Self-Assembled Quaternary Ammonium-Containing Comb-Like Polyelectrolytes for the Hydrolysis of Organophosphorous Esters: Effect of Head Groups and Counter-Ions

Article abstract of DOI:10.1002/cplu.202000417

The aim of this work was to increase the efficiency of catalytic systems for the hydrolytic cleavage of 4-nitrophenyl esters of phosphonic acids. Quaternary ammonium-containing comb-like polyelectrolytes (?polymerized micelles?) with ester cleavable fragments and a low aggregation threshold were used as catalysts. The synthesis of poly(11-acryloyloxyundecylammonium) surfactants with different counterions (Br^?, NO₃^?, CH₃C₆H₄SO₃^?) and head groups was realized by micellar free-radical polymerization. Molecular weight, critical association concentration, particle sizes and solubilization properties toward Orange OT were determined. Self-assemblies organized by poly(11-acryloyloxyundecyltrimethyl ammonium) bromide successfully catalyze the hydrolysis of 4-nitrophenyl butylchloromethylphosphonate up to two orders of magnitude compared to aqueous alkaline hydrolysis. The development of these catalysts is promising for industrial applications and organophosphorus compound detoxification.

Full text of DOI:10.1002/cplu.202000417

A Multidisciplinary Journal Centering on Chemistry
Accepted Article
Title: Self-Assembled Quaternary Ammonium-Containing Comb-Like
Polyelectrolytes for the Hydrolysis of Organophosphorous Esters:
Effect of Head Groups and Counter-Ions
Authors: Tatiana N. Pashirova, Petr Fetin, Alexey A. Lezov, Matvey V.
Kadnikov, Farida G. Valeeva, Evgenia A. Burilova, Alexander
Yu. Bilibin, and Ivan M. Zorin
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To be cited as: ChemPlusChem 10.1002/cplu.202000417
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ChemPlusChem
10.1002/cplu.202000417
FULL PAPER
Self-Assembled Quaternary Ammonium-Containing Comb-Like
Polyelectrolytes for the Hydrolysis of Organophosphorous
Esters: Effect of Head Groups and Counter-Ions
[
a]
[b]
[c]
[b]
Dr., Tatiana N. Pashirova,* Dr., Petr A. Fetin,* Dr., Alexey A. Lezov, Matvey V. Kadnikov,
[
a]
[a]
[b]
[b]
Dr., Farida G. Valeeva, Dr., Evgenia A. Burilova, Prof., Alexander Yu. Bilibin, Dr., Ivan M. Zorin*
[
[
a]
b]
Dr., Tatiana N. Pashirova, Dr., Farida G. Valeeva, Dr., Evgenia.A. Burilova,
Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences,
Arbuzov St., 8, Kazan, 420088, Russian Federation
E-mail: tatyana_pashirova@mail.ru
Dr., Petr A. Fetin, Dr., Ivan M. Zorin, Matvey V. Kadnikov, Prof., Alexander Yu. Bilibin
Institute of Chemistry
St. Petersburg State University,
7/9 Universitetskaya nab, St. Petersburg 199034, Russian Federation
E-mail: p.fetin@spbu.ru, i.zorin@spbu.ru
Dr., Alexey A. Lezov
[с]
Department of Molecular Biophysics and Polymer Physics, Physical Faculty
St. Petersburg State University,
7/9 Universitetskaya nab, St. Petersburg 199034, Russian Federation
Supporting information for this article is given via a link at the end of the document
[
3]
Abstract: The aim of this work was to increase the efficiency of
catalytic systems for the hydrolytic cleavage of 4-nitrophenyl esters
of phosphonic acids. Quaternary ammonium-containing comb-like
polyelectrolytes («polymerized micelles») with ester cleavable
fragments and a low aggregation threshold were used as catalysts.
The synthesis of poly(11-acryloyloxyundecylammonium) surfactants
applications,
environmental
and as catalysts in nucleophilic substitution
issues
(extractants
and
[24–26]
flocculants)
reaction for hydrolysis of ester bonds.
nucleophilic substitution in phosphorus esters play an important
[
17,27,28]
Reactions of
[
29]
role in biological processes.
organophosphorus pesticides
health problems,
Also, poisoning and pollution by
-
-
-
[30]
3 3 6 4 3
with different counterions (Br , NO , CH C H SO ) and head groups
and insecticides poses serious
was realized by micellar free-radical polymerization. Molecular
weight, critical association concentration, particle sizes and
solubilization properties toward Orange OT were determined. Self-
assemblies organized by poly(11-acryloyloxyundecyltrimethyl
ammonium) bromide successfully catalyze hydrolysis of 4-
nitrophenyl butylchloromethylphosphonate up to two orders of
magnitude compared to aqueous alkaline hydrolysis. The
development of these catalysts is promising for industrial
applications and organophosphorus compound detoxification.
[31]
environmental problems in water and
[32]
[33,34]
soils.
Therefore, their decomposition is relevant.
Actual
research directions in this area are improvement in the efficacy
of catalytic systems and the use of environmentally friendly
processes. The latter can be achieved by using green
[35,36]
[37]
solvents,
biodegradable surfactants,
α-nucleophilic
[38]
systems
and lowering surfactant concentration. It can be
achieved by using dimeric (gemini) or polymeric surfactants that
have much lower critical micelle concentration (CMC) and higher
[39,40]
binding constants than monomeric surfactants.
The use of
polymers as catalysts reduces their concentrations and bring
Introduction
[41][42]
reaction centers much closer.
Thus, these polymers
[43–46]
become closer to enzymatic model of catalysis.
Design of
Self-assembled systems have wide applications in biomimetic
and sensor system technologies, protective coatings,
new hybrid polymers with incorporated and covalent linked
reagents within their structure is a way to create a second-
[1–4]
[47–49]
nanocontainers.
Possible applications of self-assemblies
generation micellar nanoreactor.
In this paper we describe
results from self-organization in solution and at interfaces and
their ability to solubilize organic compounds. One of perspective
trends of self-assemblies is their use for studies of different
synthesis of comb-like polyelectrolyte and their properties
related to catalytic hydrolysis of alkylphosphoric acid esters (OP).
The reaction of hydrolysis of model organophosphorus
substrates 4-nitrophenyl esters of phosphonic acids was
examined (Scheme 1a). The so-called «polymerized micelles»
are comb-like polyelectrolytes obtained from corresponding
[5–8]
types of organic reactions.
These catalytic self-assembled
nanoreactors lead to design environmentally friendly catalysts
[
9–11]
and develop green reactions in water.
such as micelles,
Nanocompartments
[5,12–14]
[15]
[50]
polymersomes have been established
micelle-forming monomers. The term was initially used in work
[51,52]
as smart and compact devices to carry out reactions. Catalytic
acceleration of chemical reactions in surfactant solutions is
caused by micelle formation and transfer of reagents and
and there are numerous examples of such polymers,
for waste water treatment, micellar chromatography.
used
[16]
substrates in micellar pseudophase.
Catalytic efficacy is
determined by optimization of molecular structure (charge and
structure of amphiphilic molecule head group and chain
[17–19]
length
rods, vesicles etc.).
promising due to the charge of head group for biological
), concentration and type of self-assemblies (micelles,
[20–23]
Cationic surfactants are the most
1
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Scheme 1. Hydrolysis of organophosphorus substrates 1-3 in the presence of
-
-
-
comb-like polyelectrolytes: pAUTA-X , pAUTEA-Br , pAUMM-Br .
[53]
As it was shown in work,
there are no direct correlation
between shape and size of «polymerized micelles» self-
assemblies and shape and size of the parent monomer micelles.
These are separate class of surfactants with distinct differences
from the monomeric ones. Molecular architecture of most
«polymerized micelles» correspond to comb-like type
polyelectrolyte. We use three cationic micelle-forming monomers
1
1
1-acryloyloxyundecyltrimethylammonium bromide (AUTA-Br),
1-acryloyloxyundecyltriethylammonium bromide (AUTEA-Br)
and N-(11-acryloyloxyundecyl)-N-methylmorpholinium bromide
AUMM-Br) to obtain a series of polymers with ester cleavable
(
fragments depicted in Scheme 1b. Systematic study was
performed on the influence of structure and counter-ions of
[54,55]
micellar surfactants on the nucleophilic cleavage of OP
but
a limited content is available for polymeric surfactants. The
present work was initiated to use new type of cleavable
«polymerized micelles» with a low aggregation threshold as a
catalysts and to expand results about their influence on the
nucleophilic cleavage of OPs. Influence of the head group types,
counter-ions and degree of polymerization of the comb-like
polyelectrolytes were investigated.
Figure 1. Change in conductance of reaction mixture in the course of
polymerization AUTA-Br (short dots), AUMM-Br (solid), AUTEA-Br (short
dash) at 60°C and monomer concentration: C=0.27 M (a), C= 0.07M (b).
Thus we obtained
a set of polymers with degree of
polymerization (DP) ranging from 35 to 230. Determination of
molecular weight of the polymers was a special task because of
their high adsorptive properties and ability to form associates.
Thus, common methods as GPC and SLS appeared to be
inapplicable. Average molecular weights (MDƞ) of polymers were
estimated from viscometry and DLS measurements in 0.05 M
aqueous NaCl (See supplementary Fig. s1-s3). The obtained
characteristics of investigated comb-like polyelectrolytes are
presented in Table 1.
Results and Discussion
Polymerization
Micelle forming monomers undergo fast and quantitative
conversion to polymer during polymerization in solution at
concentrations higher than CMC. The polymerization
mechanism is close to microemulsion regime. Conductance
Table 1. Average molecular weights (MDƞ), degree of polymerization (DP),
measurements
polymerization process
were
convenient
(Fig. 1). As the polymerization
for
monitoring
the
1
self-diffusion coefficients (D
0
), intrinsic viscosity ([ƞ]), the jump in conductivity
[56]
m
during polymerization (Δσ), and monomers concentration (C ) during
proceeds, conductance of solution gradually decreased and
after polymerization completion, conductance becomes constant.
The causes for the conductance decrease are increase in
solution viscosity, dramatic decrease of charge carrier number
and their mobility. It may take from 10 to 15 minutes to achieve
polymerization for comb-like polyelectrolytes.
1
7
-3
Monomer
Cm
М)
Δσ
[η]
D
0×10
MDη×10
DP
.
-1
-1
2
-1
(
(mS cm
)
(dL·g
)
(cm ·s )
AUTA-Br
0.07
0.27
0.07
0.27
0.07
0.27
4.4
0.36
1.38
0.53
1.26
0.50
0.76
4.6
35
83
13
91
41
55
100
230
35
[57]
95-98% conversion.
Only monomer molecules incorporated
into the micelles undergo fast conversion to polymer, reaction of
monomer in molecular solution proceeds much slowly, so
theoretical value of conversion (p) may be calculated as fraction
of total amount of monomer incorporated in micelles p=(C-
CMC)/C.
-
8.0
2.2
AUMM-Br
4.3
5.6
-
7.6
2.2
220
100
135
AUTEA-Br
-
4.0
3.9
5.8
3.1
2
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The MDƞ for pAUTA-Br sample is correlated with molecular
Table 2. CAC values determined by fluorimetry in the presence of pyrene and
spectrophotometry using Orange OT and solubilization capacity (S), 25 ºС
weight measured by sedimentation analysis in our previous
[
58]
work.
The transient jump in conductivity during
[
a]
[b]
[b]
Polyelectrolyte
DP
I
1
/I
3
Ratio
CAC
CAC1
(mM)
S1
CAC2
(mM)
S2
polymerization (Δσ, Fig. 1, Table 1) can serve as simple
criteria of reproducibility of polymerization. The Δσ value is
decreased with decreasing averaged molecular weights of
3
3
(
mM)
10
10
pAUTA-Br
100
230
100
230
100
230
100
135
35
1.61-1.55
1.6-1.5
1.62
0.15
0.24
0.02
0.22
0.03
0.04
0.2
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
8.4
13
11
8.8
26
35
11
17
9.8
1.2
1.5
1.7
0.6
0.6
0.6
0.7
4.7
17
-
-
-
comb-like polyelectrolyte. Ion exchange of Br to NO
3
and Br
-
to toluene-4-sulfonate allows to obtain polymers pAUTA-NO
3
and pAUTA-Ts having exactly the same DP as parent pAUTA-
Br. Polymers pAUTEA-Br and pAUMM-Br have slightly
different DP due to different micellar order in monomer
solution in the course of polymerization.
pAUTA-NO
3
6.8
4.9
20
-
1.19
pAUTA-Ts
-
1.56-1.52
1.12
15
Self-assembly and solubilization properties
pAUTEA-Br
-
1.71-1.61
1.69-1.61
1.58-1.51
8.1
4.6
2.1
The concept of «polymerized micelles» in contrast to common
micelles of low-molecular weight compounds contemplates
that micelles can exist in full concentration range up to very
high dilutions. Nevertheless, formation of hydrophobic
domains in solutions of «polymerized micelles» starts at certain
0.1
0.45
1.5
pAUMM-Br
0.06
[
a] fluorimetry. [b] spectrophotometry using Orange OT.
[52,59]
The solubilization capacity of both intra-macromolecular and
inter-macromolecular self-assemblies increased 3 and 4 times,
concentration – critical association concentration (CAC)
.
The polymers are able to form self-assemblies of two types –
intra-macromolecular associates and inter-macromolecular
-
-
-
3
respectively, in the sequence of counterions Br <NO <Ts . The
highest Orange OT solubilization was achieved for pAUTA-Ts.
This S1 value is 1.6 times higher than for CTAB micelles (S =
(
multi-macromolecular) associates that can be detected by
appropriate methods. Solubilization of hydrophobic dyes is an
informative method for CAC determination and detection of
hydrophobic domains of polymers. Orange OT was used as a
spectral probe for determination of CAC and solubilization
properties. The absorption spectra of Orange OT in different
concentrations polymer solutions are shown in supplementary
Fig. s4, s5. Concentration dependences of solution optical
densities at λmax = 495 nm (Orange OT adsorption) are shown in
Figure 2. Linear increase in optical density corresponding to
Orange OT solubilization starts at very low polymer
concentration (CAC1). Solubilization capacity (S) evaluated by
equation 4 is presented in Table 2. Likely, CAC1 corresponds to
[60]
1
2
5.9 ). The same effect was observed for pAUTA-Ts with DP =
30 (See supplementary Fig. s6). Usually, the replacement of
bromide by a hydrophobic anion such as tosylate decreases
critical micelle concentration and induces the sphere-to wormlike
micelle transition in aqueous solutions of trimethylammonium
[61]
surfactants. Thus, the improvement in solubilization properties
of tosylate ion is mainly due to a change in morphology and a
[57]
stronger interaction of counterion with surfactant head group.
The effect of variation of head groups is shown in Fig. 2b.
pAUTEA-Br has the highest solubilization capacity. This may be
due to the greater hydrophobicity to the nonpolar core imparting
by ethyl substituents at the nitrogen atom. Pyrene has been
extensively used for the study of microheterogeneous systems,
the formation of intramolecular self-assemblies. The
S of
polymeric surfactant at CAC1 corresponds to the solubilization
of Orange OT by single macromolecules (S1) (Table 2). CAC2
and S2 correspond to the formation and the solubilization by
multi-macromolecular self-assemblies. Effect of the nature of
counterions on solubilization properties is observed in Fig. 2A.
[
62,63]
[64,65]
such as micellar solution
emission spectra of pyrene, intensity ratio I
nm) and I (384 nm) - is characteristic of microenvironment
polarity of pyrene.
and polymers.
In fluorescence
1
/I
3
- where I (373
1
3
[
62,63,66]
Fig. s7 and s8 in supplementary show
pyrene emission spectra in polymer solutions at different
concentrations. We can see a shift in the band at low
concentrations (0.02-0.2 mM). These changes accompany the
transfer of pyrene molecules from water environment to the
hydrophobic micellar core. The increase in the intensity of
pyrene fluorescence with increasing polymer concentration was
[67,68]
also observed.
This suggests that pyrene was transferred
from aqueous to hydrophobic phase. The incorporation of
pyrene into micelles appears to suppress the molecular motion
of pyrene, resulting in decrease in thermal deactivation of
[
69]
electronically excited state.
ratio I /I on the polymer concentration are presented in Figure 3.
As a rule, this ratio is between 1.6 and 1.9 in aqueous or
Dependences of pyrene intensity
1
3
[63,70]
similarly polar environment.
the less polar environment of the core results in a characteristic
decrease of the I /I ratio. Namely, at high polymer concentration
the limiting value of I /I represents the polarity sensed by
pyrene in the hydrophobic sites of polymer micelle.
For regular polymer micelles,
Figure 2. Orange-OT optical density in solutions of pAUTA-Br (1), pAUTA-NO
2), pAUTA-Ts (3) (a) and pAUTEA-Br (4) with DP =100, pAUMM-Br (5) with
DP = 35 (b) ,λmax = 495 nm, L=1 cm, 25 ° C.
3
(
1 3
1
3
[68]
3
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Figure 3. Dependence of intensity ratio (I
pyrene in solutions of pAUTA-Br (1), pAUTA-NO
1
/I
3
) of the first and third peaks of
(2), pAUTA-Ts (3) with DP
3
=
100 (a) and pAUTA-Br (1`), pAUTA-NO
3
(2`), pAUTA-Ts (3`) with DP = 230,
25 °C (b).
For example, I
acrylamidoundecanoyl)-L-alaninate),
b-PANa diblock copolymers,
1
/I
3
≈ 1.38 for polysoap (poly[sodium N-(11-
[71]
1 3
I ≈ 1.05-1.12 for PS-
/I
≈ 1.2 for Tetronic 908,
≈ 0.9-1.2 for hydrophobically
That is very similar to the micellar
[72]
[73]
I
1
/I
3
1 3
I /I
[
74]
≈
1.3 for Pluronic P85,
1 3
I /I
[
75]
modified polyacrylates.
[76]
environment
of ionic detergents (sodium laurate, 1.042;
sodium laurylsulfate, 1.136) and nonionic detergents (Triton-X-
1
1 3
00, 1.30). Polymers with I /I value close to 1.8 and greater
[74,77,78]
were reported in literature.
The plot in Fig. 3a shows that
the polarity ratio decreased to 1.5-1.6 for polymer solutions of
pAUTA-X with DP=100, which is less than that in water (1.8 or
1
1 3
.6). Minor but systematic changes in I /I values can be
Figure 4. Dependence of the inverse relaxation time (1/τ) on square of wave
interpreted as CAC. The polarity depends on the type of
counter-ion and DP. Thus, it is decreasing for pAUTA-X in the
2
vector (q ) (a) and hydrodynamic radius distribution (b) for pAUTA-NO
3
at С=
0.02M.
−
−
−
order Br >NO
NO and pAUTA-Ts with DP =230 have the lowest I
close to that of solvents such as toluene (1.12) and surfactant
sodium lauryl sulfate). Likely, different polarity is associated
3
>Ts and with increasing DP (Fig. 3B). pAUTA-
3
/I value,
1 3
pyrene fluorescence is fully confirmed by dynamic light
(
scattering. The dependence of the reciprocal of relaxation time
with the packing density of polymer chain in self-assemblies. It is
consistent with increase in solubilization capacity of polymeric
surfactants according to the order pAUTA-Br<pAUTA-
NO
solubilization capacity with growing DP is consistent with
decreasing polarity for pAUTA-NO and pAUTA-Ts. It may be
stated that pAUTA-Ts has more hydrophobic microdomains to
accommodate pyrene and Orange OT inside hydrophobic
domain. Hydrophobic probes more easily reach them and
2
(
1/τ) on square of wave vector (q ) passes through the origin for
all polymers. This indicates the diffusion nature of observed
processes (Fig. 4A and Fig. s2 in supplementary). Determined
diffusion coefficients correspond to the two types of polymer
3
<pAUTA-Ts. It should be noted that an increase in
3
particles. DLS data for pAUTA-NO reveal two types of particles,
3
the first one (1-10 nm) corresponds to single macromolecules
and the second are multi-macromolecular self-assemblies and
the latter appeared to be quite stable under different conditions
and dilutions (Fig. 4B). The schematic illustration of the self-
assembly process of pAUTA-Br is presented in Scheme 2.
penetrates inside. Low solubilization capacity of pAUTA-NO
likely due to the fact that hydrophobic probe Orange OT is
located on the periphery of micelles. For pAUTA-Br , the I
3
is
-
1
/I
3
value is almost equal to 1.6. This corresponds to the location of
pyrene probe in polar environment and poor solubilization of
Orange OT. The effect of head group of polymeric surfactants
slightly changes the polarity. pAUTEA-Br has the highest polarity
(
Fig. s9). Stepped decreasing polarity is observed with
increasing concentration of pAUTEA-Br and pAUMM-Br. The
rearrangement of hydrophobic domains structure is observed at
0
2
.1 and 1mM in supplementary Fig. s9. This CAC value (Table
) is correspond to the interception of the rapidly varying part
and the nearly horizontal part at high concentration of the pyrene
:3 ratio plots (See supplementary Fig. s10, s11). They are in
agreement with CAC1 determined by dye solubilization method
Scheme 2. The schematic illustration of the self-assembly process of comb-
like polyelectrolytes pAUTA-Br (short-chain branching is omitted for simplicity).
1
(
Table 2). The CAC of block copolymers are normally much
[72,79]
Unfortunately, DLS data were limited at polymer concentrations
lower than CAC2 due to low signal intensity. The number
lower than low molecular mass surfactants.
values obtained by dye (Orange OT) solubility method and by
Low CACs
4
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fraction of these particles can be estimated as 5 %. Zeta-
potentials of small particles were positive and fall in range 55-
100 mV due to positive charge of head group of polyelectrolytes.
Catalytic properties
[80–82]
As it was shown earlier
for cationic hydrophobized polymers
and surfactants, catalysis is defined by the main contribution of
hydrophobic effect. Catalytic effect of polymers on alkaline
hydrolysis of different substrates 1-3 (Scheme 1) was
investigated by means of spectrophotometric assay of the
increase in the absorbance of 4-nitrophenolate anion at 400 nm.
-1
Dependence of apparent rate constant (kobs, s ) for hydrolysis of
substrates 1-3 in the presence of comb-like polyelectrolytes are
shown in Fig. 5. Increase in rate constant was observed with
increasing of polyelectrolyte concentration. There was
a
tendency of reaching a plateau in the high concentration range,
which is typical of micellar catalyzed reactions and suggests
binding of substrate to micelles. This allows treating the data in
terms of pseudophase model of micellar catalysis, and
calculating kinetic parameters of reaction according to
equation 7. The calculated parameters for hydrolysis reaction
are collected in Table 3. The
k
m
/k
0
ratio characterizes
acceleration of the reaction comparing to reaction in the
absence of polymerized catalyst with other conditions being
[81]
equal. Data for CTAB catalytic effect for the same reaction are
given as a reference. From these data it can be seen that
catalytic efficiency of comb-like polyelectrolytes depends on DP,
type of counterion and head group of polymers. The catalytic
effect in the presence of pAUTA-Br is 59, that is two times
higher than for classical cationic surfactants CTAB. This effect is
most likely determined by high substrate-to-micelle binding
-
1
Figure 5. Observed rate constants (kobs, s ) of hydrolysis of substrates 1 (a)
and 2 (b) as functions of polyelectrolyte concentration pAUTA-Br (1), pAUTA-
3
NO (2), pAUTA-Ts (3), pAUTEA-Br (4) with DP = 230 (a), DP=100 (b)
pAUMM-Br (5), with DP = 35, 25˚C
-
1
Table 3. Kinetic parameters of the reaction of alkaline hydrolysis of substrates
constant (2600 М ) that is two times higher than for CTAB.
Catalytic effect of micelles in micellar catalysis is stipulated by
solubilization of substrate molecules and nucleophile. Usually for
surfactant micelles, the nucleophile pole is at the periphery of
the micelles. This may be affected by the rate of exchange of
substrate molecules between solution in micellar pseudophase
and by the depth of substrate molecules penetration into the
micelle (close to micellar core/center or stay in periphery area).
Here we can find the difference between polymerized self-
assemblies and micelles of common low molecular weight
surfactants known from observations in the field of micellar
1
-3 catalyzed by polymeric surfactants, 25˚C
3
[a]
Polyelectrolyte
DP
Substrate
k
s
m
,
K
М
S
,
CAC×10
М
m 0
k /k
-
1
-1
pAUTA-Br
100
230
230
100
230
100
100
100
230
100
135
35
2
1
2
2
1
1
2
3
1
2
1
2
2
0.21
2600
2000
1400
1800
224
0.5
59
-
-
0.06
0.25
0.1
15
0.38
107
41
pAUTA-NO
3
0.146
0.07
0.4
[83]
chromatography. The core of common micelles contains free
alkyl tails with relatively loose packing whereas the core of
polymerized self-assemblies contains macromolecular chain and
-
0.3
17.5
6
pAUTA-Ts
0.025
0.054
0.082
0.02
1660
2900
4100
1600
3800
941
0.3
[52]
alkyl tails attached to it by covalent bonds.
So the core of
-
-
-
0.25
0.1
15
27
5
polymerized self-assemblies is denser and have less free
volume for solubilization. Consequently, solubilized molecules
do not penetrate deep inside the core and locate in peripheral
volume of self-assemblies. This causes the faster exchange of
solubilizate with solution phase. And this may be one of the
possible reasons for increase in the catalytic effect of
polymerized surfactants compared to classical surfactants. The
increase in catalytic effect can be achieved up to 98 times by
changing the head group of polymeric surfactants in the
following sequence pAUTA-Br < pAUMM-Br < pAUTEA-Br. This
effect is due to an increase in substrate-to-micelle binding
constant (Table 3) and solubilization capacity toward to the
Orange OT dye (Table 2) in the same sequence.
0.1
pAUTEA-Br
-
0.35
0.5
98
20
79
28
0.079
0.282
0.099
0.17
0.3
pAUMM-Br
CTAB
2700
1200
0.46
[
a] catalytic effect.
5
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The catalytic effect in the case of pAUTA-Br is two times higher
with increase in the degree of polymerization from 100 to 230
and reaches 107 times. Catalytic effect of polymer surfactants
macromolecular self-assemblies starts at extremely low polymer
concentrations,
the
inter-macromolecular
self-assembly
formation begins at concentration comparable with CMC for
typical cationic surfactant (CTAB). Solubilization capacity of the
comb-like polyelectrolyte is higher than CTAB and increases
with increasing hydrophobicity of ionic groups of polyelectrolytes
and counterions. Self-assembly-forming polyelectrolytes exhibit
higher catalytic activity for hydrolysis of 4-nitrophenyl esters of
phosphonic acids than CTAB. The catalytic efficiency depends
on the structure of polyelectrolyte head-group, degree of
polymerization and type of counterion. The highest catalytic
effect (two orders of magnitude) was observed for hydrolysis of
-
with Br counterion appeared to be four times higher than with
-
CH
3
C
6
H
4
SO
3
.
4-nitrophenyl butylchloromethylphosphonate in the presence of
polymer of acryloyl-oxyundecylthriethylammonium bromide. It
was 3.5 fold higher than for common CTAB micellar systems.
Catalytic activity can be controlled by the molecular weight of
polymers and the substrate lipophilicity. New type of cleavable
comb-like polyelectrolytes with a low aggregation threshold can
be recommended as high potential catalysts for nucleophilic
cleavage of OPs. Such catalysts would be of paramount interest
for degradation of OPs under mild conditions.
Experimental Section
Chemicals
-1
Figure 6. Observed rate constants (kobs
, s ) of hydrolysis of different
1
-(o-Tolylazo)-2-naphthol (75%, Orange OT, Aldrich, USA), pyrene (99%,
substrates 1 (1), 2 (2), 3 (3) as a function of polyelectrolyte concentration
pAUTA-Ts DP=100, 25˚C.
Sigma, Switzerland), 11-Bromoundecanol (98%, Aldrich), 2,2’-azobis(2-
methylpropionamidine)dihydrochloride (AAPH, 97%, Aldrich), 4-
toluenesulfonic acid (monohydrate) (Vekton, Russia), sodium nitrate
(
Vekton, Russia) were used as received. The substrates 1-3 were
Decrease of reaction rate in
a
row pAUTA-Br>pAUTA-
[84]
prepared according to the procedure.
Organic solvents were purified
NO >pAUTA-Ts may be caused by decrease in binding constant
3
[85]
according to standard methods of purification. Purified water (18.2 MΩ),
resistivity at 25 °C) from Direct-Q 5 UV equipment (Millipore S.A.S.
Molsheim-France) was used for all sample preparations.
–
of nucleophile(OH )-to-micelle while binding constants substrate-
to-micelle in that cases are rather comparable. The solubilization
capacity of these polymeric surfactants toward the hydrophobic
dye Orange OT increases in the same sequence. Likely, in the
case of toluene-4-sulfonate counterion, more loose micelles are
formed. It can be hypothesized that bulky and hydrophobic
toluene-4-sulfonate ions screen micelle surface and push off
hydroxide anions from the proximity of micelle. This was
confirmed by the lowest polarity of pAUTA-Ts seen by the
fluorescence of pyrene (Table 2). Some substrate specificity was
observed for pAUTA-Ts (Fig. 6). Catalytic effect of micellar
polyelectrolyte pAUTA-Ts increased from 6-fold to 27-fold when
Synthesis
11-acryloyloxyundecylbromide:
11-Bromoundecanol
(3g)
was
dissolved in freshly distilled N-methylpyrrolidone (25mL) and cooled to
about -10°C. To this solution, cold freshly distilled acryloyl chloride (15%
excess) was quickly added, and the reaction mixture was allowed to stay
for two days at -18°C. After that, the reaction mixture was poured into
2
00 mL of icy HCl (0.5M) and extracted 3 times with petroleum ether;
combined extracts were dried over sodium sulfate. The 11-
acryloyloxyundecylbromide was isolated as slightly yellowish oil (2.7g,
74%) and used in the next steps without additional purification.
changing from less hydrophobic phosphonate
1 to more
hydrophobic 3 (Table 3). This effect is determined by increase in
-
1
-1
substrate-to-micelle binding constant from 1660 М to 4100 М
11-Acryloyloxyundecyltrimethylammonium bromide (AUTA-Br):
on increasing substrate hydrophobicity. It should be noted that
the CAC values determined from kinetic experiment are close to
the CAC obtained by Orange OT and pyrene solubilization
experiments (Table 2). In addition, the latter confirms that the
catalysis of the hydrolysis reaction occurs due to self-assemblies
of comb-like polyelectrolytes.
AUTA-Br was obtained by reaction of 11-acryloyloxyundecylbromide
(
(
2.7g) with trimethylamine (0.68g, 30% excess) in acetonitrile solution
25mL) for 24h at room temperature. After solvent evaporation, the
resulting AUTA-Br was purified by crystallization from methanol-acetone
mixture. The product was obtained in a yield of 2.4g (74%). The structure
1
of AUTA-Br was confirmed by H NMR (See supplementary Fig. s12).
11-Acryloyloxyundecyltriethylammonium
bromide
(AUTEA-Br):
AUTEA-Br obtained according to the above procedure from 11-
acryloyloxyundecylbromide (2.7g) with triethylamine (1.16g, 30% excess)
at 80°C, 72h under argon in a sealed tube. Resulted AUTEA-Br was
washed by hexane, and purified by crystallization from methanol-acetone
mixture. The product was obtained in a yield of 2.7g (75%).The structure
Conclusion
The investigated comb-like polyelectrolyte can form intra-
macromolecular and inter-macromolecular self-assemblies with
increasing their concentration. The formation of intra-
1
of AUTA-Br was confirmed by H NMR (See supplementary Fig. s13)
6
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N-(11-Acryloyloxyundecyl)-N-methylmorpholinium bromide (AUMM-
Br): AUMM-Br according to the above procedure from 11-
acryloyloxyundecylbromide (2.7g) with N-methylmorpholine (1.16g, 30%
excess) at 80°C 72h under argon in a sealed tube. Resulted AUMM-Br
was washed by hexane, and purified by crystallization from methanol-
acetone mixture. The product was obtained in a yield of 2.5g (70%). The
Molecular weight
Average molecular weights (MDƞ,) of the comb-like polymers were
estimated from viscometry and DLS measurements in 0.05 M aqueous
NaCl according to (3)
ꢗ
ꢔꢅꢕ
ꢎ
1
ꢑꢒꢄꢁ ꢀꢓꢄꢒꢅꢖ ꢘꢄꢙ (3)
structure of AUTA-Br was confirmed by H NMR (See supplementary
Fig. s14)
-
10
-1
-1
89]
where A0 - hydrodynamic invariant (A0= 3.2×10 , erg×mol ×K , this
[
value is typically for flexible and comb-like macromolecules) ; T –
Absolute temperature, K; ƞ – viscosity of solvent, Pa s; D0 -self-diffusion
Polymerization
.
2
-1
3 -1
coefficients, cm s ; [ƞ] – intrinsic viscosity, cm g .
Polyelectrolyte pAUTA-Br was obtained by free-radical polymerization of
the corresponding monomer at concentration 0.07M and 0.27M (Those
concentrations correspond 4×CMC of AUTA-Br and 16×CMC of AUTA-
Spectrophotometry (dye solubilization)
-
1
Br) in water under argon atmosphere using AAPH initiator (1 gL ) at
0 °C for 1h under control of conductance measurements. The resulting
6
Solubilization of the dye (Orange OT) was performed by adding an
excess of crystalline Orange OT to the polymeric surfactant solutions.
These solutions were allowed to equilibrate for about 48 h at constant
temperature, followed by filtration. Then the absorbance was measured
at 495 nm (Orange OT), using the spectrophotometer Specord 250 Plus
(Analytik Jena AG, Germany). Quartz cuvettes (L = 1 cm) containing
sample were used. Solubilization capacity of associates (S), which
corresponds to the number of moles of dye solubilized per mole of
polymers were dialyzed against water (cellulose membrane tube with
molecular weight cut-off 14000 (Sigma-Aldrich D9652) was used for
dialysis). The yields of the polymers after purification and isolation were
about 90%. The structure of pAUTA-Br samples and impurities absents
were checked by
pAUMM-Br) were obtained according to the above procedure; the yields
of polymers after purification were not less 90%. pAUTA-NO3 and
pAUTA-Ts were prepared by dialysis of pAUTA-Br solution against
sodium nitrate or sodium toluene-4-sulfonate in water followed by dialysis
1
H NMR. All other polyelectrolytes (pAUTEA-Br
[
90]
surfactant was determined according to equation 4
[
86]
ꢛ
against water and freeze-drying.
pAUTA-Br samples with DP 100 and
ꢚꢀꢁꢁꢜꢝꢞꢟꢠꢡ (4)
230 were used for this transformation to obtain two series of pAUTA-X
polymers, where DP is the degree of polymerization.
where В is the slope of dye absorbance as a function of surfactant at
concentration above CMC and εext the extinction coefficient of Orange OT
-
1
-1 [91]
Viscometry
(εext = 18720 M cm ).
Viscometric measurements were conducted on a Lovis 2000 M rolling
ball microviscometer (Anton Paar, Austria) at 25°C in a 0.05 M aqueous
NaCl or water. The intrinsic viscosity [ƞ] was calculated from Huggins
Fluorescence
-6
Fluorescence spectra of pyrene (1×10 M) in water solutions of cationic
surfactants were recorded at constant temperature on a Varian Cary
Eclipse spectrofluorimeter (Varian, Inc., California, USA) with excited
wavelength for pyrene at 335 nm, using 1 cm path length quartz cuvettes.
Emission spectra were recorded in the 350-500 nm range. Fluorescence
intensities of the first peak at 373 nm (I1), of the third peak at 384 nm (I3),
and of the peak at 394 nm were determined from the spectra. The pyrene
1:3 ratio plots were approximated by a decreasing sigmoid of Boltzmann
[
87]
and Cramer plots
of ƞspc .
by linear extrapolation of concentration dependence
-
1
DLS study
DLS measurements were performed with PhotoCor Complex (Photocor
Instruments Inc., Russia) instrument equipped with real-time correlator
[
76]
(288 channels, 10 ns) in scattering angle range 30-140° at 25±0.1°C,
type, which is given by equation 5
with laser light source having wavelength, λ=405 nm. Autocorrelation
functions of scattered light intensity was processed using DynaLS
software (providing the distributions of scattered light intensity and,
therefore, distributions of relaxation times τ). The dependence between
ꢢꢣ
ꢢꢤ
ꢔꢣꢥꢔꢦ
ꢀ
ꢁꢎꢧꢨꢩꢪꢊꢫꢬꢫ ꢮꢯꢌ (5)
ꢅ
ꢍ
ꢭꢫ
Where A1 and A2 - upper and lower bounds of I1/I3;C- surfactant
concentration, M;C0 and ∆C - approximation parameters;The CAC value
was determined as CAC = C0 + 2∆C. This CAC value corresponds to the
interception of the rapidly varying part and the nearly horizontal part at
high concentration of the pyrene 1:3 ratio plots (See supplementary Fig.
s10, s11).
1/τ and the square of the scattering vector:
ꢂꢃꢄꢅ
ꢆ
ꢋ
ꢀ
ꢁ
ꢇꢈꢉꢁꢊꢌꢍ (1)
The dependence between 1/τ and the square of the scattering for all
studied samples was a line passing through the origin, indicating the
diffusional character of the observed processes (See supplementary
[
88]
Kinetic study
Fig. S2 )
(otherwise results were discarded). Hydrodynamic radii were
-
1
calculated using Stokes-Einstein equation D=kBT×(6πηoRh) , where ƞ0-
dynamic viscosity of solvent; Rh – hydrodynamic radius; kB - Boltzmann
constant; T - absolute temperature. Translational diffusion coefficient D
was calculated from the slope of this line according to the following
relationship.
The reaction was monitored by following the release of the p-
nitrophenolate anion absorption at 400 nm. The UV spectra were
measured on Specord 250 Plus (Analytik Jena AG, Germany)
spectrophotometer. The spectra of surfactants were determined at least
three times, they were reproducible, and average parameters were taken
into account. The oscillator strength was calculated on the basis of the
integral intensity of the corresponding absorption band. The observed
ꢎ
ꢌ
ꢀ
ꢐ
(2)
ꢏ
for both single macromolecules (D1) and polymer self-assemblies (D2) for
each investigated concentration (Table s1). The self-diffusion coefficient
–
1
rate constants for the reaction (kobs, s ) were determined by the first-
order equation (6):
(D0) was calculated by linear extrapolation of concentration
dependencies of translation diffusion coefficients (D) (See supplementary
Fig. S3). All samples were centrifuged to remove dust before
investigation.
ꢰꢱꢊꢐꢲ ꢳꢐꢍꢀꢁꢳꢵꢶꢷꢸꢷꢹꢺꢻꢼꢽꢮꢾꢿꣀꣁꢽ (6)
ꢴ
7
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ChemPlusChem
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Self-assemblies of cationic comb-like polyelectrolytes with a low association threshold were used as catalysts for alkali hydrolysis of
phosphorous acid esters. The catalytic effect is up to two orders of magnitude compared to aqueous alkaline hydrolysis. The
polyelectrolytes can be recommended as high potential catalysts for degradation of OPs under mild conditions.
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