Supramolecular water systems based on the new amphiphilic phosphacoumarins: Synthesis, self-organizations and reactivity

Article abstract of DOI:10.1016/j.mencom.2010.05.008

Tensiometry, conductometry, dynamic light scattering, microelectrophoresis and kinetics of O-(4-nitrophenyl) O-ethyl chloromethylphosphonate hydrolysis in supramolecular water system based on 6-chloro-4-dodecyl-2-oxobenzo[e][1,2] oxaphosphinin-2-ol salts revealed that supramolecular nanoparticles structure of the system depended on counter-ion nature and substance concentration.

Full text of DOI:10.1016/j.mencom.2010.05.008

Mendeleev
Communications
Mendeleev Commun., 2010, 20, 148–150
Supramolecular water systems based on the new amphiphilic
phosphacoumarins: synthesis, self-organizations and reactivity
Irina S. Ryzhkina, Lyaisan I. Murtazina, Andrey V. Nemtarev,
Vladimir F. Mironov* and Alexander I. Konovalov
A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Centre of the Russian Academy
of Sciences, 420088 Kazan, Russian Federation. Fax: +7 843 273 1872; e-mail: mironov@iopc.kcn.ru
DOI: 10.1016/j.mencom.2010.05.008
Tensiometry, conductometry, dynamic light scattering, microelectrophoresis and kinetics of O-(4-nitrophenyl) O-ethyl chloro-
methylphosphonate hydrolysis in supramolecular water system based on 6-chloro-4-dodecyl-2-oxobenzo[e][1,2]oxaphosphinin-2-ol
salts revealed that supramolecular nanoparticles structure of the system depended on counter-ion nature and substance concentration.
Surfactants, including phosphorus containing ones, are indispens-
able components in industry, in particular, pharmacy. A new
synthesis of benzo[e][1,2]oxaphosphinines (phosphacoumarins)
has been developed earlier. Herein this method was used for
the preparation of new amphiphilic phosphacoumarins – 6-chloro-
In the present work new amphiphilic phosphacoumarins 1–3
were studied as self-organizing molecules in water solutions,
and reactivity of supramolecular systems based on derivatives
2 and 3 in model hydrolysis of O-(4-nitrophenyl) O-ethyl
chloromethylphosphonate 4 was investigated.
1
–3
4
-dodecyl-2-oxobenzo[e][1,2]oxaphosphinin-2-ol 1 and its sodium
The surface tension isotherms for the water solutions of com-
pounds 1–3 are shown in Figure 1. Inflection points on the con-
centration dependences of the surface tension of the solutions
correspond to the critical micelle concentrations (CMC) (Table 1).
Compound 1 is sparingly soluble in water, so its micelle-forming
properties were studied in aqueous DMF (10 vol.%). The values
of CMC for compounds 1–3, obtained by conductometry, an
average size (effective hydrodynamic diameter) for the kinetically
†
(
2) and triethylammonium (3) salts, which can serve as the
potential surfactants and bioactive compounds as well as the
model compounds for biomimetic and/or biocompatible nano-
systems.
1
8
O
2
P
O
O– R+
8
a
7
Cl
O
O
3
6
4a
P
Cl
4
Compound 1. A solution of tetradec-1-yne (26.7 ml, 0.109 mol) in
5
EtO
NO2
CH Cl (20 ml) was added dropwise to the mixture of 2,2,2-trichloro-
9–20 C12H25
2
2
benzo[1,3,2]dioxaphosphole (23.17 g, 0.094 mol), CH Cl (30 ml) and
2
2
+
+
hex-1-ene (7.9 g, 0.094 mol) under a stirring in an argon atmosphere.
The reaction mixture was stirred for 30 min (15–20 °C), then the solvent,
excess acetylene and the formed volatile products were removed in a
vacuum (12 Torr, 120 °C). The yellow glass solid, 2,6-dichloro-4-dodecyl-
1
2
3
R = H
4
+
+
R = Na
+
+
R = Et N H
3
2
-oxobenzo[e][1,2]oxaphosphorinine, was obtained. This compound was
†
Self-assembling of the solutions of species 1–3 was studied by tensio-
dissolved in pentane (40 ml) and treated with water under stirring. The
white precipitate formation gradually occurred. A precipitate was filtered
off, pentane was separated and a viscous lower layer was treated with 90%
aqueous acetone. Additional formation of compound 1 precipitate took
place. The procedure was repeated four times. All solids were combined
and dried in a vacuum (12 Torr). A total yield of compound 1 was 15.8 g
(84%), mp 95–96 °C. IR (n/cm ): 460, 495, 504, 518, 554, 580,
600, 641, 668, 723, 775, 804, 837, 871, 1018, 1141, 1178, 1227, 1268,
1305, 1377, 1463, 1512, 1552, 1601, 1659, 2295, 2725, 2854, 2924,
metry, conductometry, dynamic light scattering, microeiectrophoresis (using
Zetasizer Nano ZS, Malvern Instruments) under thermostatting of samples
at 25 °C as described. Systems based on 2, 3 in the studied region of
concentrations had a monomodal particle size distribution, which retained
for 3 months, while the system based on 1 was stable only for 0.5 h.
Relative errors in the measurement of electrical conductivity (c) and
surface tension (s) of solutions did not exceed 1%, effective hydro-
dynamic diameter (D), electrokinetic potential (z) – 5%. Catalytic activity
of supramolecular systems based on 2, 3 in the hydrolysis of O-(4-nitro-
phenyl) O-ethyl chloromethylphosphonate 4 was studied by recording
7
–
1
1
3
2
3
1
3465. C NMR ([ H ]DMSO): 115.31 [ddt (d), C , JPC 170.2 Hz,
3
6
1
3
4
4a
JHC
3
162.5 Hz, J
PCCC4a
9
3
5.1 Hz], 151.72 [m (s), C ], 124.06 [m (d), C ,
HC CC
3J
16.9 Hz], 126.58 [dd (s), C , J
5
1
165.4 Hz, J
3
5.3 Hz],
4
-nitrophenolate emission (spectrophotometer Lambda 35, Perkin–Elmer)
HC5
7
5
HC CC
6
3
2
2
under the pseudo-first order conditions. Calculations of the observed
reaction rate constants (kobs) were performed according to the first-order
equation. On the basis of the kinetic concentration dependences with an
exit to the plateau in the micellar region of the compound 3 concentra-
tions using the above-mentioned equation, parameters of the micellar
catalyzed reaction – reaction rate constants in micellar pseudophase (km),
128.25 [ddd (s), C , J
131.11 [dd (s), C , J
8
6
11.4 Hz, J
168.1 Hz, 3J
7
6
3.6 Hz, J
5
6
3.6 Hz],
HC CC
HC C
HC C
7
1
8
HC7
5
7
5.3 Hz], 121.83 [dd (d), C ,
HC CC
1
3
8a 2
JHC
J
8
165.2 Hz, J
POCC8
6.7 Hz], 150.77 [dddd (d), C , J
POC8a
7.6 Hz,
3
8a 10.0 Hz, 3J
2
7
5
8a 10.0 Hz,
J
8
8a 2.9 Hz], 34.42 [tm (s),
HC CC
PC CC
PC C
10
1
2
C , 3JPCCC
1
9
11–16
9
17.4 Hz], 32.24 [tm (s), C ], 29.7–30.0 [tm (s), C
,
17
1
18
JHC 125.2 Hz], 29.48 [tm (s), C , J
HC17
126.3 Hz], 28.39 [tm (s), C ,
1J
HC18
125.8 Hz], 23.03 [tm (s), C , J
19
1
HC19 HCC19
124.4 Hz, J 2.3], 14.26
2
constants of the substrate binding (K ) and CMC were calculated.
b
2
0
1
2
31
2
Melting points were measured on a Boetius hot-stage and are uncorrected.
[qtm (s), C , J
HC20
124.5 Hz, J
HCC20
3.1 Hz]. P NMR ([ H ]DMSO,
6
1
13
1
2
NMR spectra were recorded on Bruker Avance-600 ( H, 600 MHz; C,
1
dH and dP values were determined relative to internal (HMDS) or
external (H PO ) standard, and the d values relative to the deuterated
45 °C) d: 5.53 (d, J 17.6 Hz). H NMR ([ H ]DMSO) d: 0.85 (t, 3H,
6
3
1
20
3
10–19
9
50.9 MHz) and Bruker CXP-100 ( P, 36.48 MHz) spectrometers. The
H , JHCCH 5.9 Hz), 1.23–2.40 (m, 20H, H
), 2.64 (t, 2H, H ,
3
3
2
8
JHCCH 7.5 Hz), 6.22 (d, 1H, H , JPCH 17.4 Hz), 7.22 (d, 1H, H ,
3J
8.8 Hz), 7.46 (br. d, 1H, H , J
7
3
8.8 Hz), 7.63 (br. s, 1H, H ).
5
3
4
C
HC C H
7
8
H CC H
8
7
solvent signal. IR spectra were recorded on a Bruker Vector-22 instru-
ment in Nujol.
Found (%): C, 61.07; H, 8.75; Cl, 9.00; P, 8.59. Calc. for C H ClO P
(%): C, 62.14; H, 7.86; Cl, 9.21; P, 8.05.
20 30 2
©
2010 Mendeleev Communications. All rights reserved.
– 148 –

Mendeleev Commun., 2010, 20, 148–150
Table 1 CMC, z-potentials and micelle size (D) of compounds 1–3 in
1
1
1
60
50
40
7
6
5
4
3
0
0
0
0
0
water.
2
Com- CMC (tensiometry)/ CMC (conductometry)/
D/nm z/mV
7
6
5
4
3
0
0
0
0
0
pound mol dm–3
mol dm–3
1
130
120
1a
2
3
–4
–4
1×10
5×10
7×10
1×10
–4
–4
5×10
145
106
–55
–75.8
1
10
–5
–5
7×10
100
1
–
6
–5
–4
–3
a10% DMF, the system is unstable in time.
lg C
2
Micelle-forming properties of compound 1 and salts 2, 3 are
different (Figure 1, Table 1). CMC of compound 2 is higher,
while that of compound 3 is lower than that of compound 1.
Structural features, particularly the presence of rigid aromatic
3
–
6.0
–5.0
–4.0
–3.0
lg C
and heterocyclic fragments in sodium salt 2, result in CMC
Figure 1 Isotherm of surface tension of aqueous solutions of (1) oxaphos-
phorinine 1 and its derivatives (2) 2 and (3) 3 (25 °C). Inset: (1) isotherm of
surface tension of the aqueous solution of 3 and (2) change of particles
diameters depending on concentration of solutions of compound 3.
5×10–4 mol dm ) which is 4 times lower than CMC of the
–3
(
–
3
–3
anionic surfactant sodium deoxycholate (2×10 mol dm ), which
has also rigid fragment in its structure, and is significantly lower
than CMC of widely used sodium dodecylsulfate detergent
active particles and their z-potentials, obtained at the concen-
tration of 1×10–3 mol dm , are also given in Table 1.
Micelle formation in solution of acid 1 is stepwise, which is
indicative of structural changes in the system. As this system
is unstable in time, the study of its structural changes and
micelle sizes was impossible.
–3
–3
(
SDS, 8×10 mol dm ). Negative value of z-potential (–45 mV
–3
–4
to –68 mV) of micelles 2 in the area of concentrations 5×10 –
1
–2
–3
×10 mol dm (Figure 2) points out that compound 2 is
anionic micelle-forming surfactant.
For better understanding of micelle formation processes in
solutions of compound 2, it is important to observe concentra-
tion changes of D and z-potential of particles, especially in pre-
micellar area. As judged from surface tension isotherm appear-
ance, aggregation of molecules in the system is expected.
Figure 2 represents concentration dependences of surface tension
of solutions of 2, D and z-potential of particles formed. Comparison
of data obtained by different experimental methods evidence that in
Compound 2. Suspension of compound 1 (2.02 g, 0.005 mol) in
Na CO water solution of (0.21 g, 0.0025 mol, 15 ml) was heated until
2
3
full dissolution of the solids. After 3 h white precipitate of compound 2
was formed. The precipitate was filtered off, washed with water and dried
–1
in air. Yield 1.8 g (89%), mp 216–217 °C. IR (n/cm ): 421, 442, 465, 478,
4
8
1
95, 525, 540, 588, 632, 682, 724, 738, 756, 786, 818, 831, 852, 881,
96, 9, 1083, 1132, 1178, 1213, 1269, 1308, 1342, 1377, 1464, 1552,
603, 1643, 1754, 1890, 1909, 1959, 2168, 2283, 2672, 2726, 2958,
–
5
–4
–3
premicellar interval of concentrations 5×10 –3×10 mol dm
with maximum in the area of 1×10–4 mol dm , associates of
salt 2 are formed and rearranged in the solution; their size changes
from 100 to 200 nm depending on concentration of compound
2. Taking into account low concentrations of salt 2 and large sizes
of particles, it can be suggested that water structures similar to
the hydrated fullerene nanoparticles of 70 nm in size at con-
centration 1×10 mol dm participate in the particles forma-
tion. Similar results were obtained for analogous concentration
range of SDS solutions wherein a maximum light scattering
–3
1
3
2
3
3
JPC
072, 3364, 3576, 3610. C NMR ([ H ]DMSO) d: 123.71 [dm (d), C ,
6
1
4
4a 3
3
166.5], 142.84 [m (s), C ], 125.93 [m (d), C , J
PCCC4a
16.0 Hz],
5
1
3
6
124.96 [dd (s), C , J
HC5
162.7 Hz, J
166.2 Hz, J
7
5
6.1 Hz], 125.26 [m (s), C ],
HC CC
7
1
3
8
1
28.40 [dd (s), C , J
HC7
5
7
6.1 Hz], 121.19 [dd (d), C ,
HC CC
1
3
8a 2
J
J
HC8
162.3 Hz, J
POCC8
5.2 Hz], 155.18 [dddd (d), C , J
POC8a
7.0 Hz,
3
8a 7.3 Hz, 3
2
9
7
J
5
8a 7.3 Hz,
J 8a 3.6 Hz], 34.25 [tm (s), C ,
8
–4
–3
HC CC
PC CC
PC C
3J
15.8 Hz], 31.81 [m (s), C ], 29.4–29.6 [tm (s), C
10
11–16
], 29.17
PCCC9
4
1
7
18
19 1
[
2
tm (s), C ], 28.34 [tm (s), C ], 22.55 [tm (s), C , J 19 124.3 Hz,
JHCC19 3.5 Hz], 14.28 [qm (s), C , J
HC
5
20
1
1
2
HC20
124.0 Hz]. H NMR ([ H ]DMSO)
6.9 Hz), 1.2–1.5 (m, 20H, C
7.4 Hz), 5.97 (d, 1H, C H, J 15.5 Hz), 6.90 (d,
6
2
0
3
10–19
coefficient connected with the structural changes of the water
nearby aggregates or SDS molecules was detected.
d: 0.85 (t, 3H, C H , J
H ), 2.43
3
HCCH
2
9
3
3
2
(t, 2H, C H , J
2
HCCH
PCH
8
3
7
3
1H, C H, J
7
8
8.7 Hz), 7.16 (br. d, 1H, C H, J
8
7
8.7 Hz), 7.32
Concentration-dependent rearrangements of nanoassociates
of compound 2 are accompanied by changing of the z-potential
negative values. A nonlinear concentration dependence of size
and z-potential of nanoassociates in the solutions of compound
HC C H
5
HC C H
(
br. s, 1H, C H). Found (%): C, 58.12; H, 7.93; Cl, 8.54; P, 8.04. Calc.
for C H ClNaO P (%): C, 59.04; H, 7.18; Cl, 8.71; P, 7.61.
2
0
29
3
Compound 3. A mixture of compound 1 (2.19 g, 0.006 mol), dioxane
(10 ml) and triethylamine (1.26 ml, 0.012 mol) was refluxed for 15 min.
–5
–4
–3
2
in the region of 1×10 –3×10 mol dm looks like that of
The white solid of compound 3 was obtained after evaporation of volatiles
6
,7
size and z-potential of the nanoassociates detected in the
solutions of the ‘melaphen’ plant growth regulator and ichphan
C-10 functional cationic surfactant within the concentration range
from the reaction mixture in air. Yield 2.7 g (93%), mp 35–36 °C. IR
–1
(
n/cm ): 418, 449, 466, 514, 537, 573, 649, 667, 722, 755, 816, 836, 903,
9
1
1
1
76, 1039, 1081, 1133, 1179, 1216, 1342, 1378, 1399, 1467, 1553, 1601,
645, 2492, 2676, 2737, 2851, 2921, 3439. C NMR ([ H ]DMSO) d:
1
3
2
6
3
1
1
3
–20
21.56 [ddt (d), C , J
PC3
166.3 Hz, J
HC3
163.4 Hz, J
9
3
5.6 Hz],
HC CC
2
2
00
4
4a
3
3
70
60
50
40
30
44.44 [m (s), C ], 125.15 [dd (d), C , J
PCCC4a
15.8 Hz, J
8
4a 9.2 Hz],
HC CC
–
–
30
40
5
1
3
6
1
J
25.02 [dd (s), C , J 162.8 Hz, J
HC5
7
5
5.1 Hz], 125.82 [dm (s), C ,
HC CC
1
180
160
3
7
3
8
6
11.7 Hz], 128.87 [dd (s), C , J
HC7
167.3 Hz, J
5
7
5.1 Hz],
1
HC CC
HC CC
8
1
3
8a
1
J
21.16 [dd (d), C , J
HC8
163.8 Hz, J
POCC8
5.6 Hz], 152.22 [m (d), C ,
15.8 Hz, J 125.1 Hz], 31.81
PCCC9 HC9
2
9
3
1
POC8a
7.1 Hz], 34.06 [tm (s), C , J
–50
–60
–70
1
40
10
1
11–15 1
[
tm (s), C , J 124.1 Hz], 29.5–29.6 [tm (s), C
HC9
1
, J 125.6–126.0 Hz],
HC
17
6
1
1
2
2
1
8
9.34 [tm (s), C , J
8.07 [tm (s), C , J
HC16
126.7 Hz], 29.24 [tm (s), C , J
125.6 Hz], 22.58 [tm (s), C , J
HC17
125.6 Hz],
125.1 Hz],
3
120
100
18
1
19 1
HC18
HC19
20
1
1
4.25 [qm (s), C , J
HC20
124.6 Hz], 45.72 [t (s), NCH , J 140.4 Hz],
2 HC
1
1
2
.76 [q (s), Me, J 128.2 Hz]. H NMR ([ H ]DMSO) d: 0.82 (br. s, 3H,
HC
6
–
6
–5
–4
–3
–2
20
9–19
C H ), 1.12–1.45 (22H, C H ), 2.94 (br. s, 6H, NCH ), 3.67 (br. s, NH),
6
3
2
2
3
2
8
3
lg C
.00 (d, 1H, C H, J
16.1 Hz), 7.00 (br. d, 1H, C H, J
7
8
8.5 Hz),
PCH
HC C H
7
3
5
7.5 (br. d, 1H, C H, J
8
7
8.5 Hz), 7.37 (br. s, 1H, C H). Found (%): C,
Figure 2 Concentration dependences of (1) associates diameters, (2) sur-
face tension and (3) z-potential of nanoparticles in aqueous solution of
compound 2.
HC C H
6
3.54; H, 9.87; Cl, 7.06; P, 6.82. Calc. for C H ClNO P (%): C, 64.25;
26 45 3
H, 9.33; Cl, 7.29; P, 6.37.
–
149 –

Mendeleev Commun., 2010, 20, 148–150
of 1×10–20–1×10–4 mol dm . Probably negative z-potential values,
irrespective of the dissolved substance nature, is characteristic of
the nanoassociates formed together with water structures in the
region of the low concentrations. This follows from the fact
that hydrated fullerene nanoparticles have also negative surface
–3
2 and 3 as well as solutions of cationic cetyltrimethylammo-
nium bromide (CTAB). Solutions of the compounds effectively
catalyze hydrolysis of O-(4-nitrophenyl) O-ethyl chloromethyl-
phosphonate under mild conditions: a reactivity of the supra-
molecular system 3 exceeds approximately by one order that of
CTAB (the latter is known to be a good catalyst of carboxylic and
8
charge. Concentration dependences of surface tension, D and
z-potential of particles come to a plateau on reaching CMC, con-
firming a formation of the micelles of about 130–140 nm in size.
12
phosphoric esters hydrolysis ). This confirms that micelles of 3
+
contain Et N H groups in bound state, which can catalyze
3
+
+
Replacement of inorganic counter-ions Na by organic Et N H
hydrolysis of compound 4.
3
leads to a decrease in CMC of the compound 3 solutions in
comparison with those of 1 and 2. Triethylammonium salt 3 has
CMC of 7×10–5 mol dm , specific to the zwitterionic and non-
ionic surfactants. It can be suggested that organic counter-ions are
in a bound state, which gives to compound 3 specific micelle-
forming properties due to the absence of signified charge on a
micelle surface. Inset in Figure l shows that the size of nanoasso-
ciates of compound 3 (160 nm) in a premicellar region is larger
than the size of micelles (106 nm), which is analogous to
compound 2. However, in solutions of compound 3, contrary to
solutions of 2, in the studied region of concentrations the
nanoassociates sizes and changes of z-potential do not increase.
Therefore, concentration-defined rearrangements of nanoassociates
in the solutions of species 2 and 3 is determined by counter-ion
nature.
In spite of the negative charge of micelle 2, which usually
results in inhibition of carboxylic and phosphoric esters hydrolysis,
reactivity of system 2 in the region of concentrations over
1×10–3 mol dm is comparable with that for CTAB which
can mean an assistance of functional groups of molecule 2 in
hydrolysis. It is interesting that the reactivity of system 2 in the
region of low concentrations within 5×10 –5×10 mol dm ,
where nanoassociates are formed (Figure 3, inset), exceeds
substantially the reactivity of micelles 2, 3 and CTAB formed in
a higher concentrations region. This additionally confirms that
the reactivity of supramolecular system is determined mainly by
the structure and properties of supramolecular particles. High
reactive supramolecular nanoassociates are formed and undergo
the structural rearrangements in the studied system 2 in the
narrow range of low concentrations. When reagent concentra-
tion in solution increases these nanoassociates transform into
micellar structures, which possess lower reactivity.
–3
–3
–
5
–4
–3
According to X-ray analysis, structure of compound 1 in solid
phase represents bilayers packed by a zigzag manner and formed
due to hydrophobic interactions of the aromatic rings, hydro-
carbon substituents and hydrogen bonds between main groups
of molecules 1.9 Taking into account these data, it can be
supposed that micelles of molecules 2 and 3 represent bilayers
formed by anionic skeleton of 1, cations and ‘interlayers’ of the
hydrated water, which provides them sufficiently large sizes
Tensiometry, conductometry, dynamic light scattering, micro-
electrophoresis and kinetic data evidence that compounds 1–3
are surfactants; micelle-forming properties and reactivity of
solutions of compounds 2, 3 are determined by supramolecular
nanoparticles structure which depends on counter-ion nature
and substance concentration.
1
0
similar to myelines. Note that particles of 4 nm in size are
observed together with those of more than 100 nm in size in the
region of 10–2 mol dm exceeding CMC by two orders; and this
agrees with well known data on a concentration-dependent change
of the surfactants sizes for their organized assemblies. High
negative values of the z-potential of particles 3, which are equal
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–3
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–
(65–90) mV in the concentration range of 10 –10 mol dm
can be accounted for by the fact that electrophoresis-induced
external electric field results in dissociation of triethylammonium
groups and formation of micelles with a high negative surface
charge (‘nude’ micelles), which are probably slightly ionized
3
4
‘dressed’ micelles) under ordinary conditions.11
(
Figure 3 exhibits data on kinetics of hydrolysis of compound 4
in premicellar and micellar regions of concentrations for species
5
6
1
995, 69, 1010 (Russ. J. Phys. Chem., 1995, 69, 913).
A. I. Konovalov, I. S. Ryzhkina, L. I. Murtazina, A. P. Timosheva, R. R.
Shagidullin, A. V. Chernova, L. I. Avakumova and S. G. Fattakhov, Izv.
Akad. Nauk, Ser. Khim., 2008, 1207 (Russ. Chem. Bull, Int. Ed., 2008,
7
6
5
4
3
2
0
0
0
0
0
0
2
1
1
1
00
80
60
40
5
7, 1231).
7
I. S. Ryzhkina, L. I. Murtazina, Yu. V. Kiseleva and A. I. Konovalov, Dokl.
Akad. Nauk, 2009, 428, 487 [Dokl. Phys. Chem. (Engl. Transl.), 2009,
428, 196].
6
5
4
3
2
1
0
0
0
0
0
0
1
8
9
N. O. Mchedlov-Petrossyan, V. K. Klochkov and G. V. Andrievsky, J.
Chem. Soc., Faraday Trans., 1997, 93, 4343.
L. I. Murtazina, I. S. Ryzhkina, A. V. Nemtarev, V. F. Mironov, A. T.
Gubaidullin and A. I. Konovalov, XIV All-Russian conference ‘Structure
and dynamics of molecular systems’. Book of Abstracts. Issue XIV,
Kazan, KSU, 2007, p. 161 (in Russian).
2
10
2
120
00
0
1
0
1
2
3
4
5
6
7
8
9
3
–3
C/10 mol dm
1
10 M. Haran, A. Chowdhury, C. Manohar and J. Bellar, Colloids Surf. A:
Physicochem. Eng. Asp., 2002, 205, 21.
3
11 A. I. Rusanov, F. M. Kuni and A. K. Shchekin, Zh. Fiz. Khim., 2009,
0
1
2
3
4
5
6
7
8
9 10 11
8
3, 290 (Russ. J. Phys. Chem., 2009, 83, 223).
3
–3
C/10 mol dm
12 E. Fendler and J. Fendler, in Advances in Physical Organic Chemistry,
ed. V. Gold, Academic Press, New York, 1970, vol. 8.
Figure 3 Observed rate constant (kobs) of hydrolysis in aqueous solution
of (1) 3, (2) 2 and (3) CTAB as a function of their concentration, 25 °C,
pH 8. Inset: (1) observed rate constant (kobs) of hydrolysis of 4 and (2) par-
ticles size in aqueous solution of 2 as a function of concentration, 25 °C, pH 8.
Received: 14th September 2009; Com. 09/3394
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