Journal of Colloid and Interface Science 243, 463468 (2001)

doi:10.1006/jcis.2001.7856, available online at http://www.idealibrary.com on

The Binding of Short-Chain N-Alkylpyridinium Ions to Sodium

Dodecyl Sulfate Micelles
Ana Paula Romani,,1 Flavia Cristina Bonilha Vena, Patrcia Maria Nassar, Antonio Claudio Tedesco,
and Joao Baptista Sargi Bonilha,2
Departamento de Qumica, Faculdade de Filosofia, Ciencias e Letras de Ribeirao Preto, Universidade de Sao Paulo, CEP 14040-901 Ribeirao Preto, Brazil;
and Faculdade de Ciencias, Fundaca o Educacional de Barretos, CEP 14783-226 Barretos, Brazil
Received August 28, 2000; accepted July 21, 2001; published online October 5, 2001

Steady-state and time-resolved fluorescence quenching techniques were used to study the interaction of short-chain Nalkylpyridinium ions with sodium dodecyl sulfate (SDS) micelles
using pyrene as a probe. The rate constants of the quenching of
pyrene and binding constants of the cations to SDS micelles were
obtained in different conditions of surfactant and salt concentrations. The increase in the number of carbon atoms in the alkyl chain
(ethyl, propyl, butyl, and hexyl) of these counterions leads to a reduction of both intramicellar mobility and exchange rate with the
aqueous phase. The intramicellar quenching rate constant value is
in the range of (36) 107 s1 while the exit rate constant of the
organic cations decreased and is in the range of (18) 105 s1 . The
fluorescence decay parameters of pyrene in the presence of ethyl,
NEP+ , and propyl, NPP+ , pyridinium cations were treated based
on the ion-exchange formalism. The selectivity constants obtained,
13 1 and 47 1 for NEP+ /Na+ and NPP+ /Na+ , respectively, suggest that the highest value for NPP+ cation is ascribed to electrostatic field contribution in addition to a specific adsorption potential
due to the size of the hydrophobic chain, leading to a reduction of
the alkyl chainwater contacts of both organic cation and surfactant
monomer. These results show that the selectivity was determined
by the nature of the counterions present and it is less dependent on
the characteristics of the micellar aggregates. C 2001 Academic Press
Key Words: micelle; fluorescence; counterion exchange; quenching.

INTRODUCTION

Micelles are aggregates formed by self-association of surfactant molecules. Due to the chemical structure of these molecules,
the aggregates formed provide different regions to solubilize
substrates, depending on the nature of the solutes, and may catalyze chemical reactions (14). Micelles may be classified as anionic, cationic, zwitterionic, or nonionic according to the charge
of the hydrophilic headgroup (14) of the surfactant. Organic
and inorganic counterions and additives can affect the properties of micelles (14).
1
2

To whom correspondence should be addressed. E-mail: paularom@usp.br.

In memoriam.

Ionic micelles can attract ions or exclude them depending on

the electrical charge of the ion and the surfactant headgroup (2).
The presence of organic and inorganic ions may affect the composition of the micellar surface due to the competition between
counterions to bind to the surface of the ionic micelles (49).
Many studies have used photophysical techniques to analyze the ion-exchange process in the presence of two or
more types of counterions (715). Selectivity coefficients for
monovalentmonovalent, monovalentdivalent, and divalent
divalent counterions have been determined using the pseudophase ion-exchange formalism, and the values obtained describe a process influenced by the hydrophilichydrophobic
characteristics of the ions present in micellar solutions (715).
Quina and co-workers employed time-resolved fluorescence
decay measurements with pyrene as a probe to study the dynamics of entry and exit of the N -alkylpyridinium ions (N -ethyl-,
N -nonyl-, N -decyl-, and N -dodecylpyridinium chlorides) from
ionic micelles (16, 17). Data analysis provided a simple pseudophase model of the quenching of immobile probes by mobile
and immobile quenchers, assuming that the counterion exit from
the micelle surface is governed by the micellar surface potential
(1518). A relationship between dynamics and selectivity of ion
binding to ionic micelles was suggested (17).
In the present paper, a study of the ion exchange between sodium and short-chain N -alkylpyridinium counterions (N -ethyl-,
N -propyl-, N -butyl-, and N -hexylpyridinium) at the surface of
sodium dodecyl sulfate micelles is reported. Steady-state and
time-resolved fluorescence quenching of pyrene by these pyridinium counterions is used to investigate the counterion micellar
kinetics. Analysis of quenching data allow the determination of
the selectivity constants and, hence, evaluation of the binding
affinities of N -alkylpyridinium counterions.
MATERIALS AND METHODS

Sodium dodecyl sulfate, SDS (Aldrich), was purified by repeated extraction in a Soxhlet (48 h) using hexane, followed by
recrystallization three times from ethanol. SDS purity was confirmed by surface tension measurements and a of comparison of
the cmc with the reported value from the literature (19).

463

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C 2001 by Academic Press

Copyright
All rights of reproduction in any form reserved.

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ROMANI ET AL.

Pyrene (Aldrich) was recrystallized three times from ethanol.

Sodium chloride (Merck, p.a.) was used as received. All the
solutions were prepared in ultra-pure water from a Millipore
system and other solvents were of analytical grade.
The fluorescence quenchers N -ethyl (NEP+ ), N -propyl
(NPP+ ), N -butyl (NBP+ ), and N -hexylpyridinium (NHP+ )
chlorides were prepared from additions of the corresponding
alkyl bromides to a freshly distilled pyridine after being stirred
for 72 h at room temperature (20). The corresponding chlorides
were obtained by ion exchange from the bromide salt with silver
chloride under stirring (72 h) in the dark. The solutions obtained
were lyophilized and the products were analyzed. Absorption,
1
H-NMR spectral data, and microanalyses were in agreement
with the proposed structures (20).
Absorption spectra of N -alkylpyridinium ions were registered
on a Hitachi U-3000 spectrophotometer. Pyrene fluorescence
measurements were performed on a Hitachi F4500 spectrofluorimeter (337-nm excitation, 374-nm emission). Fluorescence
decay of pyrene was obtained by the single-photon-counting
technique using a Edinburgh Analytical Instrument FL-900 Lifetime spectrometer (H2 flash lamp, 337-nm excitation, 390-nm
emission). Fluorescence decays of samples in the absence of
quenchers were analyzed by the standard single-exponential decay routines of the FL-900 operating software. The decay curves
in the presence of quenchers were analyzed using the TachiyaInfelta equation, Eq. [1] (2123),
I (t) = I (0) exp{1/1 C[1 exp(1/2 )]},

[1]

where I (0) is the fluorescence initial intensity of pyrene, and C,

1 , and 2 are parameters of the intramicellar quenching model.
The values of C, 1 , and 2 are related to the rate constants for exit
(k ) and entry (k+ ) of the quencher from the micelle, the pseudounimolecular rate constant (kq ) for intramicellar quenching, and
the average number hni of bound quenchers per micelle, by the
following expressions:
kq = C(1/2 )2 /(1/1 1/0 + C/2 )

[2]

k = 1/2 kq

[3]

hni = C/2 2 kq 2

[4]

k+ = k hni/[Q t ] hni[M].

[5]

0 is the pyrene fluorescence lifetime in the absence of quencher,

[Q t ] is the total concentration of added quencher, and [M] is the
micelle concentration (CD cmc).
In all fluorescence measurements, pyrene stock solutions were
prepared in methanol. Aliquots of these stocks were added to
volumetric flasks containing SDS, and the solutions were stirred
for 30 min. The concentration of N -alkylpyridinium ions were
calculated based on the absorption measurements (max 258 nm).
The solutions that contained pyrene (1.6 106 M), SDS (0.04
0.08 M), and NaCl (0.00.08 M) were air-equilibrated. Aliquots
of concentrated solutions of the quenchers (0.15 M) were added

directly to the cuvette via a calibrated Hamilton microsyringe,

and the emission intensities (or probe fluorescence decay) were
registered after each addition. All measurements were performed
at 30 C.
RESULTS AND DISCUSSION

Steady-State Measurements
The fluorescence quenching experiments of pyrene in aqueous micellar solutions were monitored at different surfactant
concentrations as well as in the presence of sodium chloride.
Data were treated using the SternVolmer formalism and K SV
values were obtained from the linear portion of the plot of I 0 /I ,
where I 0 and I are the fluorescence intensities in the absence
and in the presence of the quencher, respectively, as a function
of quencher concentration. Typical SternVolmer plots obtained
are shown in Fig. 1. The upper curvature observed is related to
the statistics of the quencher micellar occupancy. In the limit of
low hni, K SV is defined in terms of the micellar parameter as
K SV =

0 k q k K
,
(kq + k )(1 + K [M])

[6]

where K is the quencher binding constant given by the ratio of

k+ /k . The values of K SV estimated for NEP+ , NPP+ , NBP+ ,
and NHP+ cations are listed in Table 1.
The N -alkylpyridinium ions employed in this study are considered mobile quenchers (23). In the absence of salt the K SV values increase in the following order: NHP+ < NBP+ < NPP+ <
NEP+ , in agreement with a diffusion-controlled quenching process. An increase in the length of the alkyl chain of the quencher
increases the hydrophobic character and reduces the mobility of the ion. K SV values decrease with an increase in SDS

FIG. 1. Fluorescence quenching of pyrene (1.6 106 M) by NPP+ ion in

a micellar solution of SDS (j 0.02 M, d 0. 04 M, m 0.06 M, and . 0.08 M) in
the presence of NaCl (0. 06 M) at 30 C.

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BINDING OF ALKYLPYRIDINIUM IONS TO SDS MICELLES

concentration due to the dilution of the probe and quencher in

the micellar phase, leading to a monodistribution of the probe
inside the micelle.
The addition of salt changes the micellar structure and may affect the partition coefficients of solubilized species. Adding salt
to an ionic micellar solution leads to a decrease in the cmc value
and increases the aggregation number, owing to the screened
electrostatic repulsion between the surfactant head groups (14,
24, 25). The SternVolmer constant (K SV ) data presented in
Table 1 show that the values increase according to the salt
concentration and the solubilization process of the probe and
quencher becomes size-dependent. In the presence of salt, K SV
values for NEP+ are lower than those found for NPP+ , NBP+ ,
and NHP+ . These results reflect changes in the specific micelle/counterion interactions.
Time-Resolved Measurements
The analysis of fluorescence time-resolved decay of micellebound probes allows parameters such as the average aggregation
number, intramicellar quenching rate constant, and the rate constant related to the binding of quencher to the micelle (23) to be
determined.
A typical time-resolved profile of the quenching of pyrene
by N -alkylpyridnium ion in SDS micelles is shown in Fig. 2.
Table 2 summarizes the experimentally determined rate constants for NEP+ , NPP+ , NBP+ , and NHP+ . The kq results for
all the examined quenchers in the SDS system change in the following order: NHP+ < NBP+ < NPP+ < NEP+ , suggesting
that the mobility of counterions bound to the micellar surface

TABLE 1
SternVolmer Constants (K SV ) for the Fluorescence Quenching
of Pyrene by AP+ Ions (NEP+ , NPP+ , NBP+ , and NHP+ ) in Different
SDS Concentrations in the Absence and in the Presence of NaCl
at 30 C
[SDS] (M)

NEP+

NPP+

NBP+

NHP+

0.04
0.06
0.08

K SV (M1 ) (in the absence of NaCl)

3850 100
2720 100
2500 90
2330 50
1610 60
1600 80
1610 40
1520 40
1470 30

2400 120
1550 80
1420 50

0.04
0.06
0.08

K SV (M1 ) [NaCl] = 0.02 M

1720 120
2290 100
3260 200
1420 60
1860 40
2380 100
850 30
1100 30
1450 30

2520 100
2300 50
1700 40

0.04
0.06
0.08

K SV (M1 ) [NaCl] = 0.04 M

1980 110
2960 70
3750 100
1770 70
1990 50
2360 120
990 30
1180 30
1650 70

3350 60
2420 50
1760 50

0.04
0.06
0.08

K SV (M1 ) [NaCl] = 0.06 M

3120 40
4370 80
4500 180
1860 60
2230 80
3000 110
1140 50
1250 60
1800 40

4000 80
2840 40
2180 70

0.04
0.06
0.08

K SV (M1 ) [NaCl] = 0.08 M

2100 100
5000 200
5500 90
2060 100
2650 150
2800 100
1350 70
1625 30
2450 200

5875 240
3120 60
2800 80

increases in the same order, as expected on the basis of the

diffusion-controlled quenching process in micelles. The increase of the micellar size, induced by added salt, reduces kq
(1, 23, 26).

FIG. 2. Decay of fluorescence quenching of pyrene (1.6 106 M) in a micellar solution of SDS (0.040 M) containig NaCl (0.02 M) in the absence of
quencher (upper curve) and in the presence of quencher NPP+ (1.57 104 M, 4.70 104 M, and 9.36 104 M).

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ROMANI ET AL.

TABLE 2
Constants of Fluorescence Quenching of Pyrene by AP+ Ions
in Micellar Solution of SDS (0.04 M) at 30 C
[NaCl] (M)

NEP+

0
0.02
0.04
0.06
0.08

5.6 0.06
4.8 0.1
4.3 0.1
3.9 0.1
3.4 0.2

0
0.02
0.04
0.06
0.08

NPP+

1.0 0.3
1.5 0.3
2.1 0.4
2.4 0.5
3.0 0.6

hkq i (s1 107 )

5.1 0.06
4.5 0.06
3.7 0.06
3.6 0.2
3.3 0.1
hk i

(s1

NBP+

NHP+

5.1 0.2
4.4 0.06
3.9 0.06
3.6 0.1
3.3 0.06

4.4 0.06
4.0 0.06
3.5 0.1
3.2 0.06
3.0 0.1

0.8 0.6
2.5 0.2
2.1 1.5
3.0 1.3
3.4 1.1

2.2 1.0
1.8 0.2
1.2 0.1
1.9 0.3
2.9 0.6

105 )

3.5 0.9
4.4 1.5
5.1 1.8
7.6 1.7
8.1 3.1

The residence time of ionic quenchers in micelles depends on

the balance between the electrostatic and hydrophobic contributions involved in the association process (23). The hydrocarbon
segment in NEP+ is short for an effective hydrophobic interaction; the values of rate constant for the exit (k ) of NEP+
from SDS micelles are higher than the corresponding values
for NPP+ , NBP+ , and NHP+ . Increasing the sodium chloride
concentration leads to changes in the electrical potential of the
micellar surface (10), thus k values increase with salt addition
and the affinity for quencher ions is weakened.
The rate constants for the entry (k+ ) of AP+ ions into the
micelles were determined only for NEP+ (3.3 1.0 1010 M1
s1 ) and NPP+ (4.0 2.0 1010 M1 s1 ), both with large
standard deviations.
Short-chain pyridinium cations may bind to the anionic surface of SDS micelles as their counterions (16)
k+x

X mic ,
X aq + Mic

[7]

kx

where X represents the N -alkylpyridinium ion. This equilibrium is governed by the rate constants for the entry and exit of
quencher from the micelle. As a result of ionic competition for
micellar headgroups, a displacement of micellar counterion (Y )
can occur (5):
ky

Yaq + Mic.
Ymic

[8]

k+y

The rate constants for entry and exit of the counterions from
the micelles are dependent on the counterion charge and the
micellar surface potential (9 0 ) according to (10, 1618)
0
k = k
exp[z x F9 0 /RT ]

k+ =

0
k+

[9]

exp[(1 )z x F9 /RT ].
0

[10]

F is the Faraday constant, R is the ideal gas constant, and z x rep-

resents the charge of the ion. Considering that AP+ ions may be
partitioned between the aqueous and micellar phases, a fraction
() of the overall electrostatic work is associated with the exit
process, while the other (1 ) is related to the entry process
(1618).
The micellar surface potential is logarithmically related to the
concentration of free micellar counterions ([Yaq ]) in the aqueous
phase (27, 28),
z y F9 0 /2.303RT = K y + log[Yaq ],

[11]

where K y is a constant. A combination of Eqs. [9] and [11]

indicates that log k is a linear function of log [Yaq ] with a slope
equal to (z x /z y ) (1618)
log k = K 0 + (z x /z y ) log[Yaq ],

[12]

where K 0 is a constant. The measured rate constants for micellar

exit of NEP+ and NPP+ quenchers as a function of salt added
can be analyzed with this treatment. The aqueous counterion
concentrations ([Naaq ]) are calculated from the pseudophase ionexchange relationship (4, 5):
[Naaq ] = CD + cmc + [Naad ].

[13]

The value used for (the apparent degree of counterion dissociation) was 0.25 for SDS micelles (16). Standard linear regression
analysis using Eqs. [12] and [13] provides the following relationship for N -alkylpyridinium ions:
log k (NEP+ ) = 7.11 + 0.63 log[Naaq ]
+

log k (NPP ) = 6.37 + 0.48 log[Naaq ].

[14]
[15]

values obtained for NEP+ and NPP+ ions are 0.63 0.08 and
0.48 0.13, respectively. The result for NEP+ is in agreement
with a previous result reported in the literature (16). The value
for NEP+ indicates that the electrical contribution to the Gibbs
energy barrier for escape the ion from the micelle is higher than
the contribution of NPP+ . This fact suggests that the association
of NEP+ is modulated mainly by the attraction of the ion by the
electrostatic field of SDS micelles while for NPP+ its binding
to the micellar surface is in addition influenced by the contribution of the adsorption potential due to the larger size of its alkyl
chain (17).
In these experiments, the concentration of SDS employed was
relatively low to avoid micelle-mediated transfer of counterions.
The basic assumption of the method employed considers that the
statistical distribution of the quenchers among the micelles obeys
a Poisson distribution. Micellemicelle collisions would result in
an aggregate with more than one quencher; this situation would
be a problem for the statistical distribution because the number
of the quencher may be restricted, less than one per micelle. The
quencher concentration used in this study (01103 M) was

467

BINDING OF ALKYLPYRIDINIUM IONS TO SDS MICELLES

low and does not cause an impact on the average aggregation

number of SDS micelles.

AP = (|z x |/Nag )(A2 1/ + A3 A4 )2 /[A3 (A4 )2 ].

Pseudophase Ion-Exchange Model

Photophysical techniques have been used to determine
counterion-exchange selectivities at the surface of ionic micelles (617). The binding of counterions to SDS micelles can be
treated in terms of competitive ion exchange between the foreign
counterion AP+ (NEP+ or NPP+ ) and the detergent counterion
Na+ (4). The micelle is considered a distinct phase of the solution
and the process is described by an equilibrium of the type
K AP/Na

APaq + Namic
APmic + Naaq .

[16]

K AP/Na is the counterion-exchange selectivity coefficient, defined as

[Naaq ]
AP
,
[17]
K AP/Na =
[APaq ]
Na
where the subscript aq refers to the analytical concentration
of the free counterions in the aqueous phase and AP and Na are
the fractions of the micellar surface coveraged by AP+ and Na+
defined by (4, 5, 8)
AP = [APmic ]/CD

[18]

Na = [Namic ]/CD ,

[19]

where CD = [SDS]-cmc is the concentration of micellized surfactant, subject to the condition

Na + AP = (1 ).

[20]

The micellar fractional coverages and the bound and free micelle counterion concentrations are related to the pseudophase
ion-exchange mass balance by (4, 5, 8)
[Namic ] = (1 )CD AP CD

equation by the relationship (13, 17)

[21]

[Naaq ] = CD + cmc + [Naad ] + AP CD

[22]

[APT ] = [APmic ] + [APaq ].

[23]

In these equations, [ APT ] and [Naad ] are the total concentrations

of added foreign and common counterion salt, respectively.
The time-resolved fluorescence decay measurements with
pyrene as a probe and the monovalent N -alkylpyridinium ions
as quenchers were employed to determine the selectivity coefficients for exchange of these two organic counterions at the
surface of SDS micelles. The quenching of pyrene depends on
the local concentration of AP+ ions at micellar surfaces (23).
Quina and co-workers demonstrated that the analysis of the fluorescence decay of pyrene in micellar solutions allows the determination of AP from the coefficients of the TachiyaInfelta

[24]

is the pyrene fluorescence lifetime in the absence of AP+ ions

and Nag is the micelle aggregation number. Using Eq. [24] and
the Ai fitting parameters, K AP/Na values obtained are 13 1
and 47 1 for NEP+ /Na+ and NPP+ /Na+ , respectively. The
lack of appreciable selectivity constants for the changes between
NBP+ /Na+ and NHP+ /Na+ are attributed to differences in the
specific adsorption potentials of these counterions due to the
size of their alkyl chains. These results indicate that the N alkylpyridinium ions bind more strongly to the micelle than the
sodium ion as would be expected. The differences observed in
the selectivity coefficients for the exchange between Na+ and
AP+ are similar to those found for the exchange between sodium
and n-alkylammonium ions at the surface of SDS micelles (12),
suggesting that the hydrophobicity of the alkyl chain is the main
factor that influences K AP/Na values. The binding of a short alkyl
chain counterion to the micellar surface reduces the alkyl chain
water contacts of both organic cation and surfactant monomer,
leading to stabilization of the micelle by entropy or hydrophobic
contribution (12).
SUMMARY

Steady-state and time-resolved fluorescence quenching techniques were used to study the interaction of short-chain N alkylpyridinium ions with SDS micelles. The rate constants of
the quenching of pyrene and binding of the cations to SDS micelles were obtained under different conditions of surfactant and
salt concentrations. The results suggest that an increase in the
number of carbon atoms in the alkyl chain of these counterions leads to the reduction of both intramicellar mobility and
exchange rate with the aqueous phase. The fluorescence decay parameters of pyrene in the presence of NEP+ and NPP+
ions were treated within the framework of the ion-exchange formalism. The selectivity constants obtained, 13 1 and 47 1
for NEP+ /Na+ and NPP+ /Na+ , respectively, suggest that the
higher value for NPP+ cation is ascribed to an electrostatic field
contribution in addition to a specific adsorption potential due
to the size of the hydrophobic chain (17), reducing the alkyl
chainwater contacts of both the organic cation and surfactant
monomer. These results show that the selectivity is determined
by the nature of the counterions present and it is less dependent
on the characteristics of the micellar aggregates (10, 11).
ACKNOWLEDGMENTS
` Pesquisa
This work was supported by grants from the Fundaca o de Amparo A
do Estado de Sao Paulo (FAPESP Thematic Projects 91/0480-1 and 94/3505-3)
and by a fellowship from FAPESP (A. P. R., Proc. No. 95/9770-3). The authors
are pleased to thank to Prof. Dr. Marcelo Henrique Gehlen for the important
suggestions that contributed to the completion of this work.

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ROMANI ET AL.

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