable of unꢀ
dergoing alkylation.
c
All solutions under study were prepared in water purified
using a DirectꢀQ 5 UV system (Millipore S.A.S. 67120 Molsheim,
France).
Results and Discussion
Scheme 1
Supramolecular systems based on similarly charged
surfactants and polyelectrolytes are less studied than polyꢀ
merꢀcolloid complexes based on surfactants and uncharged
39,41,55,56
polymers. Earlier,
we have studied systems based
on the weak polyelectrolyte, PEI, and cationic surfactant
of different structure. In the case of hydrophobized PEI,
complexation is likely defined mainly by the contribution
of hydrophobic effect and the reaction of the nonꢀalkylatꢀ
ed analog proceeds by the same mechanism as in the case
of uncharged polymers, since the portion of protonated
amino groups is low at pH ∼ 10 in the absence of a buffer
solution. The catalytic activities of the systems based on
polyethyleneimines and monoꢀ and diquaternized surꢀ
factants were studied by the example of hydrolysis of Oꢀ4ꢀ
nitrophenylꢀOꢀalkyl chloromethylphosphonates 1—3 (see
Scheme 1).
1
2
R = ClCH , R = OEt (1), OBu (2), OC H (3)
2
6 13
The reaction kinetics was studied on a Specord UV—Vis
spectrophotometer in thermostatically controlled cells by the
increase in the absorbance of 4ꢀnitrophenolate anion at 400 nm.
The apparent rate constants for the reaction (kapp, s ) were
determined by the firstꢀorder equation (1):
–
1
Catalytic activity of PEI and HPEI. The reaction kinetꢀ
ics in the presence of PEI was studied by the example of
hydrolysis of phosphonate 1. According to the data obꢀ
log(D – D ) = –0.434kappt + const,
(1)
∞
t
where D∞ and D are the absorbances after completion of the
t
41
tained earlier, the hydrolysis of phosphorus acids esters
in aqueous solutions of PEI proceeds by the mechanism of
generally base ligand. Figure 1 shows the apparent rate
constant for the hydrolysis of phosphonate 1 as a function
of the concentration of polymers for which there was
a tendency of coming to plateau in the high concentration
range, which is typical of micellar catalyzed reactions5
and suggests binding of the substrate to aggregates. The
reaction and at a time point t, respectively.
The concentrations of substrates 1—3 were 5•10–5
—
•10–4 mol L . The parameters of the micelleꢀcatalyzed proꢀ
–1
1
cess were determined by the equations of the pseudophase model
of micellar catalysis5
3,54
(2) and (3):
3,54
(2)

Polymerꢀcolloid complex catalysts
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 12, December, 2015 2881
kapp/s–1
kapp/s–1
.006
kappk0–1
4
0
0
0
600
0
0
0
.03
.02
.01
3
2
.004
.002
400
200
1
0
.2
0.4
0.6
0.8 С/mol L–1
Fig. 1. Apparent rate constant (kapp) for the hydrolysis of phosꢀ
phonate 1 as a function of the concentration of PEI (1) and
HPEI (2—4) at pH = 10.5 (1) and 10 (2—4) and at T = 25 (1, 2),
8
9
10
pH
Fig. 2. Apparent rate constant (kapp) for the hydrolysis of phosꢀ
phonate 1 and acceleration (kappk0–1) of this process as a funcꢀ
tion of pH for the HPEI—water system, CHPEI = 0.1 mol L
5 °C.
3
5 (3), and 45 °C (4).
–
1
,
2
analysis of kinetic data in terms of the pseudophase model
of micellar catalysis suggests an insignificant acceleration
–
1
of the reaction (kappk0 )max in the presence of PEI and
a high catalytic effect of HPEI (∼ 60ꢀfold). With increasing
the temperature by 20 °C, the reaction in the presence of
HPEI is accelerated more than 100ꢀfold (Table 1). The
amphiphilic HPEI polymer showing a capability of assoꢀ
ciation in the aqueous medium5 and creating favorable
conditions for binding between the substrate and the nuꢀ
cleophile can catalyze efficiently the reaction under study.
It should be noted that the resulting effect for HPEI based
on PEI with a molecular weight of 25000 is higher than
that for its hydrophobized analog based on PEI with
a molecular weight of 10000 studied by us earlier.56 With
a decrease in the pH of solution to 7.5, the catalytic effect
increases up to 600ꢀfold (Fig. 2). In the region of neutral
and slightly alkaline pH values, there occurs protonation
of the amino groups of HPEI nanoaggregates which can
bind the hydroxide ions due to the electrostatic interacꢀ
tion, i.e., can increase the contribution of the reagent conꢀ
centrating factor to the catalytic effect of the system.
Catalytic activity of cationic surfactants. The study of
hydrolysis in the presence of individual cationic surfacꢀ
tants (Fig. 3) showed that the catalytic effect obtained is
comparable in the order of magnitude with the efficiency
of systems based on the individual HPEI. The highest
catalytic effect (∼ 20ꢀfold) is reached in the case of MQD
(Table 2). The change in the structure of the head group of
5
kapp/s–1
0
0
0
0
0
.25
.20
.15
.10
.05
5
4
1
Table 1. Parameters for the hydrolysis of substrate 1 in the presꢀ
ence of PEI (pH 10.5) and HPEI (pH 10) in water
a
2
km•102 k k
/s
–1b
System Т/°С CMC •10
KS
/L mol
m
0
–1
–1
/
mol L–1
3
PEI
HPEI
25
25
0.47
3.20
1.90
1.30
37.00
20.00
8.10
0.29
2.00
3.40
4.10
112.2
157.0
197.0
117.0
2
35
5
C/mol L–1
0
.005
0.010
0.015
4
0.13
Fig. 3. Apparent rate constant (kapp) for the hydrolysis of
substrates 1 (1—3), 2 (4), and 3 (5) as a function of the concenꢀ
trations of MQD (1, 4, 5), DQDꢀ1 (2), and DQDꢀ2 (3);
CNaOH = 0.001 mol L– , 25 °C.
a
Critical micelle concentration.
b
k0 is the apparent rate constant for the hydrolysis in the absence
of PEI and HPEI at the corresponding pH value.
1

2
882
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 12, December, 2015
Pashirova et al.
a
b
Table 2. Parameters for the hydrolysis of substrates 1—3 in the presence of cationic surfactants and CS—HPEI at 25 °C
System
MQD
Substrate
k2
KS
KNu
(kappk0–1)maxc
Fm
Fc
CMCd
/mol L
,m
L mol– s–1
1
–1
/
L mol–1
1
2
3
1
1
1
1
1
1
1
1
0.9800
0.4800
0.5700
0.3200
0.2000
0.0066
0.0060
0.0130
0.0760
0.0016
0.0054
2000
4570
9300
1500
1100
1300
1600
1600
1000
1830
1400
132
110
180
155
190
126
123
120
11.0
160
123
20.50
40.60
82.00
10.60
19.75
29 (29)
23 (56)
36 (88)
0.240
0.160
0.172
0.080
0.050
0.430
0.380
0.870
0.850
0.020
0.060
183
270
470
130
180
166
160
141
114
125
150
0.00090
0.00075
0.00110
0.00290
0.00200
0.00120
0.00330
0.00270
0.00150
0.00290
0.00150
DQDꢀ1
DQDꢀ2
e
PEI—MQD
PEI—DQDꢀ1
PEI—DQDꢀ2
HPEI—MQD
HPEI—DQDꢀ1
HPEI—DQDꢀ2
e
e
e
13.8 (53)
e
12.5 (35)
e
12.9 (41)
a
CNaOH = 0.001 mol L–1, CS—PEI pH 10.5, and CPEI = 0.05 mol L–1
pH 9.5, CHPEI = 0.02 mol L–1
k0 is the apparent rate constant for the hydrolysis in the absence of cationic surfactant at the corresponding pH value.
Determined by Eq. (2).
.
b
c
d
e
.
The acceleration of alkaline hydrolysis without catalyst is given in parentheses.
cationic surfactant (the increase in the charge number and
introduction of the hydroxyethyl fragment) has an effect
on its catalytic activity. The increase in the charge number
in the head group of CSs under study affects favorably the
value of reagent concentrating factor which increases
and 40 for PEI—DQDꢀ2. The factor of micellar microꢀ
environment for the PEI—DQDꢀ2 system is equal to 0.87
which is ∼ 2ꢀfold higher than that for the PEI—MQD and
PEI—DQDꢀ1 systems. Thus, the effect obtained is caused
by a lower contribution of the nonfavorable factor of
reagent micellar microenvironment to the total catalytic
effect.
In the case of HPEI—CS composition, the reaction
acceleration depends slightly on the CS structure (Fig. 5,
see Table 2). In the presence of MQD, the acceleration
∼
2ꢀfold. However, the acceleration of hydrolysis in the
presence of DQD is 2ꢀfold less than that in the case
of MQD, which can be due to a significant decrease
(
3—5ꢀfold) in the factor of change in the microenvironꢀ
ment of solubilized reagents (F ).
m
To reveal the substrate specificity, the effect of subꢀ
strate structure on the catalytic effect of MQD was studied
2
–1
kapp•10 /s
(
see Fig. 3, curves 1, 4, and 5). According to the data given
in Table 2, the catalytic effect of MQD micelles increases
from 20 to 80ꢀfold on going from the less hydrophobic
substrate 1 to the more hydrophobic substrate 3. The reꢀ
sulting effect is caused by the increase in the reagent conꢀ
3
2
.5
centrating factor (F ) with an increase in the length of
2.0
c
1
substrate alkyl radical.
Catalytic activity of polymer—CS compositions in the
hydrolysis of phosphonate 1. According to our previous
studies, the mixed polymerꢀcolloid complexes are proꢀ
duced in aqueous solutions of polymer—CS, where the
concentration range of their formation depends signifiꢀ
cantly on the type of cationic surfactant.
The comparison between the catalytic activities of inꢀ
dividual compounds and compositions based thereon
showed the mixed polymer–CS systems to possess higher
catalytic effect compared to their components. The highꢀ
est catalytic effect is reached in the PEI—DQDꢀ2 system
2
1
1
0
.5
.0
.5
5
5
0.01
0.02
0.03
C/mol L–1
(
~
Fig. 4, see Table 2), where the reaction is accelerated
90ꢀfold compared to the noncatalyzed reaction. The reꢀ
Fig. 4. Apparent rate constant (kapp) for the hydrolysis of subꢀ
strate 1 as a function of the concentration of MQD (1), DQDꢀ1 (2),
and DQDꢀ2 (3) in the presence of PEI (0.05 mol L– ), pH 10.5,
25 °C.
1
agent concentrating factor for the CS—PEI systems changes
insignificantly to be 66 for PEI—MQD, 60 for PEI—DQDꢀ1,

Polymerꢀcolloid complex catalysts
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 12, December, 2015 2883
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m
Thus, new polymerꢀcolloid complexes based on MQD,
DQD, and PEI with different hydrophobicities exhibit high
catalytic activity in the hydrolysis of phosphorus acid esters.
The catalysis efficiency was found to depend on the strucꢀ
tures of surfactant, polymer, and substrate, the temperaꢀ
ture, and pH of the medium. The systematic data obtained
allows one to reveal the structure—property correlation
and to optimize the formulation of catalytic compositions.
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