A.E.Arbuzov Institute of Organic and Physical Chemistry
Kazan Research Center of the Russian Academy of
Sciences
Irina S. Ryzhkina

Oversimplified representation of organized structures formed from surfactants
The association of naturally occurring and man-made amphiphilic compounds in solutions results in the formation of supramolecular systems.
J.H.Fendler.
Chem.Rev. 1987, 87, 877-899

The amphiphilicity of resorcarenes was used for the formation of vesicles, mono- and multi-layers at the air-water interface or on the solid surface
The channel model of Calix-4-resorcinarenes
Self-Assembling of Calix-4resorcinarenes tetrasulfide adsorbates to monolayers on gold
Spontaneous Multilayering of Calix-4-resorcinarenes
Molecular organization in a floating mixed monolayer

Methods used for the study of aggregation
240
220
200
180
160
140
120
100
80
60
0.0000
3
1
2
4
0.0005
0.0010
0.0015
0.0020
С
А М С
, mol*l -1
0.0025
5 6
0.0030
Specific conductance of water-DMF- CTAB solutions (30% DMF) plotted against AMC (1,3,5) ,
AMP (2,3,6) concentration at 25
10 -2 ;3,4- C
CTAB
=5 10 -3 ;5,6- C
0 C ,1,2-C
CTAB
CTAB
=2 10 -3
= 1 mol l -1 .
The aggregation of the compounds was explored by tensimetry, electrical conductivity, permittivity measurements and NMR FT-PGSE (nuclear magnetic resonance Fourier transform pulsegradient spin echo) and NMR ROESY methods. The experiments were carried out in water and water-dimethyformamide solutions containing from 10 to
70 % of DMF in the presence and in the absence of cationic surfactant CTAB.

12
1
10
8
6
3
2
4
2
4
5
0
5 10 15 20
10 4 C
AM C
/ m ol l -1
25 30
The kinetics of the reactions was studied by spectrophotometry and 31 P NMR method
The quantitative treatment of the kinetic data for micellar reactions made it possible to characterize the reactivity of compounds in a micellar microenvironment (k m
), to estimate the efficiency binding of reagents with micelles (K b
) and to evaluate the critical micelle concentration. k
H 2 O
+ k m
K bond
C

AB k o bs
=
1 + k bond
C

AB k obs is the rate constant in the micellar phase, k
H2O is the rate constant in the reaction in the water-DMF phase
C
ПАВ is the concentration of AMC, AMP,PAMC or surfactant
O
O
Н
2
О
АМP +
P OC
6
H
4
NO
2
Phosphorylated products
P OH + AMP
AMC +
O
P OC
6
H
4
NO
2
Н
2
О
O
P OH + AMC

The chemical structure of the studied amphiphiles
2 3
NR R
OH
R
1
AMP
1 R
1
=C
9
H
19
; R
2
=R
3
=CH
3
2 R
1
=H; R
2
=H; R
3
=C
8
H
17
C
Surfactant
-
1 6
H
+
33
N(CH
3
)
3
Br
CTAB
R
6
R
7
O
P O
PAE
NO
2
7 R
6
=R
7
=ClCH
2
8 R
6
=OC
2
H
5
; R
7
=ClCH
2
9 R
6
=R
7
=OC
6
H
4
H O
R
4
OH
R
4
H O
H O
R
5
R
5
R
5
R
5
H O
R
4
OH
AMC
3 R
4
=CH
2
N(CH
3
)
2
; R
5
=C
9
H
19
4 R
4
=CH
2
N(C
2
H
5
)
2
; R
5
=C
11
H
23
OH
R
4
OH
PAMC
5 R
4
=CH
2
N(CH
3
)
2
;R
5
=CH
2
P(O)(OC
3
H
7
) OH
6 R
4
=CH
2
N(C
2
H
5
)
2
;R
5
=CH
2
P(O)(OC
4
H
9
)OH
We investigated the selfassociation of amphiphilic o-aminomethylphenols with different the position, the length and the amount of the hydrophobic substituents in a molecule and aminomethylated calix[4]resorcinarenes with hydrophobic and hydrophilic fragments on the lower rim of cavity.
The molecule of aminomethylated calix[4]resorcinarenes with hydrophilic fragments on the lower rim of cavity has four strong polar alkylphosphonic acid fragments instead of hydrophobic tails conventional resorcarenes.
of

The self-organization of aminomethylated calyx[4]resorcinarenes and phenols in water-DMF-media
65
60
55
50
45
40
35
0
1
2
3
4
5 10
10
15
-5
C
20 25
AM C ,AM P,QAM P
,moll
-1
35 40 45 50
Surface tension plotted against calix[4]resorcinarene (1),AMC (2), AMP (3,
4) concentration in water-DMF (30% DMF) solutions at 25 0 C.
55
The critical micelle concentration of the studied compounds depends on the pH of medium, the length and the amount of the hydrophobic substituents in a molecule. The cavity
(rigid segment) is the most important structural factors in determining the aggregate behavior of resorcarenes.

The structural features of the aggregate forming amphiphiles
Micelle forming amphiphile
+ -
T.Kunitake et al,
JACS, 1981, 103, 5401
Bilayer forming amphiphile rigid segment
-
+
+ -
+
+
flexible alkyl chain hydrophilic head
+
rigid segment
+
NH
P
O
O
-
H
+ +
N N H
-
O
O
P
P
O
O
-

The self-organization of aminomethylated amphiphilic resorcarenes
The aggregate formation of resorcarene with hydrophilic fragments proceeds basically in results of electrostatic interactions between phosphonate-anions
(tail) and ammonium group (head) of different molecule of resorcarene in the acid and neutral space of pH or between sodium cations and phosphonate-anions in the basic space of pH.
pH
8

3 pH
12
1
.
10-4
ККА
1 .10-4

8
4 .10-4
ККА
J.L.Atwood et al. Angew. Chemie, 100/10,1988, 1412.
4
.
10-4
NH
NH
O P
O
NH
O P
O
NH
C моль/л
O P
O
NH
O P
O
NH
C моль/л O P
O
O P
O
N
N
N
C моль/л
Na
O P
O
O
P O
Na
O P
O
O
P O
Na
O P
O
Na
O
P O
N N N
C моль/л

The dependence of t he critical aggregate concentrations of aminomethylated resorcarenes and surfactants on the content of DMF
6
4
2
10
8
3
4
1
2
0
0 20 40
Content of D M F ,v.%
60 80
CMC of CTAB (1, n=10 -3 ), SDS (2, n=10 -2 ) ,
Triton-X-100 (3, n=10 -4 ), AMC 10 (4, n=10 -5 ) plotted against DMF content in water-DMF solutions at 25 0 C.
The critical aggregate concentrations of
CTAB, AMP, AMC, PAMC and mixed systems based on these compounds in the water-DMF media at the neutral pH.

The hydrolytic catalytic activity of aminomethylated resorcarenes in the reaction with phosphorus acid esters
0.0035
0.0030
0.0025
0.0020
0.0015
0.0010
0.0005
0.0000
1
2
4
5
6
3
5 10 15 20 25 30
10 4 C
AMC
, mol l -1
Observed rate constant of the reaction of substrate 8 with AMC (1, 2),
AMP (3, 4, 5, 6) plotted against their concentration at 25 0 C ,pH 10.
12
1
10
6
8
3
6
2
4
4 2
5
0
0 5 10 25 30 15 20
10 4 C
AM C
, mol*l -1
Observed rate constant of the reaction of substrate 7 with AMC (1,2),
AMP (3, 4, 5, 6), plotted against their concentration at concentration of
CTAB 5 10 -3 (2,4,5) and 1 10 -2 mol l -1 , 25 0 C , pH 8.
Parameters of the reaction of substrate 8 with AMP 1,2,
* C
AMC 3 in the absence of surfactant, pH 10, 25
CTAB
=1 .
10 -2 mol .
l -1 o C.
Parameters of the reaction of substrate 7 with AMP 1, AMC 4 in the presence of CTAB (C
CTAB
=5 .
10 -3 mol .
l -1 ) pH 8, 25 o C.

1. Self-organization of aminomethylated phenols and calix[4]resorcinarenes leads to the formation of aggregates in water and water-organic medium and to the formation of mixed aggregates in water-surfactant systems. The quantitative characteristics of these aggregates confirm that aminomethylated phenols are micelle-forming amphiphiles and aminomethylated calix[4]resorcinarenes are bilayer forming amphiphiles.
2. The aggregates of aminomethylated calix[4]resorcinarenes are enzyme mimics systems which provide specific microenvironments for substratebinding and subsequent catalysis in aqueous media. The aggregates of aminomethylated calix[4]resorcinarenes and their mixed micelles , including surfactants, exhibit a higher reactivity in the hydrolysis of phosphorus acid esters as compared with the identical systems based on aminomethylated phenols and surfactants.

This work was carried out under academician A. I. Konovalov and Dr.
L. A. Kudryavtseva in the laboratory of highly organized media.
The calix[4]resorcinarenes with hydrophilic alkylphosphonic acid fragments on the “lower” rim of cavity were obtained in the laboratory of Prof. M. A. Pudovik.
Dr. S. S. Lukashenko, Dr. K.M. Enikeev, Dr. V. P. Archipov, Dr. Z. Sh.
Idiatullin, Dr. A. P. Timosheva and junior researcher Ya. A. Babkina and T.N. Pashirova took part in the work.
The work was financially supported by the Russian Foundation for
Basic Research ( Project no. 00-03-32119).